@article{
 title = {Hierarchical thermal transitions of a poly(ethylene glycol) and methacrylic acid copolymer as a solution, grafted graphene oxide dispersion and Pickering emulsion},
 type = {article},
 year = {2025},
 volume = {submitted},
 id = {41d9677c-cff3-3776-b3b6-5040c37bb81b},
 created = {2024-08-01T11:11:18.586Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-12-18T18:34:59.260Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 bibtype = {article},
 author = {Lee, Wai Hin and Bon, Stefan A. F.},
 journal = {Journal of Colloid and Interface Science}
}

@article{
 title = {Transport dynamics of microplastics within emergent vegetation featuring realistic plant morphology},
 type = {article},
 year = {2025},
 volume = {ASAP},
 websites = {https://www.sciencedirect.com/science/article/pii/S0043135425004476},
 month = {4},
 day = {4},
 id = {d5eaf0fa-a5fe-34fd-b435-5fc7cb6c4601},
 created = {2024-08-26T10:31:43.087Z},
 accessed = {2025-04-04},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2025-04-04T20:49:21.645Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {Despite the significance of rivers and streams in transporting terrestrial microplastics (MP) to the oceans, limited research has focused on the role of aquatic vegetation and their complex geometry in shaping the underlying mechanisms governing MP mixing and dispersion processes in riverine environments. This study, for the first time, investigates the transport and fate of non-buoyant MPs, specifically those with diameters of 188 nm and 6 micrometer and a density of 1.04 g/cm3,
, in floating Eichhornia crassipes canopies under flow conditions typical of natural rivers (0.0167-0.0667 m/s). Physical modelling tests reveal that aquatic vegetation significantly alters the hydrodynamic structure and enhances the dissipation of turbulence in the water column, leading to decreased velocities, diversified length scales, and increased turbulent kinetic energy (TKE) in regions with higher frontal vegetation areas. This turbulence, in turn, facilitated momentum exchange and vertical mixing, particularly in regions with the most pronounced frontal area changes. Wider canopy spacing promoted the evolution of wake turbulence and facilitated wake expansion throughout the water column, generating coherent structures that effectively doubled the integral length scales with increasing distance between canopies from 0.5 m to 1.5 m. This adjustment resulted in a more uniformly dispersed downstream movement of MPs. Notably, the presence of canopies amplified MP diffusivity by 10-40 times compared to equivalent unvegetated conditions, transitioning the primary mixing mechanism from shear-induced velocity gradients to turbulence enhanced by plant-flow interactions. This study offers a robust framework for quantifying MP mixing and predicting longitudinal dispersion coefficients within the floating vegetated flows, by developing models that depict the vertical profiles of TKE and turbulent diffusivity featured by canopy morphology and spacing. The insights from this study make a significant contribution toward improving our ability to predict the mixing and fate of MPs in riverine environments and underscore the necessity of incorporating the complex dynamics of aquatic vegetation into environmental management and MP risk assessments.},
 bibtype = {article},
 author = {Guo, Mingqi and Bon, Stefan A. F. and Abolfathi, Soroush},
 doi = {https://doi.org/10.1016/j.watres.2025.123534},
 journal = {Water Research}
}

Despite the significance of rivers and streams in transporting terrestrial microplastics (MP) to the oceans, limited research has focused on the role of aquatic vegetation and their complex geometry in shaping the underlying mechanisms governing MP mixing and dispersion processes in riverine environments. This study, for the first time, investigates the transport and fate of non-buoyant MPs, specifically those with diameters of 188 nm and 6 micrometer and a density of 1.04 g/cm3, , in floating Eichhornia crassipes canopies under flow conditions typical of natural rivers (0.0167-0.0667 m/s). Physical modelling tests reveal that aquatic vegetation significantly alters the hydrodynamic structure and enhances the dissipation of turbulence in the water column, leading to decreased velocities, diversified length scales, and increased turbulent kinetic energy (TKE) in regions with higher frontal vegetation areas. This turbulence, in turn, facilitated momentum exchange and vertical mixing, particularly in regions with the most pronounced frontal area changes. Wider canopy spacing promoted the evolution of wake turbulence and facilitated wake expansion throughout the water column, generating coherent structures that effectively doubled the integral length scales with increasing distance between canopies from 0.5 m to 1.5 m. This adjustment resulted in a more uniformly dispersed downstream movement of MPs. Notably, the presence of canopies amplified MP diffusivity by 10-40 times compared to equivalent unvegetated conditions, transitioning the primary mixing mechanism from shear-induced velocity gradients to turbulence enhanced by plant-flow interactions. This study offers a robust framework for quantifying MP mixing and predicting longitudinal dispersion coefficients within the floating vegetated flows, by developing models that depict the vertical profiles of TKE and turbulent diffusivity featured by canopy morphology and spacing. The insights from this study make a significant contribution toward improving our ability to predict the mixing and fate of MPs in riverine environments and underscore the necessity of incorporating the complex dynamics of aquatic vegetation into environmental management and MP risk assessments.

@article{
 title = {A mesh reinforced pressure-sensitive adhesive for a linerless label design},
 type = {article},
 year = {2024},
 pages = {248-261},
 volume = {2},
 websites = {https://doi.org/10.1039/D3LP00224A},
 id = {69231e3f-0113-366f-8678-36abe7fdb946},
 created = {2024-01-02T14:09:53.495Z},
 accessed = {2024-01-23},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:13:49.530Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {A concept for an on-demand linerless pressure sensitive adhesive (PSA) label is shown. Containment of a PSA has been achieved by entrapment within a scaffolding 3D hard mesh structure. The label sticks upon instant application of heat and pressure, which softens and deforms the mesh allowing for PSA release. The design eliminates the need for a release liner and release coating in labels offering a more sustainable product. Herein, the mesh reinforced PSA system was made by film formation of a binary polymer latex mixture consisting of ‘hard’ (high glass transition temperature, 𝑇𝑔,hard) polystyrene particles and a ‘soft’ (low glass transition temperature 𝑇𝑔,soft) poly(n-butyl acrylate)-based PSA latex of similar particle diameter, onto a model polyethylene terephthalate (PET) facestock. The system was annealed above 𝑇𝑔,h𝑎𝑟𝑑 to fuse the polystyrene colloids, creating a 3D interconnected open cellular network. The porous scaffold was shown by scanning electron microscopy and x-ray computed tomography. The linerless PSA label is in a dormant, ‘non-stick’ state at room temperature showing excellent blocking resistance at storage conditions. Adhesion is activated on demand with heat (𝑇 > 𝑇𝑔, hard) and light pressure. The adhesive behavior of the linerless PSA labels was probed using peel, shear strength and tack, its performance being promising.},
 bibtype = {article},
 author = {Brogden, Emily M. and Wilson, Paul F. and Hindmarsh, Steven and Hands-Portman, Ian and Unsworth, Andrew and Liarou, Evelina and Bon, Stefan A. F.},
 doi = {10.1039/D3LP00224A},
 journal = {RSC Applied Polymers}
}

A concept for an on-demand linerless pressure sensitive adhesive (PSA) label is shown. Containment of a PSA has been achieved by entrapment within a scaffolding 3D hard mesh structure. The label sticks upon instant application of heat and pressure, which softens and deforms the mesh allowing for PSA release. The design eliminates the need for a release liner and release coating in labels offering a more sustainable product. Herein, the mesh reinforced PSA system was made by film formation of a binary polymer latex mixture consisting of ‘hard’ (high glass transition temperature, 𝑇𝑔,hard) polystyrene particles and a ‘soft’ (low glass transition temperature 𝑇𝑔,soft) poly(n-butyl acrylate)-based PSA latex of similar particle diameter, onto a model polyethylene terephthalate (PET) facestock. The system was annealed above 𝑇𝑔,h𝑎𝑟𝑑 to fuse the polystyrene colloids, creating a 3D interconnected open cellular network. The porous scaffold was shown by scanning electron microscopy and x-ray computed tomography. The linerless PSA label is in a dormant, ‘non-stick’ state at room temperature showing excellent blocking resistance at storage conditions. Adhesion is activated on demand with heat (𝑇 > 𝑇𝑔, hard) and light pressure. The adhesive behavior of the linerless PSA labels was probed using peel, shear strength and tack, its performance being promising.

@article{
 title = {Exploiting a branched radical polymerization strategy to enhance the degree of grafting onto graphene oxide},
 type = {article},
 year = {2024},
 pages = {2199-2211},
 volume = {15},
 websites = {https://pubs.rsc.org/en/content/articlelanding/2024/py/d4py00300d},
 id = {7a1da8ae-6220-3ba6-be7b-d1aaad4bca19},
 created = {2024-03-15T18:25:14.967Z},
 accessed = {2024-05-09},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:13:31.212Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {The synthesis of polymer-grafted graphene oxide (GO) using a branched radical polymerization strategy is described. A methacrylate-based macromonomer is used as a chain-transfer agent to enhance the degree of grafting and prevent macroscopic gel formation. A methacrylic acid-based macromonomer was first synthesized via aqueous solution catalytic chain transfer polymerization. The resultant macromonomer was used as a chain transfer agent in the radical polymerization of poly(ethylene glycol) methacrylate (PEGMA) in the presence of a dispersion of GO in a water/ DMF mixture (50:50 w/w). The degree of grafting was determined using thermogravimetric analyses and infrared spectroscopy, and the geometrical evolution was investigated using atomic force microscopy. The grafting efficiency increased with the degree of branching.},
 bibtype = {article},
 author = {Lee, Wai Hin and Bon, Stefan A. F.},
 doi = {https://doi.org/10.1039/D4PY00300D},
 journal = {Polymer Chemistry}
}

The synthesis of polymer-grafted graphene oxide (GO) using a branched radical polymerization strategy is described. A methacrylate-based macromonomer is used as a chain-transfer agent to enhance the degree of grafting and prevent macroscopic gel formation. A methacrylic acid-based macromonomer was first synthesized via aqueous solution catalytic chain transfer polymerization. The resultant macromonomer was used as a chain transfer agent in the radical polymerization of poly(ethylene glycol) methacrylate (PEGMA) in the presence of a dispersion of GO in a water/ DMF mixture (50:50 w/w). The degree of grafting was determined using thermogravimetric analyses and infrared spectroscopy, and the geometrical evolution was investigated using atomic force microscopy. The grafting efficiency increased with the degree of branching.

@article{
 title = {Small molecule organic eutectics as candidates to replace plastics.},
 type = {article},
 year = {2024},
 pages = {14458-14470},
 volume = {15},
 websites = {https://doi.org/10.1039/D4SC02574A},
 id = {cc33f46e-0154-330a-8b52-fa546ce27239},
 created = {2024-04-03T15:16:38.020Z},
 accessed = {2024-08-12},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-09-12T07:41:35.630Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {Legislative change and shifting consumer sentiment drive a need to replace polymers in certain products. Herein, we highlight that eutectic molecular glasses and liquids are promising but underutilized candidate materials. We formulate a series of hydrophobic eutectic molecular liquids and glasses by mixing their crystalline components. The eutectic composition of each mixture was determined by both differential scanning calorimetry (DSC) and UV-vis spectroscopic measurements, which were processed and analyzed using a trained partial least squares regression model. With product shelf-life in mind, the long-term stability (up to 14 months) of the amorphous materials towards crystallization was proven using powder x-ray diffraction (PXRD). Molecular dynamics (MD) simulations put forward potential design rules in terms of the physical stability of these glasses. Rheological properties were investigated from the perspective of processability. Low fragility indices were found for all liquids, aiding processability through glassblowing, fiber pulling, film formation and molding. We show that properties can be tailored by blending two different eutectic systems or simply adding a plasticizer. To demonstrate a potential application area, the 4-hydroxychalcone and bifonazole eutectic system was used as a matrix for controlled release studies of a model active ingredient.},
 bibtype = {article},
 author = {Ryan, Joshua L. and Sosso, Gabriele C. and Bon, Stefan A. F.},
 journal = {Chem. Sci. }
}

Legislative change and shifting consumer sentiment drive a need to replace polymers in certain products. Herein, we highlight that eutectic molecular glasses and liquids are promising but underutilized candidate materials. We formulate a series of hydrophobic eutectic molecular liquids and glasses by mixing their crystalline components. The eutectic composition of each mixture was determined by both differential scanning calorimetry (DSC) and UV-vis spectroscopic measurements, which were processed and analyzed using a trained partial least squares regression model. With product shelf-life in mind, the long-term stability (up to 14 months) of the amorphous materials towards crystallization was proven using powder x-ray diffraction (PXRD). Molecular dynamics (MD) simulations put forward potential design rules in terms of the physical stability of these glasses. Rheological properties were investigated from the perspective of processability. Low fragility indices were found for all liquids, aiding processability through glassblowing, fiber pulling, film formation and molding. We show that properties can be tailored by blending two different eutectic systems or simply adding a plasticizer. To demonstrate a potential application area, the 4-hydroxychalcone and bifonazole eutectic system was used as a matrix for controlled release studies of a model active ingredient.

@article{
 title = {Branched polymer grafted graphene oxide (GO) as a 2D template for calcium phosphate growth},
 type = {article},
 year = {2024},
 pages = {438-450},
 volume = {675},
 websites = {https://doi.org/10.1016/j.jcis.2024.06.221},
 id = {78b7f7ea-8c6c-3b08-83a5-e476977c5d71},
 created = {2024-05-10T14:23:37.068Z},
 accessed = {2024-07-04},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-07-08T20:05:45.514Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {Hypothesis: 
Graphene Oxide (GO)-templated deposition of inorganic materials through synthesis on dispersed single sheets of GO is often complicated by the loss of the desired 2D morphology owing to the coagulation of GO sheets at high salt concentrations and non-templated homogenous nucleation. Modifying GO with anionic polymer is expected to solve both problems by i) enhancing electrostatic(steric) stabilization upon exposure to high concentrations of the ionic precursors, and ii) offering additional nucleation sites at the grafted anionic moieties to avoid homogeneous secondary nucleation.
Experiments:
GO was grafted with branched copolymers of poly(ethylene glycol) methacrylate (PEGMA 500) and diethylene glycol dimethacrylate (DEGDMA) and -vinyl terminated methacrylic acid macromonomer (P(MAA)), the latter serving as an addition-fragmentation chain transfer agent. The colloidal stability of GO dispersions in water toward salt was evaluated before and after modification. Precipitation of calcium phosphate (CaP) was performed by incubating modified GO in the precursor solutions. The conditions were optimized to maximize the nucleation selectively onto GO without homogeneous CaP nucleation and coagulation of the GO-sheets. 
Findings:
The copolymer grafted GO-sheets shows superior colloidal stability when dispersed in water. No aggregation occurs in the incubating ionic CaP precursor solutions. The optimum templated deposition of CaP onto the GO sheets by precipitation is to add a second shot of precursors after the nucleation stage to obtain GO sheets fully decorated with calcium phosphate nanorods without self-nucleation. Via the careful design on the GO modification and incubation process, the growth of calcium phosphate nanorods were confined in the desired 2D order exclusively, hereby achieving the goal of an efficient GO-templated synthesis.
Keywords: Graphene oxide, calcium phosphate, templated synthesis, branched polymer, colloidal stability},
 bibtype = {article},
 author = {Lee, Wai Hin and Bon, Stefan A. F.},
 journal = {J. Colloid Interface Sci. }
}

Hypothesis: Graphene Oxide (GO)-templated deposition of inorganic materials through synthesis on dispersed single sheets of GO is often complicated by the loss of the desired 2D morphology owing to the coagulation of GO sheets at high salt concentrations and non-templated homogenous nucleation. Modifying GO with anionic polymer is expected to solve both problems by i) enhancing electrostatic(steric) stabilization upon exposure to high concentrations of the ionic precursors, and ii) offering additional nucleation sites at the grafted anionic moieties to avoid homogeneous secondary nucleation. Experiments: GO was grafted with branched copolymers of poly(ethylene glycol) methacrylate (PEGMA 500) and diethylene glycol dimethacrylate (DEGDMA) and -vinyl terminated methacrylic acid macromonomer (P(MAA)), the latter serving as an addition-fragmentation chain transfer agent. The colloidal stability of GO dispersions in water toward salt was evaluated before and after modification. Precipitation of calcium phosphate (CaP) was performed by incubating modified GO in the precursor solutions. The conditions were optimized to maximize the nucleation selectively onto GO without homogeneous CaP nucleation and coagulation of the GO-sheets. Findings: The copolymer grafted GO-sheets shows superior colloidal stability when dispersed in water. No aggregation occurs in the incubating ionic CaP precursor solutions. The optimum templated deposition of CaP onto the GO sheets by precipitation is to add a second shot of precursors after the nucleation stage to obtain GO sheets fully decorated with calcium phosphate nanorods without self-nucleation. Via the careful design on the GO modification and incubation process, the growth of calcium phosphate nanorods were confined in the desired 2D order exclusively, hereby achieving the goal of an efficient GO-templated synthesis. Keywords: Graphene oxide, calcium phosphate, templated synthesis, branched polymer, colloidal stability

@article{
 title = {Water-based polymer colloids with a branched chain architecture as low-gel pressure-sensitive adhesives},
 type = {article},
 year = {2024},
 pages = {2849-2861},
 volume = {15},
 websites = {https://dx.doi.org/10.1039/D4PY00522H},
 id = {d3d36523-072c-3587-a6ff-fe90d8cb7e45},
 created = {2024-06-19T08:11:33.317Z},
 accessed = {2024-06-19},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-07-16T09:14:29.018Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {The performance of water-based acrylic pressure-sensitive adhesives, in which the latex particles had minimal gel content of typically less than a few percent and the polymer chains had a branched architecture, were investigated. A series of semi-batch emulsion copolymerizations of 2-octyl acrylate, isobornyl acrylate and acrylic acid was carried out in the presence of ethylene glycol dimethacrylate as crosslinker. The molecular weight distributions and branched chain topology were regulated by using 2-ethylhexyl thioglycolate as a chain-transfer agent. The momoners and chain-transfer agent were selected as these were already available as bio-based feedstocks, or had a realistic potential to become available from non-petrochemical resources. Adhesive films cast from the polymer dispersions demonstrated good peel, shear strength and tack adhesion energies. This is attributed to polymer chain branching, which unlocks a broader window for the design rules for pressure-sensitive adhesives. Detailed rheological studies of the viscoelastic materials were conducted to support the adhesive test results.},
 bibtype = {article},
 author = {Brogden, Emily M. and Bon, Stefan A. F.},
 doi = {10.1039/D4PY00522H},
 journal = {Polymer Chemistry}
}

The performance of water-based acrylic pressure-sensitive adhesives, in which the latex particles had minimal gel content of typically less than a few percent and the polymer chains had a branched architecture, were investigated. A series of semi-batch emulsion copolymerizations of 2-octyl acrylate, isobornyl acrylate and acrylic acid was carried out in the presence of ethylene glycol dimethacrylate as crosslinker. The molecular weight distributions and branched chain topology were regulated by using 2-ethylhexyl thioglycolate as a chain-transfer agent. The momoners and chain-transfer agent were selected as these were already available as bio-based feedstocks, or had a realistic potential to become available from non-petrochemical resources. Adhesive films cast from the polymer dispersions demonstrated good peel, shear strength and tack adhesion energies. This is attributed to polymer chain branching, which unlocks a broader window for the design rules for pressure-sensitive adhesives. Detailed rheological studies of the viscoelastic materials were conducted to support the adhesive test results.

@article{
 title = {Phase change material nanocapsules as latent function thermal fluids with tuneable thermal energy storage profiles},
 type = {article},
 year = {2024},
 pages = {3359-3377},
 volume = {15},
 websites = {https://doi.org/10.1039/D4PY00789A},
 id = {f282d875-a631-3e39-8f1d-5cb85376a4e8},
 created = {2024-06-19T11:05:29.269Z},
 accessed = {2024-07-30},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-08-22T08:58:27.377Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {Phase change materials (PCMs) can capture and release thermal energy in the form of latent heat and PCMs as liquid dispersions are known as latent function thermal fluids. For these dispersions, the PCMs are encapsulated to warrant colloidal stability. Here, capsule formation of mini-emulsions of various methacrylates in the presence of trimethylolpropane trimethacrylate (TMA) as a crosslinker, and n-hexadecane (HD), n-octadecane (OCT), and n-docosane (DOC) as PCM was investigated. An ω-unsaturated poly(n-butyl methacrylate-b-[(methacrylic acid)-co-(methyl methacrylate)]) macromonomer was used as a reactive macromolecular emulsifier. The mini-emulsion polymerizations, capsule fabrication and performance were optimized. The resulting latent function thermal fluids and their dried equivalents were studied with differential scanning calorimetry (DSC). A challenge of these materials is matching the temperature range of the application to that of their phase change. The performance of a thermal fluid of DOC nanocapsules was tested against the base fluid water with promising results. As a tunability concept, crosslinked poly(methyl methacrylate) nanocapsules of n-octadecane (OCT) and n-docosane (DOC) were blended as a tunable latent function thermal fluid.},
 bibtype = {article},
 author = {Booth, Joshua R. and Davies, Joshua D. and Bon, Stefan A. F.},
 doi = {10.1039/D4PY00789A},
 journal = {Polymer Chemistry}
}

Phase change materials (PCMs) can capture and release thermal energy in the form of latent heat and PCMs as liquid dispersions are known as latent function thermal fluids. For these dispersions, the PCMs are encapsulated to warrant colloidal stability. Here, capsule formation of mini-emulsions of various methacrylates in the presence of trimethylolpropane trimethacrylate (TMA) as a crosslinker, and n-hexadecane (HD), n-octadecane (OCT), and n-docosane (DOC) as PCM was investigated. An ω-unsaturated poly(n-butyl methacrylate-b-[(methacrylic acid)-co-(methyl methacrylate)]) macromonomer was used as a reactive macromolecular emulsifier. The mini-emulsion polymerizations, capsule fabrication and performance were optimized. The resulting latent function thermal fluids and their dried equivalents were studied with differential scanning calorimetry (DSC). A challenge of these materials is matching the temperature range of the application to that of their phase change. The performance of a thermal fluid of DOC nanocapsules was tested against the base fluid water with promising results. As a tunability concept, crosslinked poly(methyl methacrylate) nanocapsules of n-octadecane (OCT) and n-docosane (DOC) were blended as a tunable latent function thermal fluid.

@article{
 title = {Developing Hydration Maps of Polymer Latex Film Formation using Terahertz Time-Domain Spectroscopy},
 type = {article},
 year = {2024},
 pages = {25023-25033},
 volume = {40(47)},
 websites = {https://doi.org/10.1021/acs.langmuir.4c03103},
 month = {11},
 day = {13},
 id = {e76af86d-6584-3f3e-bae9-e2641257ef46},
 created = {2024-07-12T14:50:37.984Z},
 accessed = {2024-11-14},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-12-18T18:36:53.937Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {false},
 hidden = {false},
 private_publication = {false},
 abstract = {The dynamics of the drying process of polymer latexes are important to track as they influence the mechanical properties and performance of polymer films. Current methods used to follow this film formation process include gravimetric analysis, coupled with advanced techniques like GARField-NMR or Optical Coherence Tomography. These latter two methods provide height and spatial information in the z-direction, and occasionally in the xz- or yz-planes. Terahertz time-Domain spectroscopy (THz-TDS) is a welcome addition as it provides both the structural and spectroscopic information in the xy-plane, filling the geometric gap. Herein, we utilize THz-TDS to study the film formation process of various polymer latexes with a broad range of glass transition temperatures. We showcase the applicability of this
technique in obtaining 2D hydration maps of the drying dispersions, in the form of droplets, using latex-dependant calibration lines. Our findings display known phenomena arising from the drying of the colloidal dispersions.},
 bibtype = {article},
 author = {Costa, Gonçalo and Brogden, Emily M. and Young, Jacob J. and Ou, Huiliang and Hernandez-Serraro, Arturo I. and Stantchev, Rayko I. and Bon, Stefan A. F. and Pickwell-MacPherson, Emma},
 doi = {10.1021/acs.langmuir.4c03103},
 journal = {Langmuir}
}

The dynamics of the drying process of polymer latexes are important to track as they influence the mechanical properties and performance of polymer films. Current methods used to follow this film formation process include gravimetric analysis, coupled with advanced techniques like GARField-NMR or Optical Coherence Tomography. These latter two methods provide height and spatial information in the z-direction, and occasionally in the xz- or yz-planes. Terahertz time-Domain spectroscopy (THz-TDS) is a welcome addition as it provides both the structural and spectroscopic information in the xy-plane, filling the geometric gap. Herein, we utilize THz-TDS to study the film formation process of various polymer latexes with a broad range of glass transition temperatures. We showcase the applicability of this technique in obtaining 2D hydration maps of the drying dispersions, in the form of droplets, using latex-dependant calibration lines. Our findings display known phenomena arising from the drying of the colloidal dispersions.

@article{
 title = {Styrene-based polymerised High Internal Phase Emulsions using monomers in the internal phase as co-surfactants for improved liquid chromatography},
 type = {article},
 year = {2022},
 pages = {9773-9785},
 volume = {12},
 id = {d382d7e6-7e3e-36cf-ba71-2738056a35f9},
 created = {2024-01-02T14:09:27.845Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:27.845Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Poly(styrene-co-divinylbenzene)-based monoliths were prepared from the polymerisation of water-in-monomer high internal phase emulsions, where the water-soluble monomers acrylamide (AAm) or poly(ethylene glycol) diacrylate (PEGDA) (Mw 258) were also included in the 90 vol% internal phase. Both AAm and PEGDA were found to act as co-surfactants, resulting in the obtainment of monoliths with greater homogeneity in some cases. As a result these materials demonstrated significantly improved chromatographic performance for the separation of a standard mixture of proteins using reversed-phase liquid chromatography, in comparison to monoliths prepared with no internal phase monomer. In particular, the columns grafted with PEGDA were capable of separating a more complex mixture consisting of seven components. The inclusion of monomers in the internal phase also allowed for the functionalisation of the monoliths surface where the degree of polymerisation that occurred in the internal phase, which was governed by the monomer content in the internal phase and initiation location, determined whether polymeric chains or a hydrogel were grafted to the surface. A monolith grafted with AAm was also found to be capable of retaining polar analytes as a result of the increase in surface hydrophilicity.},
 bibtype = {article},
 author = {Desire, Christopher T. and Dario Arrua, R. and Mansour, Fotouh R. and Bon, Stefan A. F. and Hilder, Emily F.},
 journal = {RSC Advances}
}

Poly(styrene-co-divinylbenzene)-based monoliths were prepared from the polymerisation of water-in-monomer high internal phase emulsions, where the water-soluble monomers acrylamide (AAm) or poly(ethylene glycol) diacrylate (PEGDA) (Mw 258) were also included in the 90 vol% internal phase. Both AAm and PEGDA were found to act as co-surfactants, resulting in the obtainment of monoliths with greater homogeneity in some cases. As a result these materials demonstrated significantly improved chromatographic performance for the separation of a standard mixture of proteins using reversed-phase liquid chromatography, in comparison to monoliths prepared with no internal phase monomer. In particular, the columns grafted with PEGDA were capable of separating a more complex mixture consisting of seven components. The inclusion of monomers in the internal phase also allowed for the functionalisation of the monoliths surface where the degree of polymerisation that occurred in the internal phase, which was governed by the monomer content in the internal phase and initiation location, determined whether polymeric chains or a hydrogel were grafted to the surface. A monolith grafted with AAm was also found to be capable of retaining polar analytes as a result of the increase in surface hydrophilicity.

@article{
 title = {ω-Unsaturated methacrylate macromonomers as reactive polymeric stabilizers in mini-emulsion polymerization},
 type = {article},
 year = {2022},
 pages = {1335-1349},
 volume = {13},
 websites = {https://doi.org/10.1039/D1PY01664D},
 id = {cbc58a43-40d6-3f17-8546-622d0f8516b7},
 created = {2024-01-02T14:09:28.562Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:28.562Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Polymer latexes of poly(benzyl methacrylate) P(BzMA) were synthesized by mini-emulsion polymerization, using hexadecane as the hydrophobe and ω-unsaturated methacrylate-based macromonomers as a reactive stabilizer. The amphiphilic macromonomers were synthesized by catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via sulfur-free reversible addition-fragmentation chain transfer (SF-RAFT). Their critical micelle concentration (CMC) was determined by dynamic light scattering (DLS), and micelle size was measured using DLS and small angle x-ray scattering (SAXS). The surface activity of the stabilizers was measured by pendant drop tensiometry and compared to modelled behaviour. For the mini-emulsion polymerizations, macromonomer stabilizers were added at a range of concentrations, with respect to the dispersed phase. Using less than 5 wt.% stabilizer, SEM micrographs showed many of the particles were bowl-shaped. This morphology was studied in depth and we propose that monomer transport occurs between particles during polymerization towards the smaller particles as a direct result of compartmentalization. At concentrations of 5 wt.% and higher, bimodal droplet and particle distributions were observed by DLS and SEM. We propose shear-dependent depletion flocculation as the explanation. Lastly, the effectiveness of the reactive stabilizers was tested in terms of latex stability and molecular weight control. Resistance to coagulation during freeze-thaw cycles and prolonged dialysis were tested. Examination of P(BzMA) reaction kinetics and molecular weight indicated that the incorporation of macromonomer is gradual and less than quantitative at the end of the polymerization process, in agreement with the mechanistic understanding.},
 bibtype = {article},
 author = {Booth, Joshua R. and Davies, Joshua D. and Bon, Stefan A. F.},
 journal = {Polym. Chem.}
}

Polymer latexes of poly(benzyl methacrylate) P(BzMA) were synthesized by mini-emulsion polymerization, using hexadecane as the hydrophobe and ω-unsaturated methacrylate-based macromonomers as a reactive stabilizer. The amphiphilic macromonomers were synthesized by catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via sulfur-free reversible addition-fragmentation chain transfer (SF-RAFT). Their critical micelle concentration (CMC) was determined by dynamic light scattering (DLS), and micelle size was measured using DLS and small angle x-ray scattering (SAXS). The surface activity of the stabilizers was measured by pendant drop tensiometry and compared to modelled behaviour. For the mini-emulsion polymerizations, macromonomer stabilizers were added at a range of concentrations, with respect to the dispersed phase. Using less than 5 wt.% stabilizer, SEM micrographs showed many of the particles were bowl-shaped. This morphology was studied in depth and we propose that monomer transport occurs between particles during polymerization towards the smaller particles as a direct result of compartmentalization. At concentrations of 5 wt.% and higher, bimodal droplet and particle distributions were observed by DLS and SEM. We propose shear-dependent depletion flocculation as the explanation. Lastly, the effectiveness of the reactive stabilizers was tested in terms of latex stability and molecular weight control. Resistance to coagulation during freeze-thaw cycles and prolonged dialysis were tested. Examination of P(BzMA) reaction kinetics and molecular weight indicated that the incorporation of macromonomer is gradual and less than quantitative at the end of the polymerization process, in agreement with the mechanistic understanding.

@article{
 title = {Flower-like colloidal particles through precipitation polymerization of redox responsive liquid crystals},
 type = {article},
 year = {2021},
 pages = {27026-27030},
 volume = {60},
 websites = {https://doi.org/10.1002/anie.202111521},
 id = {4d6ef558-2aa9-3bcf-ad1c-b634a06d2883},
 created = {2024-01-02T14:09:28.762Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:28.762Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {We report on the synthesis of monodisperse, flower-like, liquid crystalline (LC) polymer particles by precipitation polymerization of an LC monomer mixture consisting of benzoic acid-functionalized acrylates and disulfide-functionalized diacrylates. Introduction of a minor amount of disulfide-functionalized diacrylates (≤ 10 wt%) induced the formation of flower-like shapes. The shape of the particles can be tuned from flower- to disk-like to spherical by elevating the polymerization temperature. The solvent environment also has a pronounced effect on the particle size. Time-resolved TEM reveals that the final particle morphology was formed in the early stages of the polymerization and that subsequent polymerization resulted in continued particle growth without affecting the morphology. Finally, the degradation of the particles under reducing conditions was much faster for flower-like particles than for spherical particles, a result of their higher surface-to-volume ratio.},
 bibtype = {article},
 author = {Liu, Xiaohong and Moradi, Mohammad-Amin and Bus, Tom and Debije, Michael G. and Bon, Stefan A. F. and Heuts, Johan P. A. and Schenning, Albert P. H. J.},
 journal = {Angewandte Chemie - International Edition},
 number = {52}
}

We report on the synthesis of monodisperse, flower-like, liquid crystalline (LC) polymer particles by precipitation polymerization of an LC monomer mixture consisting of benzoic acid-functionalized acrylates and disulfide-functionalized diacrylates. Introduction of a minor amount of disulfide-functionalized diacrylates (≤ 10 wt%) induced the formation of flower-like shapes. The shape of the particles can be tuned from flower- to disk-like to spherical by elevating the polymerization temperature. The solvent environment also has a pronounced effect on the particle size. Time-resolved TEM reveals that the final particle morphology was formed in the early stages of the polymerization and that subsequent polymerization resulted in continued particle growth without affecting the morphology. Finally, the degradation of the particles under reducing conditions was much faster for flower-like particles than for spherical particles, a result of their higher surface-to-volume ratio.

@article{
 title = {Thermoresponsive icy road sign by light scattering and enhanced fluorescence},
 type = {article},
 year = {2021},
 pages = {7174-7185},
 volume = {9},
 websites = {https://doi.org/10.1039/D1TC01189H},
 id = {63b5e2ab-571c-3866-a795-eb23572c8ec8},
 created = {2024-01-02T14:09:28.946Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:14:39.826Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Prototypes of flexible, electricity-free, ice warning signs for roads and pavements have been developed. A temperature triggered response in the form of an upper critical solution temperature (UCST) type phase separation targeted near the freezing point of water manifests itself through light scattering as a clear-to-opaque transition. It is simultaneously amplified by an enhanced photoluminescence effect. The conceptual road sign application is a multi-lamellar flexible strip with an active layer of a polystyrene-based solution. The solvent is a plasticizer, here either dioctyl phthalate (DOP) or its alternative 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH). A collection of styrene-based macromolecules were made by free radical (co)polymerization, varying molecular weight and monomer feed composition. UCST-type phase diagrams for the polymer solutions were constructed from cloud point data measured with a bespoke photographic set-up, in which up to 30 samples were analyzed simultaneously monitoring both light scattering, in the form of opacity measurements, and fluorescence. For the latter, the concept of restricted motion enhanced photoluminescence, often referred to as aggregation-induced emission (AIE), was used. Polystyrene labelled with tetraphenylethylene (TPE) was used for this. The contrast between ‘ON’ and ‘OFF’ states in the conceptual ice warning signs was optimized by tuning the polymer concentration and the active layer thickness. Our prototype signs show full reversibility over many temperature cycles. We believe the concept can be of wider use in electricity-free signs and labels.},
 bibtype = {article},
 author = {Booth, Joshua R. and Young, Robert A. and Richards Gonzales, Andrés N. and Meakin, Zachary J. and Preuss-Weber, Corinna M. and Jaggers, Ross W. and Bon, Stefan A. F.},
 journal = {J. Mater. Chem. C}
}

Prototypes of flexible, electricity-free, ice warning signs for roads and pavements have been developed. A temperature triggered response in the form of an upper critical solution temperature (UCST) type phase separation targeted near the freezing point of water manifests itself through light scattering as a clear-to-opaque transition. It is simultaneously amplified by an enhanced photoluminescence effect. The conceptual road sign application is a multi-lamellar flexible strip with an active layer of a polystyrene-based solution. The solvent is a plasticizer, here either dioctyl phthalate (DOP) or its alternative 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH). A collection of styrene-based macromolecules were made by free radical (co)polymerization, varying molecular weight and monomer feed composition. UCST-type phase diagrams for the polymer solutions were constructed from cloud point data measured with a bespoke photographic set-up, in which up to 30 samples were analyzed simultaneously monitoring both light scattering, in the form of opacity measurements, and fluorescence. For the latter, the concept of restricted motion enhanced photoluminescence, often referred to as aggregation-induced emission (AIE), was used. Polystyrene labelled with tetraphenylethylene (TPE) was used for this. The contrast between ‘ON’ and ‘OFF’ states in the conceptual ice warning signs was optimized by tuning the polymer concentration and the active layer thickness. Our prototype signs show full reversibility over many temperature cycles. We believe the concept can be of wider use in electricity-free signs and labels.

@article{
 title = {Anisotropic silica colloids for light scattering},
 type = {article},
 year = {2021},
 pages = {2695-2700},
 volume = {9},
 websites = {https://doi.org/10.1039/D1TC00072A},
 id = {3d34071d-d64c-32fd-9700-3d997d12a8b2},
 created = {2024-01-02T14:09:29.115Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:50.048Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Scattering enhancers are a class of nanomaterials used in every colored or white material surrounding us: from paints and inks to food and cosmetics to packaging and paper. Such hiding pigments usually consist of non-absorbing, high refractive index nanoparticles, for example spherically shaped titanium dioxide nanopowders. However use of TiO2 carries a high environmental burden. To offset the carbon footprint and health concerns inherent with the use of titanium dioxide, one could approach the challenge of scattering optimization by modifying the morphology of the scattering elements rather than their refractive index. Here, inspired by the bright anisotropic scattering system found in nature, we demonstrate that anisotropic sphero-cylindrical particles can outperform the scattering efficiency of their isotropic counterparts - obtaining an excellent scattering performances across the visible electromagnetic spectrum. We developed a class of micron-sized scattering enhancers composed only of silica. We show that these cylindrical colloids are easily assembled into scattering supracolloidal balls, a new class of pigment microspheres which can be used in formulations for ultrabright coatings.},
 bibtype = {article},
 author = {Jacucci, Gianni and Longbottom, Brooke W and Parkins, Christopher C and Bon, Stefan A F and Vignolini, Silvia},
 journal = {J. Mater. Chem. C}
}

Scattering enhancers are a class of nanomaterials used in every colored or white material surrounding us: from paints and inks to food and cosmetics to packaging and paper. Such hiding pigments usually consist of non-absorbing, high refractive index nanoparticles, for example spherically shaped titanium dioxide nanopowders. However use of TiO2 carries a high environmental burden. To offset the carbon footprint and health concerns inherent with the use of titanium dioxide, one could approach the challenge of scattering optimization by modifying the morphology of the scattering elements rather than their refractive index. Here, inspired by the bright anisotropic scattering system found in nature, we demonstrate that anisotropic sphero-cylindrical particles can outperform the scattering efficiency of their isotropic counterparts - obtaining an excellent scattering performances across the visible electromagnetic spectrum. We developed a class of micron-sized scattering enhancers composed only of silica. We show that these cylindrical colloids are easily assembled into scattering supracolloidal balls, a new class of pigment microspheres which can be used in formulations for ultrabright coatings.

@article{
 title = {Textured microcapsules through crystallization},
 type = {article},
 year = {2021},
 pages = {5887-5894},
 volume = {13},
 websites = {https://pubs.acs.org/doi/10.1021/acsami.0c22378},
 id = {8e444bdc-8cd3-37ab-a182-5e10d0d51e2e},
 created = {2024-01-02T14:09:29.298Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:50.299Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {This work demonstrates the fabrication of surface textured microcapsules formed from emulsion droplets which are stabilized by an interlocking mesh of needle-like crystals. Crystals of the small organic compound decane-1,10-bis(cyclohexyl carbamate) are formed within the geometric confinement of the droplets, through precipitation from a binary-solvent dispersed phase. This binary mixture consists of a volatile solvent and non-volatile carrier oil. Crystallization is facilitated upon supersaturation due to evaporation of the volatile solvent. Microcapsule diameter can be easily tuned using microfluidics. This approach also proves to be scalable when using conventional mixers, yielding spikey microcapsules with diameters in the range of 10-50 µm. It is highlighted that the capsule shape can be molded and arrested by jamming using recrystallization in geometric confinement. Moreover, it is show that these textured microcapsules show a promising enhanced deposition onto a range of fabric fibers.},
 bibtype = {article},
 author = {Wilson-Whitford, Samuel R and Jaggers, Ross W and Longbottom, Brooke W and Donald, Matt K and Clarkson, Guy J and Bon, Stefan A F},
 journal = {ACS Applied Materials & Interfaces},
 number = {4}
}

This work demonstrates the fabrication of surface textured microcapsules formed from emulsion droplets which are stabilized by an interlocking mesh of needle-like crystals. Crystals of the small organic compound decane-1,10-bis(cyclohexyl carbamate) are formed within the geometric confinement of the droplets, through precipitation from a binary-solvent dispersed phase. This binary mixture consists of a volatile solvent and non-volatile carrier oil. Crystallization is facilitated upon supersaturation due to evaporation of the volatile solvent. Microcapsule diameter can be easily tuned using microfluidics. This approach also proves to be scalable when using conventional mixers, yielding spikey microcapsules with diameters in the range of 10-50 µm. It is highlighted that the capsule shape can be molded and arrested by jamming using recrystallization in geometric confinement. Moreover, it is show that these textured microcapsules show a promising enhanced deposition onto a range of fabric fibers.

@article{
 title = {Introducing porosity in colloidal biocoatings to increase bacterial viability},
 type = {article},
 year = {2020},
 pages = {4545-4558},
 volume = {21},
 websites = {https://pubs.acs.org/doi/10.1021/acs.biomac.0c00649},
 id = {d9c8f274-cd60-375b-89c9-f915dabcf1f0},
 created = {2024-01-02T14:09:29.487Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:15:14.505Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {A biocoating confines non-growing, metabolically-active bacteria within a synthetic colloidal polymer (i.e. latex) film. Bacteria encapsulated inside biocoatings can perform useful functions, such as a biocatalyst in wastewater treatment. A biocoating needs to have high a permeability to allow a high rate of mass transfer for rehydration and the transport of both nutrients and metabolic products. It therefore requires an interconnected porous structure. Tuning the porosity architecture is a challenge. Here, we exploited rigid tubular nanoclays (halloysite) and non-toxic latex particles (with a relatively high glass transition temperature) as the colloidal “building blocks” to tailor the porosity inside biocoatings containing Escherichia coli bacteria as a model organism. Electron microscope images revealed inefficient packing of the rigid nanotubes and proved the existence of nanovoids along the halloysite/polymer interfaces. Single-cell observations using confocal laser scanning microscopy provided evidence for metabolic activity of the E. coli within the biocoatings through the expression of yellow fluorescent protein. A custom-built apparatus was used to measure the permeability of a fluorescein sodium salt in the biocoatings. Whereas there was no measurable permeability in a coating made from only latex particles, the permeability coefficient of the composite biocoatings increased with increasing halloysite content up to a value of 110-4 m h-1. The effects of this increase in permeability was demonstrated through a specially-developed resazurin reduction assay. Bacteria encapsulated in halloysite composite biocoatings had statistically significant higher metabolic activities in comparison to bacteria encapsulated in a non-optimized coating made from latex particles alone.},
 bibtype = {article},
 author = {Chen, Yuxiu and Krings, Simone and Booth, Joshua R. and Bon, Stefan A. F. and Hingley-Wilson, Suzanne and Keddie, Joseph L.},
 journal = {Biomacromolecules},
 number = {11}
}

A biocoating confines non-growing, metabolically-active bacteria within a synthetic colloidal polymer (i.e. latex) film. Bacteria encapsulated inside biocoatings can perform useful functions, such as a biocatalyst in wastewater treatment. A biocoating needs to have high a permeability to allow a high rate of mass transfer for rehydration and the transport of both nutrients and metabolic products. It therefore requires an interconnected porous structure. Tuning the porosity architecture is a challenge. Here, we exploited rigid tubular nanoclays (halloysite) and non-toxic latex particles (with a relatively high glass transition temperature) as the colloidal “building blocks” to tailor the porosity inside biocoatings containing Escherichia coli bacteria as a model organism. Electron microscope images revealed inefficient packing of the rigid nanotubes and proved the existence of nanovoids along the halloysite/polymer interfaces. Single-cell observations using confocal laser scanning microscopy provided evidence for metabolic activity of the E. coli within the biocoatings through the expression of yellow fluorescent protein. A custom-built apparatus was used to measure the permeability of a fluorescein sodium salt in the biocoatings. Whereas there was no measurable permeability in a coating made from only latex particles, the permeability coefficient of the composite biocoatings increased with increasing halloysite content up to a value of 110-4 m h-1. The effects of this increase in permeability was demonstrated through a specially-developed resazurin reduction assay. Bacteria encapsulated in halloysite composite biocoatings had statistically significant higher metabolic activities in comparison to bacteria encapsulated in a non-optimized coating made from latex particles alone.

@article{
 title = {On particle size distributions in catalytic chain transfer emulsion polymerization: chain-extension and the use of derived macromonomers as reactive surfactants in emulsion polymerization},
 type = {article},
 year = {2020},
 pages = {4599-4614},
 volume = {21},
 websites = {https://pubs.acs.org/doi/10.1021/acs.biomac.0c00766},
 id = {2eef855f-aeda-3279-a304-19ad46557c7e},
 created = {2024-01-02T14:09:29.708Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:15:54.227Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via reversible addition-fragmentation chain transfer (RAFT) were used to synthesize amphiphilic macromonomers (MM), in the form of polymer latexes. The macromonomers consisted of two blocks whose first was a random copolymer of methacrylic acid and methyl methacrylate, at 35:65 mol:mol, while the second block was n-butyl methacrylate P[(MAA-co-MMA)-block-PBMA]. The block copolymer colloids were disintegrated and micellized upon addition of ammonia. The resulting nano-sized polymer dispersions were used as reactive surfactants in the emulsion polymerization of n-butyl methacrylate. For this, a dual stage slow-fast monomer feed profile was used. The final polymer latexes were in the sub 100 nm range for particle diameter at 30 % w/w total polymer content. The emphasis of the work is to discuss and find an explanation for the observed particle size distributions in the three consecutive emulsion polymerization steps. The particle size distribution of the ω-unsaturated macromonomer latex synthesized by CCTP emulsion polymerization was found to be much broader than expected. This discrepancy is attributed to an extended particle nucleation period. The chain extension step in the macromonomer latex preparation showed considerable secondary nucleation. The presence of water soluble macromonomer species from the CCTP emulsion polymerization step assured that control of chain growth persisted. The use of the amphiphilic macromonomers as reactive surfactants in the form of a nanosized aggregate seed dispersion, showed that the average particle diameter could be tuned and that the molecular weight distributions could be regulated, when monomer starved conditions were used in the emulsion polymerizations.},
 bibtype = {article},
 author = {Lee, Wai Hin and Booth, Joshua R. and Bon, Stefan A. F.},
 journal = {Biomacromolecules},
 number = {11}
}

Catalytic chain transfer emulsion polymerization (CCTP) and subsequent chain extension via reversible addition-fragmentation chain transfer (RAFT) were used to synthesize amphiphilic macromonomers (MM), in the form of polymer latexes. The macromonomers consisted of two blocks whose first was a random copolymer of methacrylic acid and methyl methacrylate, at 35:65 mol:mol, while the second block was n-butyl methacrylate P[(MAA-co-MMA)-block-PBMA]. The block copolymer colloids were disintegrated and micellized upon addition of ammonia. The resulting nano-sized polymer dispersions were used as reactive surfactants in the emulsion polymerization of n-butyl methacrylate. For this, a dual stage slow-fast monomer feed profile was used. The final polymer latexes were in the sub 100 nm range for particle diameter at 30 % w/w total polymer content. The emphasis of the work is to discuss and find an explanation for the observed particle size distributions in the three consecutive emulsion polymerization steps. The particle size distribution of the ω-unsaturated macromonomer latex synthesized by CCTP emulsion polymerization was found to be much broader than expected. This discrepancy is attributed to an extended particle nucleation period. The chain extension step in the macromonomer latex preparation showed considerable secondary nucleation. The presence of water soluble macromonomer species from the CCTP emulsion polymerization step assured that control of chain growth persisted. The use of the amphiphilic macromonomers as reactive surfactants in the form of a nanosized aggregate seed dispersion, showed that the average particle diameter could be tuned and that the molecular weight distributions could be regulated, when monomer starved conditions were used in the emulsion polymerizations.

@article{
 title = {When Mayo falls short (Ctr >> 1): The Use of cumulative chain length distribution data in the determination of chain transfer constants (Ctr) for radical polymerizations.},
 type = {article},
 year = {2020},
 pages = {4281-4289},
 volume = {11},
 websites = {https://doi.org/10.1039/D0PY00348D},
 id = {7ff2f2ed-3f88-3bda-81a2-cd68172d0416},
 created = {2024-01-02T14:09:29.907Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:16:31.067Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {We report a new method of determining the chain transfer constant in free radical polymerisation using molecular weight distribution data. It is specifically designed for systems where its value is substantially greater than 1. In these cases the classical Mayo equation and Gilbert’s chain length distribution (CLD) method fall short, in that the concentration ratio of chain transfer agent to monomer can no longer be assumed to be constant. Marked composition drift invalidates the use of both. In our proposed method we use the analytical concentration ratio of chain transfer agent to monomer (t = 0 s) and monomer conversion data, in combination with data for the cumulative molecular weight distributions as input. We determined an analytical solution for the cumulative weight distribution, which is used to calculate the cumulative number and chain length distributions. Chain transfer constants are found either by fitting the natural logarithmic chain length distribution (CLD) data at a given monomer conversion, or by plotting the fitted values for the slopes obtained from the natural logarithmic chain length distribution (CLD) data at a set degree of polymerization, as a function of monomer conversion. Our method is validated by analyses of molecular weight data obtained from Monte Carlo simulations. We used our methodology to determine an experimental value of ca. 223 as a chain transfer constant of n-dodecanethiol in vinyl acetate free radical polymerisation at 333.15 K, which we showed was in excellent agreement with the Smith method.},
 bibtype = {article},
 author = {Donald, Matt K and Bon, Stefan A. F.},
 journal = {Polym. Chem.}
}

We report a new method of determining the chain transfer constant in free radical polymerisation using molecular weight distribution data. It is specifically designed for systems where its value is substantially greater than 1. In these cases the classical Mayo equation and Gilbert’s chain length distribution (CLD) method fall short, in that the concentration ratio of chain transfer agent to monomer can no longer be assumed to be constant. Marked composition drift invalidates the use of both. In our proposed method we use the analytical concentration ratio of chain transfer agent to monomer (t = 0 s) and monomer conversion data, in combination with data for the cumulative molecular weight distributions as input. We determined an analytical solution for the cumulative weight distribution, which is used to calculate the cumulative number and chain length distributions. Chain transfer constants are found either by fitting the natural logarithmic chain length distribution (CLD) data at a given monomer conversion, or by plotting the fitted values for the slopes obtained from the natural logarithmic chain length distribution (CLD) data at a set degree of polymerization, as a function of monomer conversion. Our method is validated by analyses of molecular weight data obtained from Monte Carlo simulations. We used our methodology to determine an experimental value of ca. 223 as a chain transfer constant of n-dodecanethiol in vinyl acetate free radical polymerisation at 333.15 K, which we showed was in excellent agreement with the Smith method.

@article{
 title = {A cross-linked primer strategy for pigment encapsulation. 1. encapsulation of calcium carbonate by emulsion polymerization},
 type = {article},
 year = {2019},
 pages = {21130-21141},
 volume = {58},
 websites = {https://dx.doi.org/10.1021/acs.iecr.9b03841},
 month = {9},
 day = {18},
 id = {e3121278-5af0-30a1-b5a0-2952b08b9857},
 created = {2024-01-02T14:09:30.100Z},
 file_attached = {false},
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 last_modified = {2024-06-19T08:16:57.718Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
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 abstract = {We demonstrate a versatile method to encapsulate calcium carbonate particles with a shell of polymer by means of a conventional free radical emulsion polymerization process. Our strategy relies on the encapsulation of the pigment particles with a thin primer layer of cross-linked poly(acrylate). Starved-fed addition and emulsion polymerization of di(ethylene glycol) diacrylate and methacrylic acid, allows the uniform decoration of the pigment particles with the polymer primer shell. We demonstrate efficient encapsulation of calcium carbonate, from which we produce hollow particles upon calcium carbonate etching. The thickness of the polymer shell can easily be controlled, which we demonstrate with sequential seeded polymerization of methyl methacrylate under starved fed conditions.},
 bibtype = {article},
 author = {Roebuck, Holly S. and Bon, Stefan A. F.},
 doi = {10.1021/acs.iecr.9b03841},
 journal = {Industrial & Engineering Chemistry Research},
 number = {46}
}

We demonstrate a versatile method to encapsulate calcium carbonate particles with a shell of polymer by means of a conventional free radical emulsion polymerization process. Our strategy relies on the encapsulation of the pigment particles with a thin primer layer of cross-linked poly(acrylate). Starved-fed addition and emulsion polymerization of di(ethylene glycol) diacrylate and methacrylic acid, allows the uniform decoration of the pigment particles with the polymer primer shell. We demonstrate efficient encapsulation of calcium carbonate, from which we produce hollow particles upon calcium carbonate etching. The thickness of the polymer shell can easily be controlled, which we demonstrate with sequential seeded polymerization of methyl methacrylate under starved fed conditions.

@article{
 title = {Effect of the addition of salt to Pickering emulsion polymerizations using polymeric nanogels as stabilizer},
 type = {article},
 year = {2019},
 pages = {6600-6608},
 volume = {10},
 websites = {https://doi.org/10.1039/C9PY01240K},
 id = {d7113106-5698-3f53-bd3f-df48beda9343},
 created = {2024-01-02T14:09:30.410Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:30.410Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Nanogels made from crosslinked block copolymer micelles are used as stabilizers in the Pickering emulsion polymerization of styrene. The effect of the addition of salt, i.e. NaCl, on the emulsion polymerization is studied. It is shown that an increase in ionic strength of the dispersing medium in these polymerizations led to the formation of latexes of larger diameters. Along with an increase in size, the morphology of these polymer colloids changed from Janus to patchy with an increase in number of nanogels adsorbed on the polymer surface, as a function of the salt concentration in water. In particular, at the highest tested ionic strength, ca. 25 mM, fully armored polymeric particles surrounded by a dense layer of adsorbed stabilizing nanogels were formed. Kinetic studies carried out at varying NaCl concentrations suggested that particle formation in the reaction followed a combination of a coagulative nucleation mechanism, characterized by a clustering process of Janus precursors to form bigger aggregates, and droplet nucleation. Preliminary film formation studies on latexes made with n-butyl acrylate as comonomer indicated the potential of this technique for the production of coherent polymer films which included a substructure of functional nanogels.},
 bibtype = {article},
 author = {Lotierzo, Andrea and Meaney, Shane P. and Bon, Stefan A. F.},
 journal = {Polymer Chemistry}
}

Nanogels made from crosslinked block copolymer micelles are used as stabilizers in the Pickering emulsion polymerization of styrene. The effect of the addition of salt, i.e. NaCl, on the emulsion polymerization is studied. It is shown that an increase in ionic strength of the dispersing medium in these polymerizations led to the formation of latexes of larger diameters. Along with an increase in size, the morphology of these polymer colloids changed from Janus to patchy with an increase in number of nanogels adsorbed on the polymer surface, as a function of the salt concentration in water. In particular, at the highest tested ionic strength, ca. 25 mM, fully armored polymeric particles surrounded by a dense layer of adsorbed stabilizing nanogels were formed. Kinetic studies carried out at varying NaCl concentrations suggested that particle formation in the reaction followed a combination of a coagulative nucleation mechanism, characterized by a clustering process of Janus precursors to form bigger aggregates, and droplet nucleation. Preliminary film formation studies on latexes made with n-butyl acrylate as comonomer indicated the potential of this technique for the production of coherent polymer films which included a substructure of functional nanogels.

@article{
 title = {Effect of shearing stress on the radial heterogeneity and chromatographic performance of styrene-based polymerised high internal phase emulsions prepared in capillary format},
 type = {article},
 year = {2019},
 pages = {7301-7313},
 volume = {9},
 websites = {http://xlink.rsc.org/?DOI=C8RA06188B},
 month = {3},
 publisher = {The Royal Society of Chemistry},
 day = {1},
 id = {86dcd388-6212-300d-b338-aa2c518e51bd},
 created = {2024-01-02T14:09:30.623Z},
 accessed = {2019-03-08},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:50.721Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Poly(styrene-co-divinylbenzene) monoliths were prepared from the polymerisation of water-in-monomer high internal phase emulsions consisting of a 90 vol% internal phase and stabilised by the non-ionic surfactant Span 80®. The materials were prepared in capillary housings of various internal diameters ranging from 150 μm to 540 μm by simply passing the emulsion through the capillaries. When low shear (300 rpm) was used for emulsification, the droplet and resulting void size distributions were observed to shift towards lower values when the emulsions were forced through capillaries of internal diameter less than 540 μm and all columns exhibited significant radial heterogeneity. When high shear was employed (14 000 rpm) the resulting emulsions preserved their structure when forced through these capillaries and possessed narrower void size distributions with no obvious radial heterogeneity observed upon curing. This resulted in significantly improved chromatographic performance for the separation of a standard mixture of proteins when compared to the materials prepared under low shear.},
 bibtype = {article},
 author = {Desire, Christopher T. and Arrua, R. Dario and Mansour, Fotouh R. and Bon, Stefan A. F. and Hilder, Emily F.},
 doi = {10.1039/C8RA06188B},
 journal = {RSC Advances},
 number = {13}
}

Poly(styrene-co-divinylbenzene) monoliths were prepared from the polymerisation of water-in-monomer high internal phase emulsions consisting of a 90 vol% internal phase and stabilised by the non-ionic surfactant Span 80®. The materials were prepared in capillary housings of various internal diameters ranging from 150 μm to 540 μm by simply passing the emulsion through the capillaries. When low shear (300 rpm) was used for emulsification, the droplet and resulting void size distributions were observed to shift towards lower values when the emulsions were forced through capillaries of internal diameter less than 540 μm and all columns exhibited significant radial heterogeneity. When high shear was employed (14 000 rpm) the resulting emulsions preserved their structure when forced through these capillaries and possessed narrower void size distributions with no obvious radial heterogeneity observed upon curing. This resulted in significantly improved chromatographic performance for the separation of a standard mixture of proteins when compared to the materials prepared under low shear.

@article{
 title = {Synthesis of Janus and patchy particles using nanogels as stabilizers in emulsion polymerization},
 type = {article},
 year = {2019},
 pages = {399-407},
 volume = {13},
 websites = {http://dx.doi.org/10.1021/acsnano.8b06557},
 id = {e8ec87cf-b818-3490-b6de-5e11002d0ba5},
 created = {2024-01-02T14:09:30.804Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:50.857Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Polymer nanogels are used as colloidal stabilisers in emulsion polymerization. The nanogels were made by the covalent crosslinking of block copolymer micelles, the macromolecular building blocks of which were synthesized using a combination of catalytic chain transfer emulsion polymerization and reversible addition fragmentation chain-transfer (RAFT) of methacrylate monomers. The use of the nanogels in an emulsion polymerization led to anisotropic Janus and patchy colloids, where a latex particle was decorated by a number of patches on its surface. Control on the particle size and patch density was achieved by tailoring of the reaction conditions, such as varying the amount of nanogels, pH and salt concentration. Overall, the emulsion polymerization process in the presence of nanogels as stabilizers is shown to be a versatile and easily scalable route towards the fabrication of Janus and patchy polymer colloids.},
 bibtype = {article},
 author = {Lotierzo, Andrea and Longbottom, Brooke W. and Lee, Wai Hin and Bon, Stefan A. F.},
 journal = {ACS nano},
 number = {1}
}

Polymer nanogels are used as colloidal stabilisers in emulsion polymerization. The nanogels were made by the covalent crosslinking of block copolymer micelles, the macromolecular building blocks of which were synthesized using a combination of catalytic chain transfer emulsion polymerization and reversible addition fragmentation chain-transfer (RAFT) of methacrylate monomers. The use of the nanogels in an emulsion polymerization led to anisotropic Janus and patchy colloids, where a latex particle was decorated by a number of patches on its surface. Control on the particle size and patch density was achieved by tailoring of the reaction conditions, such as varying the amount of nanogels, pH and salt concentration. Overall, the emulsion polymerization process in the presence of nanogels as stabilizers is shown to be a versatile and easily scalable route towards the fabrication of Janus and patchy polymer colloids.

@article{
 title = {Colloidal particles at fluid interfaces: behaviour of isolated particles},
 type = {article},
 year = {2019},
 pages = {1186-1199},
 volume = {15},
 websites = {http://dx.doi.org/10.1039/C8SM02048E},
 id = {a9a564e3-d8ce-33cc-b428-aeae19da29df},
 created = {2024-01-02T14:09:30.972Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:51.001Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {The adsorption of colloidal particles to fluid interfaces is a phenomenon that is of interest to multiple disciplines across the physical and biological sciences. In this review we provide an entry level discussion of our current understanding on the physical principles involved and experimental observations of the adsorption of a single isolated particle to a liquid-liquid interface. We explore the effects that a variation of the morphology and surface chemistry of a particle can have on its ability to adhere to a liquid interface, from a thermodynamic as well as a kinetic perspective, and the impact of adsorption behaviour on potential applications. Finally, we discuss recent developments in the measurement of the interfacial behaviour of nanoparticles and highlight open questions for future research.},
 bibtype = {article},
 author = {Ballard, Nicholas and Law, Adam D. and Bon, Stefan A. F.},
 journal = {Soft Matter}
}

The adsorption of colloidal particles to fluid interfaces is a phenomenon that is of interest to multiple disciplines across the physical and biological sciences. In this review we provide an entry level discussion of our current understanding on the physical principles involved and experimental observations of the adsorption of a single isolated particle to a liquid-liquid interface. We explore the effects that a variation of the morphology and surface chemistry of a particle can have on its ability to adhere to a liquid interface, from a thermodynamic as well as a kinetic perspective, and the impact of adsorption behaviour on potential applications. Finally, we discuss recent developments in the measurement of the interfacial behaviour of nanoparticles and highlight open questions for future research.

@article{
 title = {Structure and behaviour of vesicles in presence of colloidal particles},
 type = {article},
 year = {2018},
 pages = {6949-6960},
 volume = {14},
 websites = {http://dx.doi.org/10.1039/C8SM01223G},
 id = {7a57e1e9-9acd-36aa-a525-f42adf48c59a},
 created = {2024-01-02T14:09:31.409Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:51.119Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {This review highlights recent studies that investigate the structural changes and behaviour of synthetic vesicles when they are exposed to colloidal particles. We will show examples to demonstrate the power of combining particles and vesicles in generating exciting supracolloidal structures. These suprastructures have a wide range of often responsive behaviours that take advantage of both the mechanical and morphological support provided by the vesicle and the associated particle with preset functionality. This review includes applications spanning a variety of disciplines, including chemistry, biology, physics and medicine.},
 bibtype = {article},
 author = {Jaggers, Ross W. and Bon, Stefan A. F.},
 journal = {Soft Matter}
}

This review highlights recent studies that investigate the structural changes and behaviour of synthetic vesicles when they are exposed to colloidal particles. We will show examples to demonstrate the power of combining particles and vesicles in generating exciting supracolloidal structures. These suprastructures have a wide range of often responsive behaviours that take advantage of both the mechanical and morphological support provided by the vesicle and the associated particle with preset functionality. This review includes applications spanning a variety of disciplines, including chemistry, biology, physics and medicine.

@article{
 title = {Robust open cellular porous polymer monoliths made from cured colloidal gels of latex particles},
 type = {article},
 year = {2018},
 pages = {2499-2511},
 volume = {20},
 websites = {http://dx.doi.org/10.1039/C8GC01055B},
 id = {6439c22b-20c8-3dd2-abd7-84ee477a6694},
 created = {2024-01-02T14:09:31.608Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:51.334Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {The coagulation of oppositely charged latexes prepared from the soap-free emulsion polymerisation of styrene using water as the reaction medium resulted in colloidal gels that were porous in nature and held together by electrostatic interactions. Chemical crosslinking, involving the introduction of a water-soluble crosslinker, resulted in stronger chemical bonds between particles affording a rigid porous material known as a monolith. It was found that, in a simpler approach these materials could be prepared using a single latex where the addition of ammonium persulfate both resulted in the formation of the colloidal gel and initiated the crosslinking process. The pore size of the resulting monoliths was predictable as this was observed to directly correlate to the particle diameter, with larger pores achieved using particles of increased size. All gels obtained in this work were highly mouldable and retained their shape, which allowed for a range of formats to be easily prepared without the requirement of a mould.},
 bibtype = {article},
 author = {Desire, Christopher and Lotierzo, Andrea and Arrua, R. Dario and Hilder, Emily F. and Bon, Stefan A. F.},
 doi = {10.1039/C8GC01055B},
 journal = {Green Chemistry}
}

The coagulation of oppositely charged latexes prepared from the soap-free emulsion polymerisation of styrene using water as the reaction medium resulted in colloidal gels that were porous in nature and held together by electrostatic interactions. Chemical crosslinking, involving the introduction of a water-soluble crosslinker, resulted in stronger chemical bonds between particles affording a rigid porous material known as a monolith. It was found that, in a simpler approach these materials could be prepared using a single latex where the addition of ammonium persulfate both resulted in the formation of the colloidal gel and initiated the crosslinking process. The pore size of the resulting monoliths was predictable as this was observed to directly correlate to the particle diameter, with larger pores achieved using particles of increased size. All gels obtained in this work were highly mouldable and retained their shape, which allowed for a range of formats to be easily prepared without the requirement of a mould.

@article{
 title = {Improving the engine power of a catalytic Janus-sphere micromotor by roughening its surface},
 type = {article},
 year = {2018},
 keywords = {Humanities and Social Sciences,Science,multidisciplinary},
 pages = {4622},
 volume = {8},
 websites = {http://www.nature.com/articles/s41598-018-22917-2},
 publisher = {Nature Publishing Group},
 id = {22473da5-ba8d-3da7-85af-e01e81ffda97},
 created = {2024-01-02T14:09:31.788Z},
 accessed = {2018-03-15},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:51.488Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Microspheres with catalytic caps have become a popular model system for studying self-propelled colloids. Existing experimental studies involve predominantly “smooth” particle surfaces. In this study we determine the effect of irregular surface deformations on the propulsive mechanism with a particular focus on speed. The particle surfaces of polymer microspheres were deformed prior to depositing a layer of platinum which resulted in the formation of nanoscopic pillars of catalyst. Self-propulsion was induced upon exposure of the micromotors to hydrogen peroxide, whilst they were dispersed in water. The topological surface features were shown to boost speed (~2×) when the underlying deformations are small (nanoscale), whilst large deformations afforded little difference despite a substantial apparent catalytic surface area. Colloids with deformed surfaces were more likely to display a mixture of rotational and translational propulsion than their “smooth” counterparts.},
 bibtype = {article},
 author = {Longbottom, Brooke W. and Bon, Stefan A. F.},
 doi = {10.1038/s41598-018-22917-2},
 journal = {Scientific Reports},
 number = {1}
}

Microspheres with catalytic caps have become a popular model system for studying self-propelled colloids. Existing experimental studies involve predominantly “smooth” particle surfaces. In this study we determine the effect of irregular surface deformations on the propulsive mechanism with a particular focus on speed. The particle surfaces of polymer microspheres were deformed prior to depositing a layer of platinum which resulted in the formation of nanoscopic pillars of catalyst. Self-propulsion was induced upon exposure of the micromotors to hydrogen peroxide, whilst they were dispersed in water. The topological surface features were shown to boost speed (~2×) when the underlying deformations are small (nanoscale), whilst large deformations afforded little difference despite a substantial apparent catalytic surface area. Colloids with deformed surfaces were more likely to display a mixture of rotational and translational propulsion than their “smooth” counterparts.

@article{
 title = {Preparation of highly interconnected hydrophilic polymers from emulsion templates with improved mechanical properties},
 type = {article},
 year = {2018},
 pages = {56-67},
 volume = {102},
 websites = {https://www.sciencedirect.com/science/article/pii/S001430571731649X},
 month = {2},
 publisher = {Pergamon},
 day = {6},
 id = {1eed9bb1-c7bc-36a8-a0aa-3539a0613aee},
 created = {2024-01-02T14:09:31.970Z},
 accessed = {2018-02-16},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:31.970Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Highly interconnected hydrophilic polymers were prepared through the polymerisation of (paraffin-oil)-in-water emulsion templates using internal phases below 74 vol%. These were stabilised by Tween 85 and contained acrylamide and N,N/-methylene bisacrylamide, as monomers, in the continuous water phase. The emulsification energy was increased, resulting in increased contact between emulsion droplets, allowing open cellular and highly interconnected structures to be achieved. This was coupled with a reduction in the internal phase volume allowing the obtainment of highly interconnected materials with excellent mechanical properties under compression, producing a Young’s modulus of 490 ± 90 MPa for a material with 36 ± 3% porosity. It was also found that the morphology of these materials could be altered through variations in the internal phase volume, the surfactant level and the emulsification energy. These porous polymers also possessed quite different behaviours in different solvent environments suggesting applications in controlled release or as rigid absorbents.},
 bibtype = {article},
 author = {Desire, Christopher T. and Khodabandeh, Aminreza and Schiller, Tara L. and Wilson, Russell and Dario Arrua, R. and Bon, Stefan A. F. and Hilder, Emily F.},
 doi = {10.1016/J.EURPOLYMJ.2018.02.002},
 journal = {European Polymer Journal}
}

Highly interconnected hydrophilic polymers were prepared through the polymerisation of (paraffin-oil)-in-water emulsion templates using internal phases below 74 vol%. These were stabilised by Tween 85 and contained acrylamide and N,N/-methylene bisacrylamide, as monomers, in the continuous water phase. The emulsification energy was increased, resulting in increased contact between emulsion droplets, allowing open cellular and highly interconnected structures to be achieved. This was coupled with a reduction in the internal phase volume allowing the obtainment of highly interconnected materials with excellent mechanical properties under compression, producing a Young’s modulus of 490 ± 90 MPa for a material with 36 ± 3% porosity. It was also found that the morphology of these materials could be altered through variations in the internal phase volume, the surfactant level and the emulsification energy. These porous polymers also possessed quite different behaviours in different solvent environments suggesting applications in controlled release or as rigid absorbents.

@article{
 title = {Improving the engine power of a catalytic Janus-sphere micromotor by roughening its surface},
 type = {article},
 year = {2017},
 websites = {http://dx.doi.org/10.26434/chemrxiv.5702659.v1},
 id = {9b035426-ae93-3a48-9f90-fc0b4b4ff7b1},
 created = {2024-01-02T14:09:32.149Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:32.149Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Microspheres with catalytic caps have become a popular model system for studying self- propelled colloids. Existing experimental studies involve predominantly “smooth” particle surfaces. In this study we determine the effect of irregular surface deformations on the propulsive mechanism with a particular focus on speed. The particle surfaces were deformed prior to depositing a catalytic layer which resulted in the formation of nanoscopic pillars of catalyst. These features were shown to boost speed (~2×) when the underlying surface deformations are small (nanoscale), whilst large deformations afforded little difference despite a substantial apparent catalytic surface area. Colloids with deformed surfaces were more likely to display a mixture of rotational and translational propulsion than their “smooth” counterparts.},
 bibtype = {article},
 author = {Longbottom, Brooke W and Bon, Stefan A F},
 doi = {10.26434/chemrxiv.5702659.v1},
 journal = {ChemRxiv}
}

Microspheres with catalytic caps have become a popular model system for studying self- propelled colloids. Existing experimental studies involve predominantly “smooth” particle surfaces. In this study we determine the effect of irregular surface deformations on the propulsive mechanism with a particular focus on speed. The particle surfaces were deformed prior to depositing a catalytic layer which resulted in the formation of nanoscopic pillars of catalyst. These features were shown to boost speed (~2×) when the underlying surface deformations are small (nanoscale), whilst large deformations afforded little difference despite a substantial apparent catalytic surface area. Colloids with deformed surfaces were more likely to display a mixture of rotational and translational propulsion than their “smooth” counterparts.

@article{
 title = {Toward sulfur-free RAFT Polymerization Induced Self-Assembly},
 type = {article},
 year = {2017},
 pages = {1438-1443},
 volume = {6},
 websites = {http://pubs.acs.org/doi/abs/10.1021/acsmacrolett.7b00857},
 publisher = {American Chemical Society},
 id = {a75f1cd7-1d66-3806-9080-2a40c97de287},
 created = {2024-01-02T14:09:32.328Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:51.617Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Polymerization induced self-assembly (PISA) using methacrylate-based macromonomers as RAFT agents is an unexplored, attractive route to make self-assembled colloidal objects. The use of this class of RAFT-agents in heterogeneous polymerizations is however not trivial, because of their inherent low reactivity. In this work we demonstrate that two obstacles need to be overcome, one being control of chain-growth (propagation), the other monomer partitioning. Batch dispersion polymerizations of hydroxypropyl methacrylate in the presence of poly(glycerol methacrylate) macromonomers in water showed limited control of chain-growth. Semicontinuous experiments whereby monomer was fed improved results only to some extent. Control of propagation is essential for PISA to allow for dynamic rearrangement of colloidal structures. We tackled the problem of monomer partitioning (caused by uncontrolled particle nucleation) by starting the polymerization with an amphiphilic thermoresponsive diblock copolymer, already “phase...},
 bibtype = {article},
 author = {Lotierzo, Andrea and Schofield, Ryan M. and Bon, Stefan A. F.},
 doi = {10.1021/acsmacrolett.7b00857},
 journal = {ACS Macro Letters}
}

Polymerization induced self-assembly (PISA) using methacrylate-based macromonomers as RAFT agents is an unexplored, attractive route to make self-assembled colloidal objects. The use of this class of RAFT-agents in heterogeneous polymerizations is however not trivial, because of their inherent low reactivity. In this work we demonstrate that two obstacles need to be overcome, one being control of chain-growth (propagation), the other monomer partitioning. Batch dispersion polymerizations of hydroxypropyl methacrylate in the presence of poly(glycerol methacrylate) macromonomers in water showed limited control of chain-growth. Semicontinuous experiments whereby monomer was fed improved results only to some extent. Control of propagation is essential for PISA to allow for dynamic rearrangement of colloidal structures. We tackled the problem of monomer partitioning (caused by uncontrolled particle nucleation) by starting the polymerization with an amphiphilic thermoresponsive diblock copolymer, already “phase...

@article{
 title = {Communication between hydrogel beads via chemical signalling},
 type = {article},
 year = {2017},
 pages = {8681-8685},
 volume = {5},
 websites = {http://dx.doi.org/10.1039/C7TB02278F},
 id = {6762ab29-8559-354f-80a5-65fcf22151da},
 created = {2024-01-02T14:09:32.511Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:51.783Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {In this work, we demonstrate chemical communication between millimetre-sized soft hydrogel beads in an aqueous environment. Silver cations (Ag+) and the Ag+ chelator dithiothreitol (DTT) are used as signalling molecules. By exploiting their interplay, we conduct a series of ‘conversations’ between millimetre-sized beads. The communication process is monitored by tracking the response and behaviour of a central bead. This bead is loaded with the enzyme urease and has the ability to undergo a change in colour associated with a change in pH. Competitive communication between three beads, whereby the central bead receives two competing signals from two senders, is shown. We believe that our hydrogel-based system demonstrates an advance in the communication capabilities of small soft matter objects.},
 bibtype = {article},
 author = {Jaggers, Ross W and Bon, Stefan A F},
 doi = {10.1039/C7TB02278F},
 journal = {J. Mater. Chem. B}
}

In this work, we demonstrate chemical communication between millimetre-sized soft hydrogel beads in an aqueous environment. Silver cations (Ag+) and the Ag+ chelator dithiothreitol (DTT) are used as signalling molecules. By exploiting their interplay, we conduct a series of ‘conversations’ between millimetre-sized beads. The communication process is monitored by tracking the response and behaviour of a central bead. This bead is loaded with the enzyme urease and has the ability to undergo a change in colour associated with a change in pH. Competitive communication between three beads, whereby the central bead receives two competing signals from two senders, is shown. We believe that our hydrogel-based system demonstrates an advance in the communication capabilities of small soft matter objects.

@article{
 title = {Temporal and spatial programming in soft composite hydrogel objects},
 type = {article},
 year = {2017},
 pages = {7491-7495},
 volume = {5},
 websites = {http://xlink.rsc.org/?DOI=C7TB02011B},
 id = {0cc96501-d57d-34be-9259-f6f4b0d1b7c8},
 created = {2024-01-02T14:09:32.693Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:52.011Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {A spatial and temporal response of hydrogel objects is demonstrated using an enzyme as a programming tool.},
 bibtype = {article},
 author = {Jaggers, Ross W. and Bon, Stefan A. F.},
 doi = {10.1039/C7TB02011B},
 journal = {J. Mater. Chem. B}
}

A spatial and temporal response of hydrogel objects is demonstrated using an enzyme as a programming tool.

@article{
 title = {Synthesis and properties of polyesters from waste grapeseed oil: comparison with soybean and rapeseed oils},
 type = {article},
 year = {2017},
 keywords = {Crosslink density,Grapeseed oil,Mechanical properties,Polyester networks,Thermal properties},
 pages = {1-10},
 volume = {25},
 websites = {http://link.springer.com/10.1007/s10924-016-0883-3},
 month = {3},
 publisher = {Springer US},
 day = {22},
 id = {d6a1e97f-52c4-35e2-bcb3-1d0ac881d368},
 created = {2024-01-02T14:09:32.869Z},
 accessed = {2017-03-22},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:52.141Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. Tg’s of the polyesters ranged from −36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher Tg polymers (−17 to 17 °C) than soybean (−25 to 6 °C) and rapeseed (−36 to −27 °C). Grapeseed oil showed similar properties to soybean oil in terms of Tg, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.},
 bibtype = {article},
 author = {Clark, A. J. and Ross, A. H. and Bon, S. A. F.},
 doi = {10.1007/s10924-016-0883-3},
 journal = {Journal of Polymers and the Environment},
 number = {1}
}

The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. Tg’s of the polyesters ranged from −36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher Tg polymers (−17 to 17 °C) than soybean (−25 to 6 °C) and rapeseed (−36 to −27 °C). Grapeseed oil showed similar properties to soybean oil in terms of Tg, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.

@article{
 title = {Roughening up polymer microspheres and their diffusion in a liquid},
 type = {article},
 year = {2017},
 pages = {4285-4293},
 volume = {13},
 websites = {http://dx.doi.org/10.1039/C7SM00589J},
 id = {afa8387b-265e-3435-8da6-7bf9c3440175},
 created = {2024-01-02T14:09:33.051Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:52.262Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {A simple, versatile approach for the roughening of polymer microparticle surfaces via a deformation technique in the presence of an inorganic matrix is presented here. The process consists of straightforward steps: 1. Preparation of a bi-composite colloidal sol i.e. polymer particles + inorganic particles dispersed in a liquid, 2. Drying of the mixture onto a suitable hard substrate, 3. Heating the dried film above the glass transition temperature of the polymer, and 4. Re-dispersion and chemical etching of the inorganic medium. The primary driver is capillary imbibition of the polymer melt into the inorganic colloidal template. 2D particle tracking probes the diffusional behaviour of the roughened objects in comparison with their smooth precursors. We show that, despite large scale roughness (up to 10 % asperity size with respect to particle diameter), Stokes law is obeyed and the particles motion can be modelled simply with the Einstein-Stokes-Sutherland relation.},
 bibtype = {article},
 author = {Longbottom, Brooke W and Somuncuoglu, Birsen and Punter, Jacob and Longbottom, Sarah and Bon, Stefan A F},
 doi = {10.1039/C7SM00589J},
 journal = {Soft Matter}
}

A simple, versatile approach for the roughening of polymer microparticle surfaces via a deformation technique in the presence of an inorganic matrix is presented here. The process consists of straightforward steps: 1. Preparation of a bi-composite colloidal sol i.e. polymer particles + inorganic particles dispersed in a liquid, 2. Drying of the mixture onto a suitable hard substrate, 3. Heating the dried film above the glass transition temperature of the polymer, and 4. Re-dispersion and chemical etching of the inorganic medium. The primary driver is capillary imbibition of the polymer melt into the inorganic colloidal template. 2D particle tracking probes the diffusional behaviour of the roughened objects in comparison with their smooth precursors. We show that, despite large scale roughness (up to 10 % asperity size with respect to particle diameter), Stokes law is obeyed and the particles motion can be modelled simply with the Einstein-Stokes-Sutherland relation.

@article{
 title = {Independent responsive behaviour and communication in hydrogel objects},
 type = {article},
 year = {2017},
 pages = {402-407},
 volume = {4},
 websites = {http://xlink.rsc.org/?DOI=C7MH00033B},
 id = {753a802b-187d-3da2-be94-c1fb5c10f472},
 created = {2024-01-02T14:09:33.238Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:52.387Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {In this work, we show the fabrication of soft hydrogel alginate-based objects, namely fibres and beads, that have an individually programmed time delay in their response to a shared environmental stimulus. We utilize the enzyme urease to programme a self-regulated change in pH, which in turn activates the designed response of gel fibre disintegration or a change in gel bead colour. This design allows for independent response behaviour of a collection of bodies in a single closed system, as well as inter-material communication on shorter length scales. The incorporation of responsive time control directly into soft matter objects demonstrates an advance in the field of autonomous materials.},
 bibtype = {article},
 author = {Jaggers, Ross W. and Bon, Stefan A. F.},
 doi = {10.1039/C7MH00033B},
 journal = {Mater. Horiz.},
 number = {3}
}

In this work, we show the fabrication of soft hydrogel alginate-based objects, namely fibres and beads, that have an individually programmed time delay in their response to a shared environmental stimulus. We utilize the enzyme urease to programme a self-regulated change in pH, which in turn activates the designed response of gel fibre disintegration or a change in gel bead colour. This design allows for independent response behaviour of a collection of bodies in a single closed system, as well as inter-material communication on shorter length scales. The incorporation of responsive time control directly into soft matter objects demonstrates an advance in the field of autonomous materials.

@article{
 title = {A mechanistic investigation of Pickering emulsion polymerization},
 type = {article},
 year = {2017},
 pages = {5100-5111},
 volume = {8},
 websites = {http://pubs.rsc.org/en/content/articlelanding/2017/py/c7py00308k#!divAbstract},
 id = {cb37b575-ea63-3773-a630-3b4c097ed9af},
 created = {2024-01-02T14:09:33.430Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:53.171Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {Pickering emulsion polymerization offers a versatile way of synthetising hybrid core-shell latexes where a polymer core is surrounded by an armour of inorganic nanoparticles. A mechanistic understanding of the polymerization process is limited which restricts the use of the technique in the fabrication of more complex, multilayered colloids. In this paper clarity is provided through an in-depth investigation into the Pickering emulsion polymerization of methyl methacrylate (MMA) in the presence of nano-sized colloidal silica (Ludox TM-40). Mechanistic insights are discussed by studying both the adsorption of the stabiliser at the surface of the latex particles and polymerization kinetics. The adhesion of the Pickering nanoparticles was found not to be spontaneous, as confirmed by cryo-TEM analysis of MMA droplets in water and monomer-swollen PMMA latexes. This supports the theory that the inorganic particles are driven towards the interface as a result of a heterocoagulation event in the water phase with a growing oligoradical. The emulsion polymerizations were monitored by reaction calorimetry in order to establish accurate values for monomer conversion and the overall rate of polymerizations (RP). RP increased for higher initial silica concentrations and the polymerizations were found to follow pseudo-bulk kinetics},
 bibtype = {article},
 author = {Lotierzo, Andrea and Bon, Stefan A F},
 doi = {10.1039/C7PY00308K},
 journal = {Polymer Chemistry}
}

Pickering emulsion polymerization offers a versatile way of synthetising hybrid core-shell latexes where a polymer core is surrounded by an armour of inorganic nanoparticles. A mechanistic understanding of the polymerization process is limited which restricts the use of the technique in the fabrication of more complex, multilayered colloids. In this paper clarity is provided through an in-depth investigation into the Pickering emulsion polymerization of methyl methacrylate (MMA) in the presence of nano-sized colloidal silica (Ludox TM-40). Mechanistic insights are discussed by studying both the adsorption of the stabiliser at the surface of the latex particles and polymerization kinetics. The adhesion of the Pickering nanoparticles was found not to be spontaneous, as confirmed by cryo-TEM analysis of MMA droplets in water and monomer-swollen PMMA latexes. This supports the theory that the inorganic particles are driven towards the interface as a result of a heterocoagulation event in the water phase with a growing oligoradical. The emulsion polymerizations were monitored by reaction calorimetry in order to establish accurate values for monomer conversion and the overall rate of polymerizations (RP). RP increased for higher initial silica concentrations and the polymerizations were found to follow pseudo-bulk kinetics

@article{
 title = {Selecting phthalocyanine polymorphs using local chemical termination variations in copper iodide},
 type = {article},
 year = {2016},
 pages = {4448-4452},
 volume = {120},
 websites = {http://dx.doi.org/10.1021/acs.jpcc.6b00354},
 month = {2},
 publisher = {American Chemical Society},
 day = {6},
 id = {a406b63f-e8d0-3ee2-85f6-b341fe61a882},
 created = {2024-01-02T14:09:33.619Z},
 accessed = {2016-02-07},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:17:34.552Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Ramadan2016},
 private_publication = {false},
 abstract = {Copper(I) iodide (CuI) thin films are employed as a structural templating layer for the growth of metal-free phthalocyanine (H2Pc) thin films. Structural polymorphs are observed in X-ray diffraction patterns when microcrystalline CuI films exhibiting copper and iodine terminated grains are used. Each polymorph is nucleated from a single termination, and distinctive crystallite morphologies are observed for each.},
 bibtype = {article},
 author = {Ramadan, A. J. and Hancox, I. and Huband, S. and Parkins, C. C. and Bon, S. A.F. and Walker, M. and Fearn, S. and McConville, C. F. and Jones, T. S. and Rochford, L. A.},
 doi = {10.1021/acs.jpcc.6b00354},
 journal = {Journal of Physical Chemistry C},
 number = {8}
}

Copper(I) iodide (CuI) thin films are employed as a structural templating layer for the growth of metal-free phthalocyanine (H2Pc) thin films. Structural polymorphs are observed in X-ray diffraction patterns when microcrystalline CuI films exhibiting copper and iodine terminated grains are used. Each polymorph is nucleated from a single termination, and distinctive crystallite morphologies are observed for each.

@article{
 title = {Preparation of inverse polymerized high internal phase emulsions using an amphiphilic macro-RAFT agent as sole stabilizer},
 type = {article},
 year = {2016},
 pages = {1803-1812},
 websites = {http://pubs.rsc.org/en/Content/ArticleLanding/2016/PY/C5PY02012C},
 month = {1},
 publisher = {The Royal Society of Chemistry},
 day = {26},
 id = {cabe7543-5d39-3664-bbec-92ec21063472},
 created = {2024-01-02T14:09:33.810Z},
 accessed = {2016-01-27},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:33.810Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Khodabandeh2016},
 language = {en},
 private_publication = {false},
 abstract = {Oil-in-water (‘inverse’) High Internal Phase Emulsions (HIPEs) have been prepared using an amphiphilic macro-RAFT agent with toluene as the internal dispersed phase (~80 vol%) and an aqueous monomer solution as the continuous phase. The water phase consisted of the monomers acrylamide (AM) and N,N'-methylenebisacrylamide (MBAM), an initiator as well as the amphiphilic macro-RAFT agent, that is 2-(butylthiocarbonothioylthio)-2-poly(n-butyl acrylate)-b-poly(acrylic acid), which was used as an anionic polymeric surfactant. The presence of these amphiphilic species allowed the successful preparation of a polyHIPE upon polymerization. The effect of concentration of macro-RAFT agent, pH, initiator, hexadecane as an organic modifier and the polymerization temperature on the morphology of the resulting porous materials was investigated. Varying the lengths of the hydrophilic and hydrophobic blocks of the macro-RAFT agent resulted in polyHIPEs with different porous structures. The presence of RAFT functionality in the polyHIPE was confirmed by elemental analysis, EDX-SEM, Raman and FT-IR spectroscopies. Raman mapping revealed full coverage of the void walls with dithiocarbamate groups.},
 bibtype = {article},
 author = {Khodabandeh, Aminreza and Arrua, R. Dario and Desire, Christopher and Rodemann, Thomas and Bon, Stefan A. F. and Thickett, Stuart Craig and Hilder, Emily},
 doi = {10.1039/C5PY02012C},
 journal = {Polym. Chem.}
}

Oil-in-water (‘inverse’) High Internal Phase Emulsions (HIPEs) have been prepared using an amphiphilic macro-RAFT agent with toluene as the internal dispersed phase (~80 vol%) and an aqueous monomer solution as the continuous phase. The water phase consisted of the monomers acrylamide (AM) and N,N'-methylenebisacrylamide (MBAM), an initiator as well as the amphiphilic macro-RAFT agent, that is 2-(butylthiocarbonothioylthio)-2-poly(n-butyl acrylate)-b-poly(acrylic acid), which was used as an anionic polymeric surfactant. The presence of these amphiphilic species allowed the successful preparation of a polyHIPE upon polymerization. The effect of concentration of macro-RAFT agent, pH, initiator, hexadecane as an organic modifier and the polymerization temperature on the morphology of the resulting porous materials was investigated. Varying the lengths of the hydrophilic and hydrophobic blocks of the macro-RAFT agent resulted in polyHIPEs with different porous structures. The presence of RAFT functionality in the polyHIPE was confirmed by elemental analysis, EDX-SEM, Raman and FT-IR spectroscopies. Raman mapping revealed full coverage of the void walls with dithiocarbamate groups.

@article{
 title = {Control of vesicle membrane permeability with catalytic particles},
 type = {article},
 year = {2016},
 pages = {41-46},
 volume = {3},
 websites = {http://pubs.rsc.org/en/content/articlehtml/2016/mh/c5mh00093a},
 publisher = {Royal Society of Chemistry},
 id = {8ec85342-d727-3e7e-aab1-18a260b002a5},
 created = {2024-01-02T14:09:39.292Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:53.291Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {jaggers2016control},
 source_type = {article},
 private_publication = {false},
 abstract = {Giant polymer vesicles which have membrane-embedded catalytically active manganese oxide particles are made using droplet-based microfluidics. It is demonstrated that these colloidal particles can regulate the membrane permeability of the polymersomes upon their exposure to, and catalytic reaction with, small amounts of dissolved hydrogen peroxide.},
 bibtype = {article},
 author = {Jaggers, Ross W. and Chen, Rong and Bon, Stefan A. F.},
 doi = {10.1039/C5MH00093A},
 journal = {Mater. Horiz.},
 number = {1}
}

Giant polymer vesicles which have membrane-embedded catalytically active manganese oxide particles are made using droplet-based microfluidics. It is demonstrated that these colloidal particles can regulate the membrane permeability of the polymersomes upon their exposure to, and catalytic reaction with, small amounts of dissolved hydrogen peroxide.

@article{
 title = {Assembly of emulsion droplets into fibers by microfluidic wet spinning},
 type = {article},
 year = {2016},
 pages = {813-818},
 volume = {4},
 websites = {http://xlink.rsc.org/?DOI=C5TA08917D},
 publisher = {Royal Society of Chemistry},
 id = {ef57ecdd-193a-38aa-81ba-c7cead4d9cb3},
 created = {2024-01-02T14:09:44.583Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:53.756Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bell2015assembly},
 source_type = {article},
 private_publication = {false},
 abstract = {<p>Emulsion droplets stabilized by branched copolymers and nano-sized clay are assembled into fibers using a microfluidic wet spinning process.</p>},
 bibtype = {article},
 author = {Bell, Robert V. and Parkins, Christopher C. and Young, Robert A. and Preuss, Corinna M. and Stevens, Molly M. and Bon, Stefan A. F.},
 doi = {10.1039/C5TA08917D},
 journal = {J. Mater. Chem. A},
 number = {3}
}

Emulsion droplets stabilized by branched copolymers and nano-sized clay are assembled into fibers using a microfluidic wet spinning process.

@misc{
 title = {Pickering emulsion polymerization},
 type = {misc},
 year = {2015},
 source = {Encyclopedia of Polymeric Nanomaterials},
 pages = {1634-1639},
 websites = {http://link.springer.com/10.1007/978-3-642-29648-2_264},
 publisher = {Springer Berlin Heidelberg},
 id = {7fa0c1dc-da6d-3065-9d51-a2616d9d6f2c},
 created = {2024-01-02T14:09:33.978Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:17:48.868Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon2015pickering},
 source_type = {article},
 private_publication = {false},
 bibtype = {misc},
 author = {Bon, Stefan A. F.},
 doi = {10.1007/978-3-642-29648-2_264}
}

@inproceedings{
 title = {Balanced nanocomposite thermosetting materials for HVDC and AC applications},
 type = {inproceedings},
 year = {2015},
 keywords = {Epoxy Resin,HVA C,HVDC,Nanocomposite,Nanodielectric,Power Transmission},
 pages = {193-196},
 websites = {http://ieeexplore.ieee.org/xpl/login.jsp?tp=&arnumber=7223516&url=http%3A%2F%2Fieeexplore.ieee.org%2Fxpls%2Fabs_all.jsp%3Farnumber%3D7223516},
 institution = {IEEE},
 id = {df73b190-7818-3553-9227-3bcbb25199b6},
 created = {2024-01-02T14:09:38.354Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:38.354Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {stevens2015balanced},
 source_type = {inproceedings},
 private_publication = {false},
 abstract = {Email Print Request Permissions There is a need to develop materials with controlled electrical resistivity, reduced space charge accumulation, higher thermal conductivity, higher dielectric strength and enhanced voltage endurance to cope with DC stresses in High Voltage Direct Current (HVDC) transmission systems in addition to HVAC requirements. If the balance of properties, performance and process requirements are achieved this may lead to HVDC insulation systems and equipment having a reduced footprint, larger power densities, and greater multi-stress resilience with longer service lifetimes. It reports findings of a project that is engaging this challenge and investigates the development and scaling of new thermoset based nanocomposite electrical insulation materials for HVDC power transmission applications. Some of the results such as increased electrical breakdown strength and reduced electrical conductivity for reactively surface functionalised nanosilica, and increased thermal conductivity for nano boron nitride and their significance in regard to the wider application of these electrical insulation materials are also discussed. With sufficient understanding of these properties, their trade-offs and process requirements it is possible to tailor balanced materials for specific use in HVAC or HVDC components.},
 bibtype = {inproceedings},
 author = {Stevens, G. C. and Freebody, N. A. and Vaughan, A. S. and Virtanen, S. and Hyde, A. and Perrot, F. and Szkoda-Giannaki, I. and Baker, P. and Bon, S. A.F. and Coles, S. R. and Medlam, J. A.},
 doi = {10.1109/ICACACT.2014.7223516},
 booktitle = {33rd Electrical Insulation Conference, EIC 2015}
}

Email Print Request Permissions There is a need to develop materials with controlled electrical resistivity, reduced space charge accumulation, higher thermal conductivity, higher dielectric strength and enhanced voltage endurance to cope with DC stresses in High Voltage Direct Current (HVDC) transmission systems in addition to HVAC requirements. If the balance of properties, performance and process requirements are achieved this may lead to HVDC insulation systems and equipment having a reduced footprint, larger power densities, and greater multi-stress resilience with longer service lifetimes. It reports findings of a project that is engaging this challenge and investigates the development and scaling of new thermoset based nanocomposite electrical insulation materials for HVDC power transmission applications. Some of the results such as increased electrical breakdown strength and reduced electrical conductivity for reactively surface functionalised nanosilica, and increased thermal conductivity for nano boron nitride and their significance in regard to the wider application of these electrical insulation materials are also discussed. With sufficient understanding of these properties, their trade-offs and process requirements it is possible to tailor balanced materials for specific use in HVAC or HVDC components.

@book{
 title = {Particle-Stabilized Emulsions and Colloids: Formation And Applications},
 type = {book},
 year = {2015},
 websites = {http://pubs.rsc.org/en/content/ebook/978-1-84973-881-1},
 publisher = {Royal Society of Chemistry},
 id = {e74b5719-583e-356d-988a-41de4ba50b02},
 created = {2024-01-02T14:09:38.536Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:38.536Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ngai2015particle},
 source_type = {book},
 private_publication = {false},
 abstract = {There has been much scientific interest in the behaviour of colloidal particles at liquid interfaces. From a research aspect they provide model systems for fundamental studies of condensed matter physics. From a commercial aspect they provide applications for making new materials in the cosmetics, food and paint industries.In many cases of colloidal particles at interfaces, the mechanism of particle interactions is still unknown. Particle-Stabilized Emulsions and Colloids looks at recent studies on the behaviour of particles at liquid interfaces. The book first introduces the basic concepts and principles of colloidal particles at liquid-liquid interfaces including the interactions and conformations. The book then discusses the latest advances in emulsions and bicontinuous emulsions stabilized by both solid and soft particles and finally the book covers applications in food science and oil extraction.With contributions from leading experts in these fields, this book will provide a background to academic researchers, engineers, and graduate students in chemistry, physics and materials science. The commercial aspects will also be of interest to those working in the cosmetics, food and oil industry.},
 bibtype = {book},
 author = {Ngai, To and Bon, Stefan A F},
 editor = {Ngai, To and Bon, Stefan A F},
 doi = {10.1039/9781782620143}
}

There has been much scientific interest in the behaviour of colloidal particles at liquid interfaces. From a research aspect they provide model systems for fundamental studies of condensed matter physics. From a commercial aspect they provide applications for making new materials in the cosmetics, food and paint industries.In many cases of colloidal particles at interfaces, the mechanism of particle interactions is still unknown. Particle-Stabilized Emulsions and Colloids looks at recent studies on the behaviour of particles at liquid interfaces. The book first introduces the basic concepts and principles of colloidal particles at liquid-liquid interfaces including the interactions and conformations. The book then discusses the latest advances in emulsions and bicontinuous emulsions stabilized by both solid and soft particles and finally the book covers applications in food science and oil extraction.With contributions from leading experts in these fields, this book will provide a background to academic researchers, engineers, and graduate students in chemistry, physics and materials science. The commercial aspects will also be of interest to those working in the cosmetics, food and oil industry.

@article{
 title = {Nanoscale hybrid silica/polymer Janus particles with a double-responsive hemicorona},
 type = {article},
 year = {2015},
 keywords = {Hybrid particles,Janus particles,Pickering emulsion,Stimuli-responsive nanoparticles},
 pages = {299-308},
 volume = {79},
 websites = {http://www.sciencedirect.com/science/article/pii/S0032386115303086},
 publisher = {Elsevier},
 id = {d0a3ff56-d40e-38d5-b342-6e254260e409},
 created = {2024-01-02T14:09:39.490Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:39.490Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ruhland2015nanoscale},
 source_type = {article},
 private_publication = {false},
 abstract = {We report a versatile large-scale synthesis strategy for hybrid Janus nanoparticles with a silica core and a unilaterally attached polymer corona in a size range below 100 nm. The stimuli-responsive behavior of these nanoparticles with a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) hemicorona is investigated. The synthesis is based on a modified version of the Pickering emulsion polymerization technique in combination with surface-initiated atom transfer radical polymerization (ATRP) in a "grafting from" approach. In a first step, poly(vinyl acetate) (PVAc) latex particles are prepared via Pickering emulsion polymerization. Colloidal stability is provided by 30 nm silica nanoparticles that adhere to the surface of the growing polymer particles. This results in polymer latexes which are armored with a layer of tightly immobilized nanoparticles, one side of which is immersed in the polymer particle and thus protected. After modification of the exposed side of the particles through chemisorption of an ATRP initiator, that is (2-bromo-2-methyl)propionyl-oxyhexyltriethoxysilane, and the removal of the particles from the interface, PDMAEMA chains are grown from this modified side of the silica particles, yielding well-defined Janus nanoparticles with a stimuli-responsive PDMAEMA hemicorona. Transmission and scanning electron microscopy, dynamic light scattering, thermogravimetric analysis and turbidity measurements were used to characterize the Janus particles. Most importantly, this synthetic approach is easily scalable and can be amended to furnish a wide range of nanoscale hybrid Janus particles. Furthermore, we demonstrate reversible switching behavior upon pH and temperature changes and find a peculiar self-assembly behavior of the Janus particles into linear strings at low pH and high concentration.},
 bibtype = {article},
 author = {Ruhland, Thomas M. and McKenzie, Holly S. and Skelhon, Thomas S. and Bon, Stefan A F and Walther, Andreas and M??ller, Axel H E},
 doi = {10.1016/j.polymer.2015.10.022},
 journal = {Polymer}
}

We report a versatile large-scale synthesis strategy for hybrid Janus nanoparticles with a silica core and a unilaterally attached polymer corona in a size range below 100 nm. The stimuli-responsive behavior of these nanoparticles with a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) hemicorona is investigated. The synthesis is based on a modified version of the Pickering emulsion polymerization technique in combination with surface-initiated atom transfer radical polymerization (ATRP) in a "grafting from" approach. In a first step, poly(vinyl acetate) (PVAc) latex particles are prepared via Pickering emulsion polymerization. Colloidal stability is provided by 30 nm silica nanoparticles that adhere to the surface of the growing polymer particles. This results in polymer latexes which are armored with a layer of tightly immobilized nanoparticles, one side of which is immersed in the polymer particle and thus protected. After modification of the exposed side of the particles through chemisorption of an ATRP initiator, that is (2-bromo-2-methyl)propionyl-oxyhexyltriethoxysilane, and the removal of the particles from the interface, PDMAEMA chains are grown from this modified side of the silica particles, yielding well-defined Janus nanoparticles with a stimuli-responsive PDMAEMA hemicorona. Transmission and scanning electron microscopy, dynamic light scattering, thermogravimetric analysis and turbidity measurements were used to characterize the Janus particles. Most importantly, this synthetic approach is easily scalable and can be amended to furnish a wide range of nanoscale hybrid Janus particles. Furthermore, we demonstrate reversible switching behavior upon pH and temperature changes and find a peculiar self-assembly behavior of the Janus particles into linear strings at low pH and high concentration.

@inbook{
 type = {inbook},
 year = {2015},
 pages = {1-7},
 websites = {http://pubs.rsc.org/en/content/chapter/bk9781849738811-00001/978-1-84973-881-1},
 publisher = {Royal Society of Chemistry},
 chapter = {CHAPTER 1. The Phenomenon of Pickering Stabilization: A Basic Introduction},
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 author = {Bon, Stefan Antonius Franciscus},
 editor = {Ngai, To and Bon, Stefan A F},
 doi = {10.1039/9781782620143-00001},
 title = {Particle-Stabilized Emulsions and Colloids: Formation and Applications}
}

@article{
 title = {Mechanistic insight into the synthesis of silica-based "matchstick" colloids},
 type = {article},
 year = {2015},
 pages = {9017-9025},
 volume = {31},
 websites = {http://pubs.acs.org/doi/abs/10.1021/acs.langmuir.5b02645},
 publisher = {American Chemical Society},
 id = {abfcd041-657a-3e08-8332-0dbeae5f195e},
 created = {2024-01-02T14:09:42.511Z},
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 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-06-19T08:18:11.322Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {longbottom2015mechanistic},
 source_type = {article},
 private_publication = {false},
 abstract = {We report an insight into the synthesis of silica-based “matchstick”-shaped colloidal particles, which are of interest in the area of self-propulsion on small length scales. The generation of aqueous emulsion droplets dispersed in an n-pentanol-rich continuous phase and their use as reaction centers allows for the fabrication of siliceous microparticles that exhibit anisotropy in both particle morphology, that is, a “matchstick” shape, and chemistry, that is, a transition-metal oxide-enriched head. We provide a series of kinetic studies to gain a mechanistic understanding and unravel the particle formation and growth processes. Additionally, we demonstrate the ability to select the aspect ratio of the “matchstick” particle in a straightforward manner.},
 bibtype = {article},
 author = {Longbottom, Brooke W. and Rochford, Luke A. and Beanland, Richard and Bon, Stefan A F},
 doi = {10.1021/acs.langmuir.5b02645},
 journal = {Langmuir},
 number = {33}
}

We report an insight into the synthesis of silica-based “matchstick”-shaped colloidal particles, which are of interest in the area of self-propulsion on small length scales. The generation of aqueous emulsion droplets dispersed in an n-pentanol-rich continuous phase and their use as reaction centers allows for the fabrication of siliceous microparticles that exhibit anisotropy in both particle morphology, that is, a “matchstick” shape, and chemistry, that is, a transition-metal oxide-enriched head. We provide a series of kinetic studies to gain a mechanistic understanding and unravel the particle formation and growth processes. Additionally, we demonstrate the ability to select the aspect ratio of the “matchstick” particle in a straightforward manner.

@article{
 title = {Fabrication of calcium phosphate microcapsules using emulsion droplets stabilized with branched copolymers as templates},
 type = {article},
 year = {2015},
 pages = {5544-5552},
 volume = {3},
 websites = {http://dx.doi.org/10.1039/C5TB00893J},
 publisher = {Royal Society of Chemistry},
 id = {4e1455eb-97be-3e1d-9eff-5b9b7aa8f0ca},
 created = {2024-01-02T14:09:42.703Z},
 file_attached = {true},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:53.409Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bell2015fabrication},
 source_type = {article},
 private_publication = {false},
 abstract = {We report on a versatile and time-efficient method to fabricate calcium phosphate (CaP) microcapsules by utilizing oil-in-water emulsion droplets stabilized with synthetic branched copolymer (BCP) as templates. The BCP was designed to provide a suitable architecture and functionality to produce stable emulsion droplets, and to permit the mineralization of CaP at the surface of the oil droplet when incubated in a solution containing calcium and phosphate ions. The CaP shells of the microcapsules were established to be calcium deficient hydroxyapatite with incorporated chlorine and carbonate species. These capsule walls were made fluorescent by decoration with a fluorescein–bisphosphonate conjugate.},
 bibtype = {article},
 author = {Bell, Robert V and Rochford, Luke A and De Rosales, Rafael T M and Stevens, Molly and Weaver, Jonathan V M and Bon, Stefan A F},
 doi = {10.1039/c5tb00893j},
 journal = {Journal of Materials Chemistry B},
 number = {3}
}

We report on a versatile and time-efficient method to fabricate calcium phosphate (CaP) microcapsules by utilizing oil-in-water emulsion droplets stabilized with synthetic branched copolymer (BCP) as templates. The BCP was designed to provide a suitable architecture and functionality to produce stable emulsion droplets, and to permit the mineralization of CaP at the surface of the oil droplet when incubated in a solution containing calcium and phosphate ions. The CaP shells of the microcapsules were established to be calcium deficient hydroxyapatite with incorporated chlorine and carbonate species. These capsule walls were made fluorescent by decoration with a fluorescein–bisphosphonate conjugate.

@article{
 title = {Equilibrium orientations of non-spherical and chemically anisotropic particles at liquid-liquid interfaces and the effect on emulsion stability},
 type = {article},
 year = {2015},
 keywords = {Interfacial adsorption,Janus particle,Pickering},
 pages = {533-544},
 volume = {448},
 websites = {http://www.sciencedirect.com/science/article/pii/S0021979715002453},
 publisher = {Academic Press},
 id = {55319206-08ea-315e-8200-863115655a85},
 created = {2024-01-02T14:09:43.474Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:43.474Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ballard2015equilibrium},
 source_type = {article},
 private_publication = {false},
 abstract = {The effective stabilization of emulsions by solid particles, a phenomenon known as Pickering stabilization, is well known to be highly dependent on the wettability and the adhesion energy of the stabilizer employed at the liquid-liquid interface. We present a user-friendly computational model that can be used to determine equilibrium orientations and the adhesion energy of colloidal particles at interfaces. The model determines the free energy profile of particle adsorption at liquid-liquid interfaces using a triangular tessellation scheme. We demonstrate the use of the model, using a variety of anisotropic particles and demonstrate its ability to predict and explain experimental observations of particle behaviour at interfaces. In particular, we show that the concept of hydrophilic lipophilic balance commonly applied to molecular surfactants is insufficient to explain the complexity of the activity of colloidal particles at interfaces. In addition, we show the importance of the knowledge of the free energy adsorption profile of single particles at interfaces and the impact on overall free energy of emulsification of packed ensembles of particles. The delicate balance between optimization of adhesion energy, adsorption dynamics and particle packing is shown to be of great importance in the formation of thermodynamically stable emulsions. In order to use the model, the code is implemented by freely available software that can be readily deployed on personal computers.},
 bibtype = {article},
 author = {Ballard, Nicholas and Bon, Stefan A F},
 doi = {10.1016/j.jcis.2015.02.069},
 journal = {Journal of Colloid and Interface Science}
}

The effective stabilization of emulsions by solid particles, a phenomenon known as Pickering stabilization, is well known to be highly dependent on the wettability and the adhesion energy of the stabilizer employed at the liquid-liquid interface. We present a user-friendly computational model that can be used to determine equilibrium orientations and the adhesion energy of colloidal particles at interfaces. The model determines the free energy profile of particle adsorption at liquid-liquid interfaces using a triangular tessellation scheme. We demonstrate the use of the model, using a variety of anisotropic particles and demonstrate its ability to predict and explain experimental observations of particle behaviour at interfaces. In particular, we show that the concept of hydrophilic lipophilic balance commonly applied to molecular surfactants is insufficient to explain the complexity of the activity of colloidal particles at interfaces. In addition, we show the importance of the knowledge of the free energy adsorption profile of single particles at interfaces and the impact on overall free energy of emulsification of packed ensembles of particles. The delicate balance between optimization of adhesion energy, adsorption dynamics and particle packing is shown to be of great importance in the formation of thermodynamically stable emulsions. In order to use the model, the code is implemented by freely available software that can be readily deployed on personal computers.

@inbook{
 type = {inbook},
 year = {2015},
 pages = {65-92},
 websites = {http://ebook.rsc.org/?DOI=10.1039/9781782620143-00065},
 publisher = {Royal Society of Chemistry},
 chapter = {CHAPTER 4. Pickering Suspension, Mini-Emulsion and Emulsion Polymerization},
 id = {9a009e78-46f2-3bf1-a451-aa8584bc2699},
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 last_modified = {2024-01-02T14:09:44.401Z},
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 starred = {false},
 authored = {false},
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 hidden = {false},
 citation_key = {bon2015pickering},
 source_type = {incollection},
 private_publication = {false},
 abstract = {This chapter gives an overview of the development of suspension, mini-emulsion and emulsion polymerization processes in which solid particles are used as Pickering stabilizers. These three heterogeneous polymerization techniques are briefly defined, after which early studies of the phenomenon of Pickering stabilization and its use in suspension polymerization are discussed. After a historic overview of the development of Pickering suspension polymerization, attention is drawn to its use in the fabrication of armoured microstructures. Next, the development of Pickering mini-emulsion polymerization is discussed, looking at the particle and droplet size distributions, Ostwald ripening and coarsening, particle nucleation and coagulation, and rates of polymerization. Finally, the dawn of and advances in Pickering emulsion polymerization are discussed, with comments on particle formation and particle growth.},
 bibtype = {inbook},
 author = {Bon, Stefan A. F.},
 editor = {Ngai, To and Bon, Stefan A F},
 doi = {10.1039/9781782620143-00065},
 title = {Particle-Stabilized Emulsions and Colloids: Formation and Applications}
}

This chapter gives an overview of the development of suspension, mini-emulsion and emulsion polymerization processes in which solid particles are used as Pickering stabilizers. These three heterogeneous polymerization techniques are briefly defined, after which early studies of the phenomenon of Pickering stabilization and its use in suspension polymerization are discussed. After a historic overview of the development of Pickering suspension polymerization, attention is drawn to its use in the fabrication of armoured microstructures. Next, the development of Pickering mini-emulsion polymerization is discussed, looking at the particle and droplet size distributions, Ostwald ripening and coarsening, particle nucleation and coagulation, and rates of polymerization. Finally, the dawn of and advances in Pickering emulsion polymerization are discussed, with comments on particle formation and particle growth.

@article{
 title = {Synthesis of "hard-soft" janus particles by seeded dispersion polymerization},
 type = {article},
 year = {2014},
 pages = {13525-13532},
 volume = {30},
 websites = {http://pubs.acs.org/doi/abs/10.1021/la503366h},
 publisher = {American Chemical Society},
 id = {2236fe54-e3f2-346a-9a8d-6f489b6624e1},
 created = {2024-01-02T14:09:34.957Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:34.957Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {skelhon2014synthesis},
 source_type = {article},
 private_publication = {false},
 abstract = {The majority of studies on Janus particles focus on those that show amphiphilicity, with distinct hydrophilic and hydrophobic domains. Here, we demonstrate the synthesis of a different class of Janus particles: "hard-soft" biphasic dumbbell- or peanut-shaped particles with distinct lobes of "soft" poly(n-butyl acrylate) and "hard" poly(styrene). The particles are made by seeded dispersion polymerization of butyl acrylate in the presence of poly(styrene) seed particles. Surface nucleation by capture of the oligoradicals onto the surface of the seed particles thereby forming a distinct new polymer phase is found to be the formation mechanism of these particles. The total available poly(styrene) seed surface area plays a significant role in the size and number of poly(butyl acrylate) lobes grown off a single particle. At particularly low values of the surface area, we observe the formation of multilobe particles. We further demonstrate that our synthesis method is versatile and can be extended to the submicrometer domains by using seed particles of 200 nm in diameter.},
 bibtype = {article},
 author = {Skelhon, Thomas S. and Chen, Yunhua and Bon, Stefan A F},
 doi = {10.1021/la503366h},
 journal = {Langmuir},
 number = {45}
}

The majority of studies on Janus particles focus on those that show amphiphilicity, with distinct hydrophilic and hydrophobic domains. Here, we demonstrate the synthesis of a different class of Janus particles: "hard-soft" biphasic dumbbell- or peanut-shaped particles with distinct lobes of "soft" poly(n-butyl acrylate) and "hard" poly(styrene). The particles are made by seeded dispersion polymerization of butyl acrylate in the presence of poly(styrene) seed particles. Surface nucleation by capture of the oligoradicals onto the surface of the seed particles thereby forming a distinct new polymer phase is found to be the formation mechanism of these particles. The total available poly(styrene) seed surface area plays a significant role in the size and number of poly(butyl acrylate) lobes grown off a single particle. At particularly low values of the surface area, we observe the formation of multilobe particles. We further demonstrate that our synthesis method is versatile and can be extended to the submicrometer domains by using seed particles of 200 nm in diameter.

@article{
 title = {Dynamic uptake and release from poly(methacryloyl hydrazide) microgel particles through reversible hydrazide-aldehyde chemistry},
 type = {article},
 year = {2014},
 pages = {6789-6796},
 volume = {5},
 websites = {http://xlink.rsc.org/?DOI=C4PY00726C},
 publisher = {Royal Society of Chemistry},
 id = {aa94d9ce-3505-3dbc-8664-470aa2af9f02},
 created = {2024-01-02T14:09:36.113Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:36.113Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ballard2014dynamic},
 source_type = {article},
 private_publication = {false},
 abstract = {The synthesis of poly(methacryloyl hydrazide) microgels via dispersion polymerization for the controlled release of carbonyl containing compounds is described. The kinetics of the dynamic reaction that occurs between the hydrazide containing colloidal particles and aldehyde compounds are explored for aqueous dispersions and it is shown that the aldehyde release profiles at conditions of physiological significance indicate a dynamic balance between the reaction components providing a route to sustained release of functional molecules.},
 bibtype = {article},
 author = {Ballard, Nicholas and Bon, Stefan A. F.},
 doi = {10.1039/C4PY00726C},
 journal = {Polym. Chem.},
 number = {23}
}

The synthesis of poly(methacryloyl hydrazide) microgels via dispersion polymerization for the controlled release of carbonyl containing compounds is described. The kinetics of the dynamic reaction that occurs between the hydrazide containing colloidal particles and aldehyde compounds are explored for aqueous dispersions and it is shown that the aldehyde release profiles at conditions of physiological significance indicate a dynamic balance between the reaction components providing a route to sustained release of functional molecules.

@article{
 title = {Dynamic control of volume phase transitions of poly( <i>N</i> -isopropylacrylamide) based microgels in water using hydrazide-aldehyde chemistry},
 type = {article},
 year = {2014},
 pages = {1745-1754},
 volume = {52},
 websites = {http://doi.wiley.com/10.1002/pola.27177},
 publisher = {Wiley Periodicals, Inc.},
 id = {bf1299bc-4f7b-379e-94d0-597179e1d4e3},
 created = {2024-01-02T14:09:41.565Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:41.565Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {chen2014dynamic},
 source_type = {article},
 private_publication = {false},
 abstract = {We demonstrate that the volume phase transition temperature (VPTT) of copolymer microgel particles made from N-isopropylacrylamide (NIPAm) and methacryloyl hydrazide (MH) can be tailored in a reversible manner upon the reaction of the hydrazide functional groups with aldehydes. The microgels were synthesized by precipitation polymerization in water. Due to the water-soluble nature of the MH monomer, the VPTT at which the microgel particles contract shifts to higher values by increasing the incorporated amounts of methacryloyl hydrazide from 0 to 5.0 mol %. The VPTT of the copolymer microgel dispersions in water can be fine-tuned upon addition of hydrophobic/hydrophilic aldehydes, which react with the hydrazide moiety to produce the hydrazone analogue. This hydrazone formation is reversible, which allows for flexible, dynamic control of the thermo-responsive behavior of the microgels. The ability to switch the VPTT was demonstrated by exposing hydrophilic streptomycin sulfate salt incubated microgel particles to an excess of a hydrophobic aldehyde, that is benzaldehyde. The temperature at which these microgels contracted in size upon heating was markedly lowered in these aldehyde exchange experiments. Transformation into benzaldehyde hydrazone derivatives led to assembly of the microgel particles into small colloidal clusters at elevated temperatures. This control of supracolloidal cluster formation was also demonstrated with polystyrene particles which had a hydrazide functionalised microgel shell. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1745-1754},
 bibtype = {article},
 author = {Chen, Yunhua and Ballard, Nicholas and Coleman, Oliver D. and Hands-Portman, Ian J. and Bon, Stefan A. F.},
 doi = {10.1002/pola.27177},
 journal = {Journal of Polymer Science Part A: Polymer Chemistry},
 number = {12}
}

We demonstrate that the volume phase transition temperature (VPTT) of copolymer microgel particles made from N-isopropylacrylamide (NIPAm) and methacryloyl hydrazide (MH) can be tailored in a reversible manner upon the reaction of the hydrazide functional groups with aldehydes. The microgels were synthesized by precipitation polymerization in water. Due to the water-soluble nature of the MH monomer, the VPTT at which the microgel particles contract shifts to higher values by increasing the incorporated amounts of methacryloyl hydrazide from 0 to 5.0 mol %. The VPTT of the copolymer microgel dispersions in water can be fine-tuned upon addition of hydrophobic/hydrophilic aldehydes, which react with the hydrazide moiety to produce the hydrazone analogue. This hydrazone formation is reversible, which allows for flexible, dynamic control of the thermo-responsive behavior of the microgels. The ability to switch the VPTT was demonstrated by exposing hydrophilic streptomycin sulfate salt incubated microgel particles to an excess of a hydrophobic aldehyde, that is benzaldehyde. The temperature at which these microgels contracted in size upon heating was markedly lowered in these aldehyde exchange experiments. Transformation into benzaldehyde hydrazone derivatives led to assembly of the microgel particles into small colloidal clusters at elevated temperatures. This control of supracolloidal cluster formation was also demonstrated with polystyrene particles which had a hydrazide functionalised microgel shell. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1745-1754

@article{
 title = {Hierarchical self-assembly of ‘hard–soft’ Janus particles into colloidal molecules and larger supracolloidal structures},
 type = {article},
 year = {2014},
 pages = {7730-7735},
 volume = {10},
 websites = {http://xlink.rsc.org/?DOI=C4SM01708K},
 month = {8},
 publisher = {The Royal Society of Chemistry},
 day = {8},
 id = {b419c6e8-582c-33a4-a269-5eeadb42f0e0},
 created = {2024-01-02T14:09:44.778Z},
 accessed = {2014-08-12},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:44.778Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Skelhon2014},
 language = {en},
 private_publication = {false},
 abstract = {<p>We demonstrate the self-assembly of ‘hard–soft’ micron-sized Janus particles into clusters in aqueous media. Upon the coalescence of the soft polymeric lobes, the newly formed clusters adopt a minimized surface area to volume ratio forming distinct microscopic supracolloidal structures.</p>},
 bibtype = {article},
 author = {Skelhon, Thomas S. and Chen, Yunhua and Bon, Stefan A. F.},
 doi = {10.1039/C4SM01708K},
 journal = {Soft Matter},
 number = {39}
}

We demonstrate the self-assembly of ‘hard–soft’ micron-sized Janus particles into clusters in aqueous media. Upon the coalescence of the soft polymeric lobes, the newly formed clusters adopt a minimized surface area to volume ratio forming distinct microscopic supracolloidal structures.

@article{
 title = {Chemotaxis of catalytic silica–manganese oxide “matchstick” particles},
 type = {article},
 year = {2014},
 pages = {65},
 volume = {1},
 websites = {http://pubs.rsc.org/en/content/articlehtml/2014/mh/c3mh00003f},
 month = {11},
 publisher = {The Royal Society of Chemistry},
 day = {19},
 id = {897e6f1f-cb75-3e6a-9ffc-53f38a550669},
 created = {2024-01-02T14:09:44.956Z},
 accessed = {2014-08-22},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:44.956Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Morgan2014},
 language = {en},
 private_publication = {false},
 abstract = {Particles that can undergo directed self-propulsion are desirable for colloidal cargo delivery and self-assembly. Herein we describe the synthesis of silica–manganese oxide “matchstick” colloids that undergo catalytic self-propulsion by consumption of hydrogen peroxide. Chemotaxis is observed when particles are placed in a fuel gradient. Movement opposes convective flow which is tracked by following inert polymer microspheres simultaneously.},
 bibtype = {article},
 author = {Morgan, Adam R. and Dawson, Alan B. and Mckenzie, Holly S. and Skelhon, Thomas S. and Beanland, Richard and Franks, Henry P. W. and Bon, Stefan a. F.},
 doi = {10.1039/c3mh00003f},
 journal = {Materials Horizons},
 number = {1}
}

Particles that can undergo directed self-propulsion are desirable for colloidal cargo delivery and self-assembly. Herein we describe the synthesis of silica–manganese oxide “matchstick” colloids that undergo catalytic self-propulsion by consumption of hydrogen peroxide. Chemotaxis is observed when particles are placed in a fuel gradient. Movement opposes convective flow which is tracked by following inert polymer microspheres simultaneously.

@article{
 title = {High internal phase agar hydrogel dispersions in cocoa butter and chocolate as a route towards reducing fat content},
 type = {article},
 year = {2013},
 pages = {1314},
 volume = {4},
 websites = {http://xlink.rsc.org/?DOI=c3fo60122f},
 publisher = {Royal Society of Chemistry},
 id = {7f56bf14-824c-3a9c-b11d-a9a3f4b75ca3},
 created = {2024-01-02T14:09:34.564Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:34.564Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {skelhon2013high},
 source_type = {article},
 private_publication = {false},
 abstract = {Reducing the fat content of chocolate formulations is a major challenge for the confectionery industry. We report the suspension of aqueous microgel agar particles of up to 80% v/v within sunflower oil, cocoa butter, and ultimately chocolate. The optimised emulsification process involves a shear-cooling step. We demonstrate the versatility of our method when applied to white, milk, and dark chocolate formulations, whilst preserving the desired polymorph V of the cocoa butter matrix. In addition, we show that this technology can be used as a strategy to disperse alcoholic beverages into chocolate confectionery.},
 bibtype = {article},
 author = {Skelhon, Thomas S. and Olsson, Patrik K. A. and Morgan, Adam R. and Bon, Stefan A. F.},
 doi = {10.1039/c3fo60122f},
 journal = {Food & Function},
 number = {9}
}

Reducing the fat content of chocolate formulations is a major challenge for the confectionery industry. We report the suspension of aqueous microgel agar particles of up to 80% v/v within sunflower oil, cocoa butter, and ultimately chocolate. The optimised emulsification process involves a shear-cooling step. We demonstrate the versatility of our method when applied to white, milk, and dark chocolate formulations, whilst preserving the desired polymorph V of the cocoa butter matrix. In addition, we show that this technology can be used as a strategy to disperse alcoholic beverages into chocolate confectionery.

@article{
 title = {Moldable high internal phase emulsion hydrogel objects from non-covalently crosslinked poly(N-isopropylacrylamide) nanogel dispersions.},
 type = {article},
 year = {2013},
 pages = {1524-6},
 volume = {49},
 websites = {http://pubs.rsc.org/en/content/articlehtml/2013/cc/c2cc38200h},
 publisher = {Royal Society of Chemistry},
 id = {7264cc0e-8427-30b4-a326-8e90ed6fda5d},
 created = {2024-01-02T14:09:36.459Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:36.459Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {chen2013moldable},
 source_type = {article},
 private_publication = {false},
 abstract = {High Internal Phase Emulsion hydrogels are prepared from waterborne poly(N-isopropylacrylamide) nanogel dispersions which are non-covalently crosslinked through 2-ureido-4[1H] pyrimidinone (UPy) quadruple hydrogen bond groups. The reversible UPy crosslinks allow for the HIPE-hydrogels to be molded into objects which are thermo-responsive in nature.},
 bibtype = {article},
 author = {Chen, Yunhua and Ballard, Nicholas and Bon, Stefan A F},
 doi = {10.1039/c2cc38200h},
 journal = {Chemical communications (Cambridge, England)},
 number = {15}
}

High Internal Phase Emulsion hydrogels are prepared from waterborne poly(N-isopropylacrylamide) nanogel dispersions which are non-covalently crosslinked through 2-ureido-4[1H] pyrimidinone (UPy) quadruple hydrogen bond groups. The reversible UPy crosslinks allow for the HIPE-hydrogels to be molded into objects which are thermo-responsive in nature.

@article{
 title = {Waterborne polymer nanogels non-covalently crosslinked by multiple hydrogen bond arrays},
 type = {article},
 year = {2013},
 pages = {387-392},
 volume = {4},
 websites = {http://xlink.rsc.org/?DOI=C2PY20615C},
 publisher = {Royal Society of Chemistry},
 id = {f77e7caf-7658-359c-a597-4820563de5ee},
 created = {2024-01-02T14:09:37.999Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:37.999Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {chen2013waterborne},
 source_type = {article},
 private_publication = {false},
 abstract = {Synthetic colloidal hydrogel particles of sub-micron dimensions, often referred to as microgels and/or nanogels, generally consist of water-soluble polymers held together through chemical crosslinking by covalent bonds in order to preserve the distinct colloidal particle identity. Here we demonstrate the synthesis of non-covalently crosslinked nanogel particles in which the crosslinking through covalent bonds is replaced by physical crosslinking induced by strong self-complementary quadruple hydrogen bond interactions. The multiple hydrogen bond (MHB) arrays were introduced in the form of a 2-ureido4[1H]pyrimidinone (UPy) functionalized polyethylene glycol methacrylate (PEGMA) comonomer, which was employed in the synthesis of colloidal nanogels made from N-isopropylacrylamide (NIPAm) or a mixture of 2-(2-methoxyethoxy) ethyl methacrylate and oligo(ethylene glycol) methacrylate (MEO(2)MA-co-OEGMA) following conventional free radical polymerization routes. The temperature-dependent swelling properties of the non-covalently crosslinked nanogels with differences in UPy loadings were studied, clearly demonstrating that MHB arrays can work as crosslinking moieties warranting the colloidal particle identity of the prepared hydrogels.},
 bibtype = {article},
 author = {Chen, Yunhua and Ballard, Nicholas and Bon, Stefan A. F.},
 doi = {10.1039/C2PY20615C},
 journal = {Polym. Chem.},
 number = {2}
}

Synthetic colloidal hydrogel particles of sub-micron dimensions, often referred to as microgels and/or nanogels, generally consist of water-soluble polymers held together through chemical crosslinking by covalent bonds in order to preserve the distinct colloidal particle identity. Here we demonstrate the synthesis of non-covalently crosslinked nanogel particles in which the crosslinking through covalent bonds is replaced by physical crosslinking induced by strong self-complementary quadruple hydrogen bond interactions. The multiple hydrogen bond (MHB) arrays were introduced in the form of a 2-ureido4[1H]pyrimidinone (UPy) functionalized polyethylene glycol methacrylate (PEGMA) comonomer, which was employed in the synthesis of colloidal nanogels made from N-isopropylacrylamide (NIPAm) or a mixture of 2-(2-methoxyethoxy) ethyl methacrylate and oligo(ethylene glycol) methacrylate (MEO(2)MA-co-OEGMA) following conventional free radical polymerization routes. The temperature-dependent swelling properties of the non-covalently crosslinked nanogels with differences in UPy loadings were studied, clearly demonstrating that MHB arrays can work as crosslinking moieties warranting the colloidal particle identity of the prepared hydrogels.

@article{
 title = {Surfactant-free miniemulsion polymerization of n-BA/S stabilized by NaMMT: Films with improved water resistance},
 type = {article},
 year = {2013},
 pages = {2397-2405},
 volume = {29},
 websites = {http://pubs.acs.org/doi/abs/10.1021/la3047033},
 publisher = {American Chemical Society},
 id = {3391736f-be64-3b95-bd45-35985231f2bd},
 created = {2024-01-02T14:09:38.172Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:38.172Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bonnefond2013surfactant},
 source_type = {article},
 private_publication = {false},
 abstract = {The use of sodium montmorillonite clay as a stabilizer in the surfactant-free emulsion polymerization of n-butyl acrylate/styrene (n-BA/S) was assessed. It was shown that the use of the clay alone did not yield the desired armored latex particles. A functional comonomer, that is, a phosphate ester of poly(ethylene glycol) monomethacrylate, was used to improve the interaction between the polymer and clay, thus allowing for the clay platelets to adhere to the surface of the polymer particles. The morphology of the films obtained for these two different scenarios was similar and resembled a honeycomb structure. However, their water-resistance properties differed drastically. The water absorption and water vapor permeation rate were much lower in the hybrid n-BA/S/clay films in the presence of the functional monomer than in the films obtained without the functional monomer.},
 bibtype = {article},
 author = {Bonnefond, Audrey and Paulis, Maria and Bon, Stefan A F and Leiza, José R.},
 doi = {10.1021/la3047033},
 journal = {Langmuir},
 number = {7}
}

The use of sodium montmorillonite clay as a stabilizer in the surfactant-free emulsion polymerization of n-butyl acrylate/styrene (n-BA/S) was assessed. It was shown that the use of the clay alone did not yield the desired armored latex particles. A functional comonomer, that is, a phosphate ester of poly(ethylene glycol) monomethacrylate, was used to improve the interaction between the polymer and clay, thus allowing for the clay platelets to adhere to the surface of the polymer particles. The morphology of the films obtained for these two different scenarios was similar and resembled a honeycomb structure. However, their water-resistance properties differed drastically. The water absorption and water vapor permeation rate were much lower in the hybrid n-BA/S/clay films in the presence of the functional monomer than in the films obtained without the functional monomer.

@article{
 title = {Multicompartmental Janus microbeads from branched polymers by single-emulsion droplet microfluidics},
 type = {article},
 year = {2013},
 pages = {12657-12662},
 volume = {29},
 websites = {http://pubs.acs.org/doi/abs/10.1021/la402417h},
 publisher = {American Chemical Society},
 id = {b2791457-043f-37b9-95f3-ebc9bac0648b},
 created = {2024-01-02T14:09:38.749Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:38.749Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {chen2013multicompartmental},
 source_type = {article},
 private_publication = {false},
 abstract = {We describe a versatile and facile route for the preparation of Janus microbeads using single emulsion droplet-based microfluidics, in which water droplets that contain a mixture of branched poly(N-isopropylacrylamide)-co-(poly(ethylene glycol)diacrylate)-co-(methacrylic acid) and colloidal particles form the basis of our approach. The colloidal particles, poly(methyl methacrylate) microspheres or titanium dioxide particles, and iron oxide nanoparticles are spatially positioned within the water droplets through gravity and an externally applied magnetic force, respectively. Evaporation of water leads to gel formation of the branched copolymer matrix as a result of physical cross-linking through hydrogen bond interactions, fixing the spatial position of the colloidal particles. The thermo- and pH-responsive nature of the branched poly(N-isopropylacrylamide) (PNIPAm)-based copolymer allows for the disintegration of the polymer network of the Janus microbeads and a triggered release of the colloidal content ...},
 bibtype = {article},
 author = {Chen, Yunhua and Nurumbetov, Gabit and Chen, Rong and Ballard, Nicholas and Bon, Stefan A F},
 doi = {10.1021/la402417h},
 journal = {Langmuir},
 number = {41}
}

We describe a versatile and facile route for the preparation of Janus microbeads using single emulsion droplet-based microfluidics, in which water droplets that contain a mixture of branched poly(N-isopropylacrylamide)-co-(poly(ethylene glycol)diacrylate)-co-(methacrylic acid) and colloidal particles form the basis of our approach. The colloidal particles, poly(methyl methacrylate) microspheres or titanium dioxide particles, and iron oxide nanoparticles are spatially positioned within the water droplets through gravity and an externally applied magnetic force, respectively. Evaporation of water leads to gel formation of the branched copolymer matrix as a result of physical cross-linking through hydrogen bond interactions, fixing the spatial position of the colloidal particles. The thermo- and pH-responsive nature of the branched poly(N-isopropylacrylamide) (PNIPAm)-based copolymer allows for the disintegration of the polymer network of the Janus microbeads and a triggered release of the colloidal content ...

@article{
 title = {Morphological transitions in polymer vesicles upon bilayer swelling with small hydrophobic molecules in water},
 type = {article},
 year = {2013},
 pages = {6890},
 volume = {9},
 websites = {http://xlink.rsc.org/?DOI=c3sm50184a},
 publisher = {Royal Society of Chemistry},
 id = {840e0907-6783-3358-80a0-9b576f5045c2},
 created = {2024-01-02T14:09:43.659Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:43.659Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {parmenter2013morphological},
 source_type = {article},
 private_publication = {false},
 abstract = {We show that when unilamellar polymer vesicles dispersed in water made from a blockcopolymer, in this case poly((ethylene oxide)45-block-(methyl methacrylate)164), poly((ethylene oxide)45-block-(methyl methacrylate)170), or poly(n-butyl methacrylate)81-block-(2-(dimethylamino)ethyl methacrylate)20, are exposed to small hydrophobic molecules, here methyl methacrylate as well as n-butyl methacrylate, they can undergo morphological transitions. Upon swelling, the polymersomes lose their original simple bilayer morphology and transform into more complex coil-like and patchy colloidal structures, as investigated experimentally by cryogenic electron microscopy (cryo-EM). Dissipative particle dynamics (DPD) simulations on a model flat bilayer indeed show that transitions can occur upon bilayer swelling, which is accompanied by a change in the mechanical bilayer properties. The transition involves the formation of water pockets in the interior regions of the bilayer. Co-existence of the various morphologies in the experiments suggests an activation barrier towards morphological changes and a possibility of multiple meta-stable states. The latter indeed is supported by the existence of multiple minima in the surface tension as a function of bilayer area, as found in the simulations.},
 bibtype = {article},
 author = {Parmenter, Christopher D. J. and Chen, Rong and Cheung, David L. and Bon, Stefan A. F.},
 doi = {10.1039/c3sm50184a},
 journal = {Soft Matter},
 number = {29}
}

We show that when unilamellar polymer vesicles dispersed in water made from a blockcopolymer, in this case poly((ethylene oxide)45-block-(methyl methacrylate)164), poly((ethylene oxide)45-block-(methyl methacrylate)170), or poly(n-butyl methacrylate)81-block-(2-(dimethylamino)ethyl methacrylate)20, are exposed to small hydrophobic molecules, here methyl methacrylate as well as n-butyl methacrylate, they can undergo morphological transitions. Upon swelling, the polymersomes lose their original simple bilayer morphology and transform into more complex coil-like and patchy colloidal structures, as investigated experimentally by cryogenic electron microscopy (cryo-EM). Dissipative particle dynamics (DPD) simulations on a model flat bilayer indeed show that transitions can occur upon bilayer swelling, which is accompanied by a change in the mechanical bilayer properties. The transition involves the formation of water pockets in the interior regions of the bilayer. Co-existence of the various morphologies in the experiments suggests an activation barrier towards morphological changes and a possibility of multiple meta-stable states. The latter indeed is supported by the existence of multiple minima in the surface tension as a function of bilayer area, as found in the simulations.

@article{
 title = {Influence of janus particle shape on their interfacial behavior at liquid-liquid interfaces},
 type = {article},
 year = {2013},
 keywords = {Adsorption,Nanoparticles,Nanoparticles: chemistry,Particle Size,Surface Properties,Toluene,Toluene: chemistry,Water,Water: chemistry,Wettability},
 pages = {1388-1394},
 volume = {29},
 websites = {http://pubs.acs.org/doi/abs/10.1021/la3048642},
 month = {2},
 publisher = {American Chemical Society},
 day = {5},
 id = {3dffebbf-1d3d-3494-ac89-6b00270f9418},
 created = {2024-01-02T14:09:45.464Z},
 accessed = {2014-08-22},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:45.464Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Ruhland2013},
 private_publication = {false},
 abstract = {We investigate the self-assembly behavior of Janus particles with different geometries at a liquid-liquid interface. The Janus particles we focus on are characterized by a phase separation along their major axis into two hemicylinders of different wettability. We present a combination of experimental and simulation data together with detailed studies elucidating the mechanisms governing the adsorption process of Janus spheres, Janus cylinders, and Janus discs. Using the pendant drop technique, we monitor the assembly kinetics following changes in the interfacial tension of nanoparticle adsorption. According to the evolution of the interfacial tension and simulation data, we will specify the characteristics of early to late stages of the Janus particle adsorption and discuss the effect of Janus particle shape and geometry. The adsorption is characterized by three adsorption stages which are based on the different assembly kinetics and different adsorption mechanisms depending on the particle shape.},
 bibtype = {article},
 author = {Ruhland, Thomas M. and Gröschel, André H. and Ballard, Nicholas and Skelhon, Thomas S. and Walther, Andreas and Müller, Axel H E and Bon, Stefan A F},
 doi = {10.1021/la3048642},
 journal = {Langmuir},
 number = {5}
}

We investigate the self-assembly behavior of Janus particles with different geometries at a liquid-liquid interface. The Janus particles we focus on are characterized by a phase separation along their major axis into two hemicylinders of different wettability. We present a combination of experimental and simulation data together with detailed studies elucidating the mechanisms governing the adsorption process of Janus spheres, Janus cylinders, and Janus discs. Using the pendant drop technique, we monitor the assembly kinetics following changes in the interfacial tension of nanoparticle adsorption. According to the evolution of the interfacial tension and simulation data, we will specify the characteristics of early to late stages of the Janus particle adsorption and discuss the effect of Janus particle shape and geometry. The adsorption is characterized by three adsorption stages which are based on the different assembly kinetics and different adsorption mechanisms depending on the particle shape.

@article{
 title = {Understanding the multiple orientations of isolated superellipsoidal hematite particles at the oil–water interface},
 type = {article},
 year = {2013},
 pages = {487-491},
 volume = {9},
 websites = {http://xlink.rsc.org/?DOI=C2SM26556G},
 month = {12},
 publisher = {The Royal Society of Chemistry},
 day = {6},
 id = {8686bd37-586c-3a9e-a2cb-42fc42f57487},
 created = {2024-01-02T14:09:45.722Z},
 accessed = {2014-05-29},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:45.722Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Morgan2013},
 language = {en},
 private_publication = {false},
 abstract = {Non-spherical particles have the potential to adopt multiple orientations once adhered to a liquid–liquid interface. In this work we combine simulations and experiments to investigate the behaviour of an isolated microscopic hematite particle of superellipsoidal shape. We show that this microparticle can adopt one of three orientations when adhered to a hexadecane–water interface. Two of the orientations, and estimates for their relative populations, could be assigned to two thermodynamic minima on the energy landscape as generated through both free-energy minimization and particle trajectory simulations. The third orientation was found to correspond to a kinetically trapped state, existing on certain particle trajectories in a region of a negligible gradient in free energy. To underpin the simulations the individual orientation of a set of 100 isolated particles was explored by means of scanning electron microscopy (SEM) using the gel trapping technique as a tool. Atomic force microscopy (AFM) was additionally used to support the experimental findings. This is the first example of such a kinetic metastable state being observed for particles at liquid–liquid interfaces.},
 bibtype = {article},
 author = {Morgan, Adam R. and Ballard, Nicholas and Rochford, Luke A. and Nurumbetov, Gabit and Skelhon, Thomas S. and Bon, Stefan A. F.},
 doi = {10.1039/C2SM26556G},
 journal = {Soft Matter},
 number = {2}
}

Non-spherical particles have the potential to adopt multiple orientations once adhered to a liquid–liquid interface. In this work we combine simulations and experiments to investigate the behaviour of an isolated microscopic hematite particle of superellipsoidal shape. We show that this microparticle can adopt one of three orientations when adhered to a hexadecane–water interface. Two of the orientations, and estimates for their relative populations, could be assigned to two thermodynamic minima on the energy landscape as generated through both free-energy minimization and particle trajectory simulations. The third orientation was found to correspond to a kinetically trapped state, existing on certain particle trajectories in a region of a negligible gradient in free energy. To underpin the simulations the individual orientation of a set of 100 isolated particles was explored by means of scanning electron microscopy (SEM) using the gel trapping technique as a tool. Atomic force microscopy (AFM) was additionally used to support the experimental findings. This is the first example of such a kinetic metastable state being observed for particles at liquid–liquid interfaces.

@article{
 title = {Morphology and properties of waterborne adhesives made from hybrid polyacrylic/montmorillonite clay colloidal dispersions showing improved tack and shear resistance},
 type = {article},
 year = {2013},
 keywords = {Adhesive properties,Miniemulsion polymerization,Waterborne acrylic/montmorillonite clay nanocompos},
 pages = {167-180},
 volume = {291},
 websites = {http://link.springer.com/article/10.1007/s00396-012-2649-3},
 month = {1},
 id = {a5f873ca-43d9-375d-9bf2-814e50a299c5},
 created = {2024-01-02T14:09:48.224Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:48.224Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000313345300017},
 source_type = {article},
 private_publication = {false},
 abstract = {The morphology and adhesive properties of waterborne films from n-butyl acrylate/methyl methacrylate/montmorillonite clay hybrid polymer latexes which were synthesized by miniemulsion polymerization in the presence of a reactive organoclay ((2-methacryloylethyl) hexadecyldimethylammonium modified montmorillonite, CMA16) were investigated. It was found by cryo-TEM analysis that the hybrid dispersions were a mixture of colloidal particles composed of a small fraction of free montmorillonite clay platelets, polymer latex particles, polymer particles to which one or more clay platelets where adhered onto its surface and a fraction of colloidal material consisted of a clay platelet with a polymer lob adhered to either side, in other words hybrid particles with a dumbbell-like morphology. The films made from these waterborne hybrid dispersions presented a homogeneous dispersion of the clay platelets and exfoliated morphology. The shear adhesion failure temperature (SAFT) and shear resistance of the hybrid latex films synthesized with CMA16 were better than those prepared with a commercial clay (Cloisite 30B), but presented a liquid-like probe-tack performance. When allyl methacrylate (AMA) was added in the formulation, SAFT and shear resistance improved, but the film had a very low energy of adhesion due to the excessively crosslinked matrix. In order to reduce crosslink density and thus improve the adhesion energy, small amounts of chain transfer agent, in this case n-dodecyl mercaptan (n-DDM), were used in the miniemulsion polymerization process. Adhesive films made from these waterborne hybrid dispersions showed excellent SAFT and shear resistance, and good energy of adhesion.},
 bibtype = {article},
 author = {Bonnefond, Audrey and Mičušík, Matej and Paulis, Maria and Leiza, Jose R. and Teixeira, Roberto F A and Bon, Stefan A F},
 doi = {10.1007/s00396-012-2649-3},
 journal = {Colloid and Polymer Science},
 number = {1}
}

The morphology and adhesive properties of waterborne films from n-butyl acrylate/methyl methacrylate/montmorillonite clay hybrid polymer latexes which were synthesized by miniemulsion polymerization in the presence of a reactive organoclay ((2-methacryloylethyl) hexadecyldimethylammonium modified montmorillonite, CMA16) were investigated. It was found by cryo-TEM analysis that the hybrid dispersions were a mixture of colloidal particles composed of a small fraction of free montmorillonite clay platelets, polymer latex particles, polymer particles to which one or more clay platelets where adhered onto its surface and a fraction of colloidal material consisted of a clay platelet with a polymer lob adhered to either side, in other words hybrid particles with a dumbbell-like morphology. The films made from these waterborne hybrid dispersions presented a homogeneous dispersion of the clay platelets and exfoliated morphology. The shear adhesion failure temperature (SAFT) and shear resistance of the hybrid latex films synthesized with CMA16 were better than those prepared with a commercial clay (Cloisite 30B), but presented a liquid-like probe-tack performance. When allyl methacrylate (AMA) was added in the formulation, SAFT and shear resistance improved, but the film had a very low energy of adhesion due to the excessively crosslinked matrix. In order to reduce crosslink density and thus improve the adhesion energy, small amounts of chain transfer agent, in this case n-dodecyl mercaptan (n-DDM), were used in the miniemulsion polymerization process. Adhesive films made from these waterborne hybrid dispersions showed excellent SAFT and shear resistance, and good energy of adhesion.

@article{
 title = {Quiescent water-in-oil Pickering emulsions as a route toward healthier fruit juice infused chocolate confectionary},
 type = {article},
 year = {2012},
 pages = {19289},
 volume = {22},
 websites = {http://xlink.rsc.org/?DOI=c2jm34233b},
 publisher = {Royal Society of Chemistry},
 id = {40cd17c8-880e-3fbd-9055-5bc9cbfb398a},
 created = {2024-01-02T14:09:35.311Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:35.311Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {skelhon2012quiescent},
 source_type = {article},
 private_publication = {false},
 abstract = {We demonstrate a route toward the preparation of healthier fruit juice infused chocolate candy. Up to 50 wt% of the fat content in chocolate, that is cocoa butter and milk fats, is replaced with fruit juice in the form of emulsion droplets using a quiescent Pickering emulsion fabrication strategy. Fumed silica particles are used in combination with chitosan under acidic conditions (pH 3.2-3.8) to prepare water-in-oil emulsions, the oil phase being sunflower oil, molten cocoa butter, and ultimately white, milk, and dark chocolate. Adsorption of the polycationic chitosan molecules onto the surface of the silica particles influenced the particle wettability making it an effective Pickering stabilizer, as shown by cryogenic scanning electron microscopy analysis. The formation of a colloidal gel in the continuous (molten) oil phase provided the system with a yield stress, hereby giving it a gel-like and thus quiescent behaviour under low shear conditions, as determined by rheological measurements. This warrants a homogeneous distribution of emulsion droplets as settling through gravity upon storage under molten/liquid conditions is arrested. In our low-fat chocolate formulations the cocoa butter has the desired polymorph V structure, and neither sugar nor fat bloom was observed upon storage of the fruit juice containing chocolate confectionaries. This journal is © The Royal Society of Chemistry.},
 bibtype = {article},
 author = {Skelhon, Thomas S. and Grossiord, Nadia and Morgan, Adam R. and Bon, Stefan A. F.},
 doi = {10.1039/c2jm34233b},
 journal = {Journal of Materials Chemistry},
 number = {36}
}

We demonstrate a route toward the preparation of healthier fruit juice infused chocolate candy. Up to 50 wt% of the fat content in chocolate, that is cocoa butter and milk fats, is replaced with fruit juice in the form of emulsion droplets using a quiescent Pickering emulsion fabrication strategy. Fumed silica particles are used in combination with chitosan under acidic conditions (pH 3.2-3.8) to prepare water-in-oil emulsions, the oil phase being sunflower oil, molten cocoa butter, and ultimately white, milk, and dark chocolate. Adsorption of the polycationic chitosan molecules onto the surface of the silica particles influenced the particle wettability making it an effective Pickering stabilizer, as shown by cryogenic scanning electron microscopy analysis. The formation of a colloidal gel in the continuous (molten) oil phase provided the system with a yield stress, hereby giving it a gel-like and thus quiescent behaviour under low shear conditions, as determined by rheological measurements. This warrants a homogeneous distribution of emulsion droplets as settling through gravity upon storage under molten/liquid conditions is arrested. In our low-fat chocolate formulations the cocoa butter has the desired polymorph V structure, and neither sugar nor fat bloom was observed upon storage of the fruit juice containing chocolate confectionaries. This journal is © The Royal Society of Chemistry.

@article{
 title = {Synthesis, characterization and thermal properties of novel nanoencapsulated phase change materials for thermal energy storage},
 type = {article},
 year = {2012},
 keywords = {Miniemulsion,N-octadecane,Nanocapsules,PEMA,Thermal physical property},
 pages = {1149-1154},
 volume = {86},
 websites = {http://www.sciencedirect.com/science/article/pii/S0038092X12000199},
 publisher = {Elsevier},
 id = {2cd4d421-9695-340e-a51e-bbcb60b67d7a},
 created = {2024-01-02T14:09:35.684Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:35.684Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {zhang2012synthesis},
 source_type = {article},
 private_publication = {false},
 abstract = {In this paper, nanocapsules containing n-octadecane with an average 50. nm thick shell of poly(ethyl methacrylate) (PEMA) and poly(methyl methacrylate) (PMMA), and a core/shell weight ratio of 80/20 were synthesized by the direct miniemulsion method, respectively. The average size of the capsules is 140. nm and 119. nm, respectively. The chemical structure of the sample was analyzed using Fourier Transformed Infrared Spectroscopy (FTIR). Crystallography of nanocapsules was investigated by X-ray diffractometer. The surface morphology was studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The thermal properties and thermal stability of the sample were obtained from Differential Scanning Calorimeter (DSC) and Thermal Gravimetric Analysis (TGA). The temperatures and latent heats of melting and crystallizing of PEMA nanocapsule were determined as 32.7 and 29.8 ??C, 198.5 and -197.1. kJ/kg, respectively. TGA analysis indicated that PEMA/octadecane nanocapsule had good thermal stability. The nanocapsules prepared in this work had a much higher encapsulation ratio (89.5%) and encapsulation efficiency (89.5%). Therefore, the findings of the work lead to the conclusion that the present work provides a novel method for fabricating nanoencapsulated phase change material, and it has a better potential for thermal energy storage. ?? 2012 Elsevier Ltd.},
 bibtype = {article},
 author = {Zhang, G. H. and Bon, S. A F and Zhao, C. Y.},
 doi = {10.1016/j.solener.2012.01.003},
 journal = {Solar Energy},
 number = {5}
}

In this paper, nanocapsules containing n-octadecane with an average 50. nm thick shell of poly(ethyl methacrylate) (PEMA) and poly(methyl methacrylate) (PMMA), and a core/shell weight ratio of 80/20 were synthesized by the direct miniemulsion method, respectively. The average size of the capsules is 140. nm and 119. nm, respectively. The chemical structure of the sample was analyzed using Fourier Transformed Infrared Spectroscopy (FTIR). Crystallography of nanocapsules was investigated by X-ray diffractometer. The surface morphology was studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The thermal properties and thermal stability of the sample were obtained from Differential Scanning Calorimeter (DSC) and Thermal Gravimetric Analysis (TGA). The temperatures and latent heats of melting and crystallizing of PEMA nanocapsule were determined as 32.7 and 29.8 ??C, 198.5 and -197.1. kJ/kg, respectively. TGA analysis indicated that PEMA/octadecane nanocapsule had good thermal stability. The nanocapsules prepared in this work had a much higher encapsulation ratio (89.5%) and encapsulation efficiency (89.5%). Therefore, the findings of the work lead to the conclusion that the present work provides a novel method for fabricating nanoencapsulated phase change material, and it has a better potential for thermal energy storage. ?? 2012 Elsevier Ltd.

@article{
 title = {Multiple hydrogen-bond array reinforced cellular polymer films from colloidal crystalline assemblies of soft latex particles},
 type = {article},
 year = {2012},
 pages = {603-608},
 volume = {1},
 websites = {http://pubs.acs.org/doi/abs/10.1021/mz300126u},
 publisher = {ACS Publications},
 id = {46363e97-e027-3b1f-ac58-a27c22c2eac8},
 created = {2024-01-02T14:09:39.699Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:39.699Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {chen2012multiple},
 source_type = {article},
 private_publication = {false},
 abstract = {Waterborne polymer films made from soft polymer latex dispersions generally suffer from deterioration of chemical resistance and physical barrier properties under high humidity conditions and upon solvent exposure. Here we demonstrate the fabrication of robust polyhedral cellular polymer films from poly(methyl methacrylate-co-butyl acrylate) latexes, which were made by emulsion polymerization using a 2-ureido-4-pyrimidinone (UPy) functional methacrylate comonomer. Multiple hydrogen bond (MHB) arrays provided by UPy groups arrest the film formation process thereby creating a cellular reinforcement. The cellular polymer films exhibit impressive physical and mechanical properties. Upon solvent exposure, the films show colloidal crystalline-type Bragg diffraction features and do not suffer excessive and deteriorative uptake of water and, more remarkably, can absorb high amounts of organic solvents, thereby turning into an organogel with preservation of shape, up to a 14-fold volumetric swelling ratio of the polymer films in case of chloroform.},
 bibtype = {article},
 author = {Chen, Yunhua and Jones, Samuel T. and Hancox, Ian and Beanland, Richard and Tunnah, Edward J. and Bon, Stefan A F},
 doi = {10.1021/mz300126u},
 journal = {ACS Macro Letters},
 number = {5}
}

Waterborne polymer films made from soft polymer latex dispersions generally suffer from deterioration of chemical resistance and physical barrier properties under high humidity conditions and upon solvent exposure. Here we demonstrate the fabrication of robust polyhedral cellular polymer films from poly(methyl methacrylate-co-butyl acrylate) latexes, which were made by emulsion polymerization using a 2-ureido-4-pyrimidinone (UPy) functional methacrylate comonomer. Multiple hydrogen bond (MHB) arrays provided by UPy groups arrest the film formation process thereby creating a cellular reinforcement. The cellular polymer films exhibit impressive physical and mechanical properties. Upon solvent exposure, the films show colloidal crystalline-type Bragg diffraction features and do not suffer excessive and deteriorative uptake of water and, more remarkably, can absorb high amounts of organic solvents, thereby turning into an organogel with preservation of shape, up to a 14-fold volumetric swelling ratio of the polymer films in case of chloroform.

@article{
 title = {High internal phase emulsion gels (HIPE-gels) from polymer dispersions reinforced with quadruple hydrogen bond functionality.},
 type = {article},
 year = {2012},
 pages = {1117-9},
 volume = {48},
 websites = {http://www.ncbi.nlm.nih.gov/pubmed/22159305},
 publisher = {The Royal Society of Chemistry},
 id = {ebb08a58-3bed-3ce1-afe4-573db9088775},
 created = {2024-01-02T14:09:40.613Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:40.613Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {chen2012high},
 source_type = {article},
 private_publication = {false},
 abstract = {A convenient route to organogels templated by high internal phase emulsions has been developed. Key is the use of a waterborne polymer latex loaded with a multiple hydrogen bond (MHB) functionality that becomes disentangled and transfers across the oil-water interface forming a gel network in the oil phase via hydrogen bond interactions.},
 bibtype = {article},
 author = {Chen, Yunhua and Ballard, Nicholas and Gayet, Florence and Bon, Stefan a F},
 doi = {10.1039/c2cc16670d},
 journal = {Chemical communications (Cambridge, England)},
 number = {8}
}

A convenient route to organogels templated by high internal phase emulsions has been developed. Key is the use of a waterborne polymer latex loaded with a multiple hydrogen bond (MHB) functionality that becomes disentangled and transfers across the oil-water interface forming a gel network in the oil phase via hydrogen bond interactions.

@article{
 title = {A simple microfluidic device for fabrication of double emulsion droplets and polymer microcapsules},
 type = {article},
 year = {2012},
 pages = {1043},
 volume = {3},
 websites = {http://xlink.rsc.org/?DOI=c2py00605g},
 publisher = {Royal Society of Chemistry},
 id = {c9087ed6-3103-34e4-ad75-148d9f0d5dde},
 created = {2024-01-02T14:09:40.784Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:40.784Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {nurumbetov2012simple},
 source_type = {article},
 private_publication = {false},
 abstract = {We demonstrate that by using a syringe needle, plastic tubing, two glass capillaries and epoxy glue a microfluidic device can be fabricated straightforwardly that allows for the production of double emulsions, or in other words the generation of droplets-in-droplets. The device in essence is a serial combination of droplet generation by co-flow and a T-junction. To reduce potential issues with channel wetting, we established that an "obstructed" T-junction outperformed a conventional T-junction. We illustrate the versatility of our device through production of a range of polymer microcapsules, including ones that contain a waterborne dispersion of colour changing pigment, and microcapsules with compartmentalized ferrofluidic segments, that is capsules that contain more than one droplet of ferrofluid. © 2012 The Royal Society of Chemistry.},
 bibtype = {article},
 author = {Nurumbetov, Gabit and Ballard, Nicholas and Bon, Stefan A. F.},
 doi = {10.1039/c2py00605g},
 journal = {Polymer Chemistry},
 number = {4}
}

We demonstrate that by using a syringe needle, plastic tubing, two glass capillaries and epoxy glue a microfluidic device can be fabricated straightforwardly that allows for the production of double emulsions, or in other words the generation of droplets-in-droplets. The device in essence is a serial combination of droplet generation by co-flow and a T-junction. To reduce potential issues with channel wetting, we established that an "obstructed" T-junction outperformed a conventional T-junction. We illustrate the versatility of our device through production of a range of polymer microcapsules, including ones that contain a waterborne dispersion of colour changing pigment, and microcapsules with compartmentalized ferrofluidic segments, that is capsules that contain more than one droplet of ferrofluid. © 2012 The Royal Society of Chemistry.

@article{
 title = {"Sandwich" microcontact printing as a mild route towards monodisperse Janus particles with tailored bifunctionality},
 type = {article},
 year = {2011},
 keywords = {Janus particles,epoxides,microcontact printing,microfluidics,polymers},
 pages = {79-83},
 volume = {23},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/adma.201003564/full},
 publisher = {WILEY-VCH Verlag},
 id = {6194a56f-01e4-36d6-a668-39d7a8fb3902},
 created = {2024-01-02T14:09:37.311Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:37.311Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {kaufmann2011sandwich},
 source_type = {article},
 private_publication = {false},
 abstract = {A “sandwich” microcontact printing method is reported. A monolayer of porous epoxy polymer microspheres is transformed into Janus particles with distinct functionality on each face by reaction with amine functional fluorescent dyes, carbohydrates, and magnetic nanoparticles.},
 bibtype = {article},
 author = {Kaufmann, Tobias and Gokmen, M. Talha and Wendeln, Christian and Schneiders, Martin and Rinnen, Stefan and Arlinghaus, Heinrich F. and Bon, Stefan A F and Du Prez, Filip E. and Ravoo, Bart Jan},
 doi = {10.1002/adma.201003564},
 journal = {Advanced Materials},
 number = {1}
}

A “sandwich” microcontact printing method is reported. A monolayer of porous epoxy polymer microspheres is transformed into Janus particles with distinct functionality on each face by reaction with amine functional fluorescent dyes, carbohydrates, and magnetic nanoparticles.

@article{
 title = {Hybrid biological spores wrapped in a mesh composed of interpenetrating polymer nanoparticles as “patchy” Pickering stabilizers},
 type = {article},
 year = {2011},
 keywords = {QD Chemistry},
 pages = {823-827},
 volume = {2},
 websites = {http://dx.doi.org/10.1039/C0PY00335B},
 month = {3},
 publisher = {The Royal Society of Chemistry},
 day = {15},
 id = {832c2d97-92ad-31c9-91e3-f5d059cc19bb},
 created = {2024-01-02T14:09:45.930Z},
 accessed = {2014-05-29},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:45.930Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Ballard2011},
 language = {en},
 private_publication = {false},
 abstract = {We describe a new method for the decoration of the intricate morphology of spore particles with polymer nanoparticles and investigate their behaviour at liquid–liquid interfaces. We found a large difference in the interfacial activity between spherical microspheres and the anisotropic particles synthesized here and describe this in terms of particle wettability.},
 bibtype = {article},
 author = {Ballard, Nicholas and Bon, Stefan Antonius Franciscus},
 doi = {10.1039/C0PY00335B},
 journal = {Polymer Chemistry},
 number = {4}
}

We describe a new method for the decoration of the intricate morphology of spore particles with polymer nanoparticles and investigate their behaviour at liquid–liquid interfaces. We found a large difference in the interfacial activity between spherical microspheres and the anisotropic particles synthesized here and describe this in terms of particle wettability.

@article{
 title = {Polymer vesicles with a colloidal armor of nanoparticles},
 type = {article},
 year = {2011},
 pages = {2151-2153},
 volume = {133},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ja110359f},
 month = {2},
 publisher = {American Chemical Society},
 day = {23},
 id = {912fc811-29f6-333d-b282-6d52ebc7f4cd},
 created = {2024-01-02T14:09:46.470Z},
 accessed = {2014-04-14},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:46.470Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Chen2011},
 private_publication = {false},
 abstract = {The fabrication of polymer vesicles with a colloidal armor made from a variety of nanoparticles is demonstrated. In addition, it is shown that the armored supracolloidal structure can be postmodified through film-formation of soft polymer latex particles on the surface of the polymersome, hereby effectively wrapping the polymersome in a plastic bag, as well as through formation of a hydrogel by disintegrating an assembled polymer latex made from poly(ethyl acrylate-co-methacrylic acid) upon increasing the pH. Furthermore, ordering and packing patterns are briefly addressed with the aid of Monte Carlo simulations, including patterns observed when polymersomes are exposed to a binary mixture of colloids of different size.},
 bibtype = {article},
 author = {Chen, Rong and Pearce, Daniel J G and Fortuna, Sara and Cheung, David L. and Bon, Stefan A F},
 doi = {10.1021/ja110359f},
 journal = {Journal of the American Chemical Society},
 number = {7}
}

The fabrication of polymer vesicles with a colloidal armor made from a variety of nanoparticles is demonstrated. In addition, it is shown that the armored supracolloidal structure can be postmodified through film-formation of soft polymer latex particles on the surface of the polymersome, hereby effectively wrapping the polymersome in a plastic bag, as well as through formation of a hydrogel by disintegrating an assembled polymer latex made from poly(ethyl acrylate-co-methacrylic acid) upon increasing the pH. Furthermore, ordering and packing patterns are briefly addressed with the aid of Monte Carlo simulations, including patterns observed when polymersomes are exposed to a binary mixture of colloids of different size.

@article{
 title = {Pickering emulsion polymerization using Laponite clay as stabilizer to prepare armored "soft" polymer latexes},
 type = {article},
 year = {2011},
 pages = {7415-7422},
 volume = {44},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma201691u},
 month = {9},
 id = {67188ad4-04cf-34da-bff0-4df76d282b13},
 created = {2024-01-02T14:09:48.012Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:48.012Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000295058400038},
 source_type = {article},
 private_publication = {false},
 abstract = {The fabrication of “soft” nanocomposite clay armored polymer latexes is described. Laponite clay XLS is used as stabilizer in the Pickering emulsion polymerization of a variety of monomer mixtures, that is, methyl methacrylate and n-butyl acrylate, styrene and n-butyl acrylate, and styrene and 2-ethylhexyl acrylate. Overall solids contents of the hybrid latexes in complete absence of coagulation of up to 24 wt % are reported under batch conditions. Key mechanistic aspects of the Pickering emulsion polymerization process are discussed. The use of monomers that have high water solubility and are prone to hydrolyze under basic conditions, for example methyl methacrylate, should be restricted. The use of small amounts of methacrylic acid as auxiliary monomer promotes clay adhesion to the surface of the particles in the Pickering emulsion (co)polymerization of hydrophobic monomers. Detailed kinetic studies at both 60 and 80 °C of the Pickering emulsion copolymerization of styrene and n-butyl acrylate (Sty:BA = 0.67 w/w) are reported, with varying amounts of Pickering stabilizer. The Laponite clay discs play a crucial role in the particle formation (nucleation) stage of the Pickering emulsion polymerization process. Use of increasing amounts leads to smaller average particle sizes but inflicts longer nucleation periods, thereby broadening the particle size distributions. We report the occurrence of a catastrophic coagulation phenomenon for Pickering emulsion polymerizations carried out at a low initiator (ammonium persulfate) flux at 60 °C, for a small window of concentrations of Laponite clay discs.},
 bibtype = {article},
 author = {Teixeira, Roberto F A and McKenzie, Holly S. and Boyd, Ashton A. and Bon, Stefan A F},
 doi = {10.1021/ma201691u},
 journal = {Macromolecules},
 number = {18}
}

The fabrication of “soft” nanocomposite clay armored polymer latexes is described. Laponite clay XLS is used as stabilizer in the Pickering emulsion polymerization of a variety of monomer mixtures, that is, methyl methacrylate and n-butyl acrylate, styrene and n-butyl acrylate, and styrene and 2-ethylhexyl acrylate. Overall solids contents of the hybrid latexes in complete absence of coagulation of up to 24 wt % are reported under batch conditions. Key mechanistic aspects of the Pickering emulsion polymerization process are discussed. The use of monomers that have high water solubility and are prone to hydrolyze under basic conditions, for example methyl methacrylate, should be restricted. The use of small amounts of methacrylic acid as auxiliary monomer promotes clay adhesion to the surface of the particles in the Pickering emulsion (co)polymerization of hydrophobic monomers. Detailed kinetic studies at both 60 and 80 °C of the Pickering emulsion copolymerization of styrene and n-butyl acrylate (Sty:BA = 0.67 w/w) are reported, with varying amounts of Pickering stabilizer. The Laponite clay discs play a crucial role in the particle formation (nucleation) stage of the Pickering emulsion polymerization process. Use of increasing amounts leads to smaller average particle sizes but inflicts longer nucleation periods, thereby broadening the particle size distributions. We report the occurrence of a catastrophic coagulation phenomenon for Pickering emulsion polymerizations carried out at a low initiator (ammonium persulfate) flux at 60 °C, for a small window of concentrations of Laponite clay discs.

@article{
 title = {Self-assembly of amphiphilic peanut-shaped nanoparticles},
 type = {article},
 year = {2010},
 pages = {074901},
 volume = {132},
 websites = {http://scitation.aip.org/content/aip/journal/jcp/132/7/10.1063/1.3316794},
 month = {2},
 publisher = {AIP Publishing},
 day = {21},
 id = {2faea6ae-c25a-31d3-b057-3596fa1b1edc},
 created = {2024-01-02T14:09:45.126Z},
 accessed = {2014-08-10},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:45.126Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Whitelam2010},
 private_publication = {false},
 abstract = {We use computer simulation to investigate the self-assembly of Janus-like amphiphilic peanut-shaped nanoparticles, finding phases of clusters, bilayers, and micelles in accord with ideas of packing familiar from the study of molecular surfactants. However, packing arguments do not explain the hierarchical self-assembly dynamics that we observe, nor the coexistence of bilayers and faceted polyhedra. This coexistence suggests that experimental realizations of our model can achieve multipotent assembly of either of two competing ordered structures.},
 bibtype = {article},
 author = {Whitelam, Stephen and Bon, Stefan A F},
 doi = {10.1063/1.3316794},
 journal = {Journal of Chemical Physics},
 number = {7}
}

We use computer simulation to investigate the self-assembly of Janus-like amphiphilic peanut-shaped nanoparticles, finding phases of clusters, bilayers, and micelles in accord with ideas of packing familiar from the study of molecular surfactants. However, packing arguments do not explain the hierarchical self-assembly dynamics that we observe, nor the coexistence of bilayers and faceted polyhedra. This coexistence suggests that experimental realizations of our model can achieve multipotent assembly of either of two competing ordered structures.

@inbook{
 type = {inbook},
 year = {2010},
 keywords = {Colloids,Heterocoagulation,Nanocomposites,Pickering stabilization,Polymer latex,Self-assembly,Supracolloidal structures},
 pages = {19-52},
 volume = {233},
 websites = {http://link.springer.com/chapter/10.1007/12_2010_65},
 series = {Advances in Polymer Science},
 id = {afdda3be-cbea-34be-8688-f74b495d2dfc},
 created = {2024-01-02T14:09:48.670Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:48.670Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000283625600002},
 source_type = {incollection},
 private_publication = {false},
 abstract = {In this chapter,we will highlight conceptual physical approaches towards the fabrication of nanocomposite polymer latexes inwhich each individual latex par- ticle contains one or more “hard” nanoparticles, such as clays, silicates, titanates, or other metal(oxides). By “physical approaches” we mean that the “hard” nanoparti- cles are added as pre-existing entities, and are not synthesized in situ as part of the nanocomposite polymer latex fabrication process.We will narrow our discussion to focus on physical methods that rely on the assembly of nanoparticles onto the la- tex particles after the latex particles have been formed, or its reciprocal analogue, the adhesion of polymer onto an inorganic nanoparticle. First, will discuss the phe- nomenon of heterocoagulation and its various driving forces, such as electrostatic interactions, the hydrophobic effect, and secondary molecular interactions.We will then address methods that involve assembly of nanoparticles onto or around the more liquid precursors (i.e., swollen/growing latex particles or monomer droplets). We will focus on the phenomenon of Pickering stabilization.We will then discuss features of particle interaction with soft interfaces, and see how the adhesion of particles onto emulsion droplets can be applied in suspension, miniemulsion, and emulsion polymerization. Finally, we will very briefly mention some interesting methods that make use of interface-driven templating for making well-defined assembled clusters and supracolloidal structures.},
 bibtype = {inbook},
 author = {Teixeira, Roberto F.A. and Bon, Stefan A.F.},
 editor = {van Herk, Alex M and Landfester, K},
 doi = {10.1007/12-2010-65},
 chapter = {Physical methods for the preparation of hybrid nanocomposite polymer latex particles},
 title = {Advances in Polymer Science}
}

In this chapter,we will highlight conceptual physical approaches towards the fabrication of nanocomposite polymer latexes inwhich each individual latex par- ticle contains one or more “hard” nanoparticles, such as clays, silicates, titanates, or other metal(oxides). By “physical approaches” we mean that the “hard” nanoparti- cles are added as pre-existing entities, and are not synthesized in situ as part of the nanocomposite polymer latex fabrication process.We will narrow our discussion to focus on physical methods that rely on the assembly of nanoparticles onto the la- tex particles after the latex particles have been formed, or its reciprocal analogue, the adhesion of polymer onto an inorganic nanoparticle. First, will discuss the phe- nomenon of heterocoagulation and its various driving forces, such as electrostatic interactions, the hydrophobic effect, and secondary molecular interactions.We will then address methods that involve assembly of nanoparticles onto or around the more liquid precursors (i.e., swollen/growing latex particles or monomer droplets). We will focus on the phenomenon of Pickering stabilization.We will then discuss features of particle interaction with soft interfaces, and see how the adhesion of particles onto emulsion droplets can be applied in suspension, miniemulsion, and emulsion polymerization. Finally, we will very briefly mention some interesting methods that make use of interface-driven templating for making well-defined assembled clusters and supracolloidal structures.

@article{
 title = {Unraveling mechanistic events in solids-stabilized emulsion polymerization by monitoring the concentration of nanoparticles in the water phase},
 type = {article},
 year = {2010},
 pages = {7915-7921},
 volume = {26},
 websites = {http://pubs.acs.org/doi/abs/10.1021/la904817f},
 month = {6},
 id = {cdff83aa-0f4b-3d23-9312-8a12f2191434},
 created = {2024-01-02T14:09:49.547Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:49.547Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000277928100039},
 source_type = {article},
 private_publication = {false},
 abstract = {The fate of nanoparticles used as stabilizers in solids-stabilized, or Pickering, emulsion polymerization for the formation of armored hybrid polymer latexes was studied. We showed that disk centrifugation can be used as a powerful quantitative tool to analyze and determine the concentration of nanoparticles in the water phase throughout solids-stabilized emulsion polymerizations. We performed a series of emulsion polymerizations using vinyl acetate, vinyl pivalate, methyl methacrylate, or butyl acrylate in presence of silica nanoparticles (Ludox TM-40, ca. 25 nm in diameter). The developed method to quantify the number of silica nanoparticles in the water phase proved to be an invaluable tool for determining key features of the polymerization process. The obtained concentration profiles versus monomer conversion explained the existence of limited coalescence of armored particles in the later stages of the solids-stabilized emulsion polymerization process of vinyl acetate, leading to nonspherical structur...},
 bibtype = {article},
 author = {Colard, Catheline A L and Teixeira, Roberto F A and Bon, Stefan A F},
 doi = {10.1021/la904817f},
 journal = {Langmuir},
 number = {11}
}

The fate of nanoparticles used as stabilizers in solids-stabilized, or Pickering, emulsion polymerization for the formation of armored hybrid polymer latexes was studied. We showed that disk centrifugation can be used as a powerful quantitative tool to analyze and determine the concentration of nanoparticles in the water phase throughout solids-stabilized emulsion polymerizations. We performed a series of emulsion polymerizations using vinyl acetate, vinyl pivalate, methyl methacrylate, or butyl acrylate in presence of silica nanoparticles (Ludox TM-40, ca. 25 nm in diameter). The developed method to quantify the number of silica nanoparticles in the water phase proved to be an invaluable tool for determining key features of the polymerization process. The obtained concentration profiles versus monomer conversion explained the existence of limited coalescence of armored particles in the later stages of the solids-stabilized emulsion polymerization process of vinyl acetate, leading to nonspherical structur...

@article{
 title = {Conducting nanocomposite polymer foams from lce-crystal-templated assembly of mixtures of colloids},
 type = {article},
 year = {2009},
 pages = {2894-2898},
 volume = {21},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/adma.200803007/abstract},
 publisher = {WILEY-VCH Verlag},
 id = {62381197-d882-37c2-a15f-163d674fc2c4},
 created = {2024-01-02T14:09:34.764Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:34.764Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {colard2009conducting},
 source_type = {article},
 private_publication = {false},
 abstract = {Fabrication of conducting nanocomposite-reinforced soft polymer foams is demonstrated. These multicomponent cellular materials are built from a mixture of colloids dispersed in water by freeze-drying, thereby using ice crystals as template for the porous structure. An excluded-volume effect armors the "soft"-polymer cell walls with "hard" nanoparticles, thereby enhancing the mechanical robustness of the foams.},
 bibtype = {article},
 author = {Colard, Catheline A L and Cave, Richard A. and Grossiord, Nadia and Covington, James A. and Bon, Stefan A F},
 doi = {10.1002/adma.200803007},
 journal = {Advanced Materials},
 number = {28}
}

Fabrication of conducting nanocomposite-reinforced soft polymer foams is demonstrated. These multicomponent cellular materials are built from a mixture of colloids dispersed in water by freeze-drying, thereby using ice crystals as template for the porous structure. An excluded-volume effect armors the "soft"-polymer cell walls with "hard" nanoparticles, thereby enhancing the mechanical robustness of the foams.

@article{
 title = {Open-cellular organic semiconductor thin films by vertical co-deposition using sub-100 nm nanosphere templates},
 type = {article},
 year = {2009},
 pages = {6478-6480},
 volume = {42},
 websites = {http://www.ncbi.nlm.nih.gov/pubmed/19841815},
 id = {0bf8552d-7945-32fe-8141-69864abc2678},
 created = {2024-01-02T14:09:35.930Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:35.930Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {schumann2009vertical},
 source_type = {article},
 private_publication = {false},
 abstract = {Vertical co-deposition of sub-100 nm polystyrene sphere templates with water-soluble small molecule or polymeric semiconductors, followed by solvent vapour assisted sphere removal, is shown to be an excellent method for generating porous large area organic semiconductor thin films with sub-100 nm open-cellular networks, with numerous potential applications in areas such as sensing and photovoltaics.},
 bibtype = {article},
 author = {Schumann, S and Bon, S A and Hatton, R A and Jones, T S},
 doi = {10.1039/b914136g},
 journal = {Chem Commun (Camb)},
 number = {42}
}

Vertical co-deposition of sub-100 nm polystyrene sphere templates with water-soluble small molecule or polymeric semiconductors, followed by solvent vapour assisted sphere removal, is shown to be an excellent method for generating porous large area organic semiconductor thin films with sub-100 nm open-cellular networks, with numerous potential applications in areas such as sensing and photovoltaics.

@article{
 title = {Water-Soluble and Water Dispersible Polymers by Living Radical Polymerisation BT  - Stimuli Responsive Water-Soluble and Amphiphilic (Co)polymers},
 type = {article},
 year = {2009},
 pages = {148-161},
 volume = {780},
 websites = {http://pubs.acs.org/doi/abs/10.1021/bk-2001-0780.ch009%5Cnpapers3://publication/doi/10.1021/bk-2001-0780.ch009},
 publisher = {ACS Publications},
 id = {3c145f49-41b6-36db-aa86-9100ee681ab2},
 created = {2024-01-02T14:09:41.364Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:41.364Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon2001water},
 source_type = {article},
 private_publication = {false},
 abstract = {An overview of recent advances in living radical polymerisation under aqueous conditions and the synthesis of water-soluble and dispersible polymers by living radical polymerisation techniques is given. Living radical polymerisation involving nitroxide stabilised radicals, transition metal mediated and reversible addition fragmentation (RAFT) is covered. This overview is followed by some specific examples of the use of copper(I) mediated living radical polymerisation for the synthesis of some water soluble/dispersible polymers. Firstly the use of a modified SPAN surfactant to polymerise 2-(dimethylamino)ethyl methacrylate (DMAEMA) producing polymers with narrow polydispersity and controlled Mn is described (Mn = 6700, PDI = 1.27). These polymers disperse in acidic aqueous media with a CAC of 0.16 gL-1. Derivatised solketal is described as an initator for sequential atom transfer polymerisation of methyl methacrylate (MMA) and DMAEMA to give Y-shaped water soluble polymers. These two examples serve to illustrate the range of topology and hydrophilic functionality which can easily be incorporated into vinyl polymers through living radical methodology.},
 bibtype = {article},
 author = {Bon, Stefan A F and Ohno, Kohji and Haddleton, David M},
 doi = {10.1021/bk-2001-0780.ch009},
 journal = {Stimuli Responsive Water-Soluble and Amphiphilic (Co)polymers}
}

An overview of recent advances in living radical polymerisation under aqueous conditions and the synthesis of water-soluble and dispersible polymers by living radical polymerisation techniques is given. Living radical polymerisation involving nitroxide stabilised radicals, transition metal mediated and reversible addition fragmentation (RAFT) is covered. This overview is followed by some specific examples of the use of copper(I) mediated living radical polymerisation for the synthesis of some water soluble/dispersible polymers. Firstly the use of a modified SPAN surfactant to polymerise 2-(dimethylamino)ethyl methacrylate (DMAEMA) producing polymers with narrow polydispersity and controlled Mn is described (Mn = 6700, PDI = 1.27). These polymers disperse in acidic aqueous media with a CAC of 0.16 gL-1. Derivatised solketal is described as an initator for sequential atom transfer polymerisation of methyl methacrylate (MMA) and DMAEMA to give Y-shaped water soluble polymers. These two examples serve to illustrate the range of topology and hydrophilic functionality which can easily be incorporated into vinyl polymers through living radical methodology.

@article{
 title = {Fabrication of porous clickable polymer beads and rods through generation of high internal phase emulsion (HIPE) droplets in a simple microfluidic device},
 type = {article},
 year = {2009},
 pages = {9289-9294},
 volume = {42},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma9018679},
 publisher = {American Chemical Society},
 id = {4046d7fd-bdf2-3244-8234-51624ead4775},
 created = {2024-01-02T14:09:42.145Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:42.145Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {gokmen2009fabrication},
 source_type = {article},
 private_publication = {false},
 abstract = {The fabrication of micrometer-sized monodisperse highly porous polymer particles. of both spherical and rodlike shapes, using a simple microfluidic setup is demonstrated. Droplets were generated in a coflow device from a water-in-oil high internal phase emulsion (HIPE), hereby creating a water-in-oil-water (W/O/W) emulsion, The individual droplets of monomer HIPE were polymerized downstream in the channel through photopolymerization. The polymer particles produced via this strategy possess very large macropores in comparison with the more conventional porous polymer beads synthesized by inducing in situ phase separation throughout the polymerization process through the use of porogenic solvents. Epoxy-functionalized Porous particles made using the HIPE microfluidic method showed superior performance in consecutive azide and cycloaddition "click"-"click" modification procedure monitored by IR. Our microfluidic approach led to the successful miniaturization of monodisperse submillimeter spherical poly(HIPE) beads, down to diameters of 400 mu m. More strikingly is the production of poly(HIPE) rods, which were obtained by using a Viscous HIPE, which in coflow emulsification formed an unstable jet that broke up into rodlike sections. These rodlike droplets maintained their shapes throughout the microfluidic channel and did not relax back into spherical droplets, allowing for production of poly(HIPE) rods upon photopolymerization. The nonspherical shape in this case is not determined by confined channel geometries, which to the best Of Our knowledge is unprecedented as a strategy to produce nonspherical polymer particles with microfluidics.},
 bibtype = {article},
 author = {Gokmen, M. Talha and Van Camp, Wim and Colver, Patrick J. and Bon, Stefan A.F. and Du Prez, Filip E.},
 doi = {10.1021/ma9018679},
 journal = {Macromolecules},
 number = {23}
}

The fabrication of micrometer-sized monodisperse highly porous polymer particles. of both spherical and rodlike shapes, using a simple microfluidic setup is demonstrated. Droplets were generated in a coflow device from a water-in-oil high internal phase emulsion (HIPE), hereby creating a water-in-oil-water (W/O/W) emulsion, The individual droplets of monomer HIPE were polymerized downstream in the channel through photopolymerization. The polymer particles produced via this strategy possess very large macropores in comparison with the more conventional porous polymer beads synthesized by inducing in situ phase separation throughout the polymerization process through the use of porogenic solvents. Epoxy-functionalized Porous particles made using the HIPE microfluidic method showed superior performance in consecutive azide and cycloaddition "click"-"click" modification procedure monitored by IR. Our microfluidic approach led to the successful miniaturization of monodisperse submillimeter spherical poly(HIPE) beads, down to diameters of 400 mu m. More strikingly is the production of poly(HIPE) rods, which were obtained by using a Viscous HIPE, which in coflow emulsification formed an unstable jet that broke up into rodlike sections. These rodlike droplets maintained their shapes throughout the microfluidic channel and did not relax back into spherical droplets, allowing for production of poly(HIPE) rods upon photopolymerization. The nonspherical shape in this case is not determined by confined channel geometries, which to the best Of Our knowledge is unprecedented as a strategy to produce nonspherical polymer particles with microfluidics.

@article{
 title = {Stability of Janus nanoparticles at fluid interfaces},
 type = {article},
 year = {2009},
 keywords = {computer-simulation,crystals,emulsions,liquid-liquid interfaces,particles,tension,vapor interface,water,wettability,wetting behavior},
 pages = {3969-3976},
 volume = {5},
 month = {10},
 publisher = {The Royal Society of Chemistry},
 day = {6},
 id = {dd66a1c7-b0e9-3342-887d-27443d84fb2b},
 created = {2024-01-02T14:09:45.295Z},
 accessed = {2014-08-22},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:45.295Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Cheung2009},
 language = {en},
 private_publication = {false},
 abstract = {Using Monte Carlo simulations the interaction of a nanometre-sized, spherical Janus particle (a particle with two distinct surface regions of different functionality, in this case showing amphiphilic behaviour) with an ideal fluid interface is studied. In common with previous simulations of spherical, isotropic particles, the range of the nanoparticle-interface interaction is significantly larger than the nanoparticle radius due to the broadening of the interface due to capillary waves. For a uniform particle (an isotropic particle with one surface characteristic) the stability of the particle at a liquid interface is decreased as the affinity for one liquid phase is increased relative to the other; for large affinity differences the detachment energies calculated from continuum theory become increasingly accurate. For a symmetric Janus particle (where the two different surface regions are of equal area), the presence of the particle at the interface becomes more stable upon increasing the difference in affinity between the two faces, with each face having a high affinity for the respective liquid phase. In the case studied here, where surface tension between the A-region of the particle with the A-component is identical to the surface tension between the B-region and B-component, the interaction is symmetric with respect to the nanoparticle interface separation. The particle is found to have a large degree of orientational freedom, in sharp contrast to micrometre-sized colloidal particles. Comparison with continuum theory shows that this significantly overestimates the detachment energy, due to its neglect of nanoparticle rotation; simulations of nanoparticles with fixed orientations show a considerably larger detachment energy. As the areas of the surface regions become asymmetric the stability of the Janus nanoparticle is decreased and, in the case of large differences in affinities of the two faces, the difference between detachment energies from simulation and continuum theory diminishes.},
 bibtype = {article},
 author = {Cheung, D L and Bon, S A F},
 doi = {10.1039/b908462b},
 journal = {Soft Matter},
 number = {20}
}

Using Monte Carlo simulations the interaction of a nanometre-sized, spherical Janus particle (a particle with two distinct surface regions of different functionality, in this case showing amphiphilic behaviour) with an ideal fluid interface is studied. In common with previous simulations of spherical, isotropic particles, the range of the nanoparticle-interface interaction is significantly larger than the nanoparticle radius due to the broadening of the interface due to capillary waves. For a uniform particle (an isotropic particle with one surface characteristic) the stability of the particle at a liquid interface is decreased as the affinity for one liquid phase is increased relative to the other; for large affinity differences the detachment energies calculated from continuum theory become increasingly accurate. For a symmetric Janus particle (where the two different surface regions are of equal area), the presence of the particle at the interface becomes more stable upon increasing the difference in affinity between the two faces, with each face having a high affinity for the respective liquid phase. In the case studied here, where surface tension between the A-region of the particle with the A-component is identical to the surface tension between the B-region and B-component, the interaction is symmetric with respect to the nanoparticle interface separation. The particle is found to have a large degree of orientational freedom, in sharp contrast to micrometre-sized colloidal particles. Comparison with continuum theory shows that this significantly overestimates the detachment energy, due to its neglect of nanoparticle rotation; simulations of nanoparticles with fixed orientations show a considerably larger detachment energy. As the areas of the surface regions become asymmetric the stability of the Janus nanoparticle is decreased and, in the case of large differences in affinities of the two faces, the difference between detachment energies from simulation and continuum theory diminishes.

@article{
 title = {Interaction of nanoparticles with ideal liquid-liquid interfaces},
 type = {article},
 year = {2009},
 pages = {066103},
 volume = {102},
 websites = {http://link.aps.org/doi/10.1103/PhysRevLett.102.066103},
 month = {2},
 id = {48a381e4-e089-30f4-b511-b191b3bbf84c},
 created = {2024-01-02T14:09:46.260Z},
 accessed = {2014-05-29},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:46.260Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Cheung2009a},
 private_publication = {false},
 abstract = {Using molecular simulations the interaction between a noncharged nanoparticle and an ideal liquid-liquid interface is studied. The free energy profile as function of nanoparticle-interface separation is determined using Wang-Landau sampling. Comparison between the simulation results and macroscopic theories shows that the latter give a poor description of the free energy profile. In particular, they underestimate both the range of interaction between the particle and the interface and its strength, with the discrepancy lessening as the particle radius increases. On increasing the solvent chemical potential the interaction strength increases and the interaction range decreases due to the increase in interfacial tension and consequent decrease in interfacial width.},
 bibtype = {article},
 author = {Cheung, David L. and Bon, Stefan A F},
 doi = {10.1103/PhysRevLett.102.066103},
 journal = {Physical Review Letters},
 number = {6}
}

Using molecular simulations the interaction between a noncharged nanoparticle and an ideal liquid-liquid interface is studied. The free energy profile as function of nanoparticle-interface separation is determined using Wang-Landau sampling. Comparison between the simulation results and macroscopic theories shows that the latter give a poor description of the free energy profile. In particular, they underestimate both the range of interaction between the particle and the interface and its strength, with the discrepancy lessening as the particle radius increases. On increasing the solvent chemical potential the interaction strength increases and the interaction range decreases due to the increase in interfacial tension and consequent decrease in interfacial width.

@article{
 title = {Soft polymer and nano-clay supracolloidal particles in adhesives : synergistic effects on mechanical properties},
 type = {article},
 year = {2009},
 keywords = {QD Chemistry,TA Engineering (General). Civil engineering (Gener,TP Chemical technology},
 pages = {3842-3849},
 volume = {5},
 websites = {http://dx.doi.org/10.1039/b904740a},
 id = {77fbd1f7-3bb4-33ed-af79-993326ba1d68},
 created = {2024-01-02T14:09:49.119Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:49.119Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000270542600010},
 source_type = {article},
 private_publication = {false},
 abstract = {Numerous synthesis routes toward nanostructured polymer particles have emerged, but few examples demonstrate the essential need for such complex particle structures to achieve any added benefit in a target application. Here, polymer particles having Laponite clay armor were prepared by the Pickering miniemulsion polymerization of n-lauryl acrylate. The resulting "soft-hard'' poly(lauryl acrylate) (PLA) -Laponite hybrid particles were blended at various low concentrations with a standard poly(butyl acrylate-co-acrylic acid) (PBA) latex for application as a waterborne pressure-sensitive adhesive (PSA). The tack adhesion properties of the resulting nanocomposite films were compared with the performance of the PBA when blended with either a conventional non-armored PLA latex, with Laponite RD nanosized clay discs, or a mixture of both. A true synergistic effect was discovered showing that the clay-armored supracolloidal structure of the hybrid particles was essential to achieve a superior balance of viscoelastic properties. The addition of small amounts, e. g. 2.7 wt%, of the "soft-hard'' clay-armored PLA particles increased the tack adhesion energy considerably more than found for the two individual components or for the sum of their individual contributions. The soft PLA core ensures that the adhesives are not stiffened too much by the nanosized Laponite clay. Slippage at the interface between the nanoclay platelets and the PBA matrix introduces an additional energy dissipation mechanism during deformation. Through the synergistic effect of the clay and PLA in the supracolloidal armored latex structure, the tack adhesion energy is increased by 45 J m(-2), which is about 70% greater than found for the PBA adhesive alone.},
 bibtype = {article},
 author = {Wang, Tao and Colver, Patrick J. and Bon, Stefan Antonius Franciscus and Keddie, Joseph L.},
 doi = {10.1039/b904740a},
 journal = {Soft Matter},
 number = {20}
}

Numerous synthesis routes toward nanostructured polymer particles have emerged, but few examples demonstrate the essential need for such complex particle structures to achieve any added benefit in a target application. Here, polymer particles having Laponite clay armor were prepared by the Pickering miniemulsion polymerization of n-lauryl acrylate. The resulting "soft-hard'' poly(lauryl acrylate) (PLA) -Laponite hybrid particles were blended at various low concentrations with a standard poly(butyl acrylate-co-acrylic acid) (PBA) latex for application as a waterborne pressure-sensitive adhesive (PSA). The tack adhesion properties of the resulting nanocomposite films were compared with the performance of the PBA when blended with either a conventional non-armored PLA latex, with Laponite RD nanosized clay discs, or a mixture of both. A true synergistic effect was discovered showing that the clay-armored supracolloidal structure of the hybrid particles was essential to achieve a superior balance of viscoelastic properties. The addition of small amounts, e. g. 2.7 wt%, of the "soft-hard'' clay-armored PLA particles increased the tack adhesion energy considerably more than found for the two individual components or for the sum of their individual contributions. The soft PLA core ensures that the adhesives are not stiffened too much by the nanosized Laponite clay. Slippage at the interface between the nanoclay platelets and the PBA matrix introduces an additional energy dissipation mechanism during deformation. Through the synergistic effect of the clay and PLA in the supracolloidal armored latex structure, the tack adhesion energy is increased by 45 J m(-2), which is about 70% greater than found for the PBA adhesive alone.

@article{
 title = {Packing patterns of silica nanoparticles on surfaces of armored polystyrene latex particles},
 type = {article},
 year = {2009},
 pages = {12399-12403},
 volume = {25},
 websites = {http://pubs.acs.org/doi/abs/10.1021/la9010289},
 month = {11},
 id = {804f9ea4-32fd-3d51-86e7-02818553a15b},
 created = {2024-01-02T14:09:49.344Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:49.344Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000271106600001},
 source_type = {article},
 private_publication = {false},
 abstract = {Fascinating packing patterns of identical spherical and discotic objects on curved surfaces occur readily in nature and science. Examples include C60 fullerenes,(1, 2)13-atom cuboctahedral metal clusters,(3) and S-layer proteins on outer cell membranes.(4) Numerous situations with surface-arranged objects of variable size also exist, such as the lenses on insect eyes, biomineralized shells on coccolithophorids,(5) and solid-stabilized emulsion droplets(6) and bubbles.(7) The influence of size variations on these packing patterns, however, is studied sparsely. Here we investigate the packing of nanosized silica particles on the surface of polystyrene latex particles fabricated by Pickering miniemulsion polymerization of submicrometer-sized armored monomer droplets. We are able to rationalize the experimental morphology and the nearest-neighbor distribution with the help of Monte Carlo simulations. We show that broadening of the nanoparticle size distribution has pronounced effects on the self-assembled equilibrium packing structures, with original 12-point dislocations or grain-boundary scars gradually fading out.\nFascinating packing patterns of identical spherical and discotic objects on curved surfaces occur readily in nature and science. Examples include C60 fullerenes,(1, 2)13-atom cuboctahedral metal clusters,(3) and S-layer proteins on outer cell membranes.(4) Numerous situations with surface-arranged objects of variable size also exist, such as the lenses on insect eyes, biomineralized shells on coccolithophorids,(5) and solid-stabilized emulsion droplets(6) and bubbles.(7) The influence of size variations on these packing patterns, however, is studied sparsely. Here we investigate the packing of nanosized silica particles on the surface of polystyrene latex particles fabricated by Pickering miniemulsion polymerization of submicrometer-sized armored monomer droplets. We are able to rationalize the experimental morphology and the nearest-neighbor distribution with the help of Monte Carlo simulations. We show that broadening of the nanoparticle size distribution has pronounced effects on the self-assembled equilibrium packing structures, with original 12-point dislocations or grain-boundary scars gradually fading out.},
 bibtype = {article},
 author = {Fortuna, Sara and Colard, C. A L and Troisi, Alessandro and Bon, S. A F},
 doi = {10.1021/la9010289},
 journal = {Langmuir},
 number = {21}
}

Fascinating packing patterns of identical spherical and discotic objects on curved surfaces occur readily in nature and science. Examples include C60 fullerenes,(1, 2)13-atom cuboctahedral metal clusters,(3) and S-layer proteins on outer cell membranes.(4) Numerous situations with surface-arranged objects of variable size also exist, such as the lenses on insect eyes, biomineralized shells on coccolithophorids,(5) and solid-stabilized emulsion droplets(6) and bubbles.(7) The influence of size variations on these packing patterns, however, is studied sparsely. Here we investigate the packing of nanosized silica particles on the surface of polystyrene latex particles fabricated by Pickering miniemulsion polymerization of submicrometer-sized armored monomer droplets. We are able to rationalize the experimental morphology and the nearest-neighbor distribution with the help of Monte Carlo simulations. We show that broadening of the nanoparticle size distribution has pronounced effects on the self-assembled equilibrium packing structures, with original 12-point dislocations or grain-boundary scars gradually fading out.\nFascinating packing patterns of identical spherical and discotic objects on curved surfaces occur readily in nature and science. Examples include C60 fullerenes,(1, 2)13-atom cuboctahedral metal clusters,(3) and S-layer proteins on outer cell membranes.(4) Numerous situations with surface-arranged objects of variable size also exist, such as the lenses on insect eyes, biomineralized shells on coccolithophorids,(5) and solid-stabilized emulsion droplets(6) and bubbles.(7) The influence of size variations on these packing patterns, however, is studied sparsely. Here we investigate the packing of nanosized silica particles on the surface of polystyrene latex particles fabricated by Pickering miniemulsion polymerization of submicrometer-sized armored monomer droplets. We are able to rationalize the experimental morphology and the nearest-neighbor distribution with the help of Monte Carlo simulations. We show that broadening of the nanoparticle size distribution has pronounced effects on the self-assembled equilibrium packing structures, with original 12-point dislocations or grain-boundary scars gradually fading out.

@article{
 title = {An "inside-out" microfluidic approach to monodisperse emulsions stabilized by solid particles},
 type = {article},
 year = {2008},
 pages = {16508-16509},
 volume = {130},
 websites = {http://dx.doi.org/10.1021/ja807764m},
 month = {12},
 publisher = {American Chemical Society},
 day = {10},
 id = {89136198-9ac5-3d3b-94e4-c637f031df66},
 created = {2024-01-02T14:09:46.701Z},
 accessed = {2014-01-26},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:46.701Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Nie2008},
 private_publication = {false},
 abstract = {Particle-stabilized emulsions (Pickering emulsions) have recently seen a surge in interest, owing to their extremely high stability against coalescence and a broad range of applications in the fabrication of functional materials, for example, hollow permeable structures, 1 foams, 2,3 and hybrid supracolloidal assemblies. 4-6 Adsorption of colloidal particles to liquid-liquid interfaces occurs when they are not completely wetted by any of the phases. The attachment of a particle of radius a p to a water-oil interface is governed by a reduction of surface energy, E) πa p 2 γ(1 -|cos θ|) 2 , where γ is the interfacial tension between the two liquid phases and θ is the contact angle of the particle at the fluid interface. 7-10 Pickering emulsions are generated by injection methods or by the shearing of a mixture of two immiscible fluids with the solid particles present in excess, that is, in an amount that is significantly larger than is required for the complete coverage and stabilization of the droplets. Lower particle concentrations result in droplet coalescence 11 whereas an excess of particles in the system leads to their undesired loss and in principle, can affect the properties of the material derived from the Pickering emulsions. For a particular system, the concentration of particles required for the efficient stabilization of droplets depends on many factors, including the ratio between the dimensions of droplets and particles, and the number of particles. 9 Current methods for producing particle-coated emulsions generate droplets with a broad distribution of sizes, which complicates the rationalization of the amount of particles introduced in the system. Recently, microfluidic emulsi-fication has provided a means for the formation of highly mono-disperse droplets. 12,13 Furthermore, Subramaniam et al. 14 have shown that the deposition of microbeads from the continuous phase to the bubble-liquid interface is greatly assisted by hydrodynamic flow. Herein, we describe a microfluidic " inside-out " approach to the generation of monodisperse water-in-oil and oil-in-water Pickering emulsions, as well as the supracolloidal polymer microspheres. Our strategy has the following new features: the microfluidic emulsifica-tion of a dispersion of colloidal particles in the particle-free continuous phase and a rationalized, based on geometric consid-erations, approach to controlling the coverage of the droplets with a layer of solid particles. Emulsification was conducted in a microfluidic flow-focusing droplet generator. 13 A dispersion of 3.5 µm-diameter poly(divinyl-benzene-methacrylic acid) (poly(DVB-MAA)) particles in the water-ethanol (85/15 v/v) mixture was emulsified in hexadecane. The value of θ between the polymer film derived from the particles and the water-ethanol mixture was 82.2 (2.1°. Upon the formation of droplets with polydispersity below 5%, the microbeads rapidly migrated from the interior of the droplets to the droplet surface. Since the diameter of the particles used in the present work was significantly smaller than the diameter of the droplets, the surface coverage of the droplets, δ, was estimated as δ) A p /A d) C p F d a d / (4F p a p) (eq 1), where A d and A p are the surface area of the droplet and the area of the droplet coated with particles, respectively; F d is the density of the droplet phase, and C p and F p are the concentration and the density of particles, respectively. In Figure 1 the broken line shows the estimated variation in the concentration of particles required to achieve complete coverage of the droplets with varying size with a colloidal monolayer, with the assumptions that (i) all particles migrate from the droplet interior to the droplet surface and (ii) at the interface the particles form a hexagonal lattice with a packing density of 0.906. Below the line, the amount of particles is not sufficient for the complete coverage of the droplets; whereas above the line, the microbeads present in excess form a multilayer shell or remain in the droplet interior. Since the number of particles is proportional to the droplet volume (∼a d 3) and A d ≈ a d 2 , complete coverage of droplets with larger radii requires a lower concentration of the particles. In the experiments, we controlled the surface coverage of the droplets by varying independently the value of C p from 4 to 16 wt % and the values of a d from 40 to 100 µm (by tuning the ratio of flow rates of the droplet-to-continuous phases. 14 Filled symbols in Figure 1 show the experimental results. Droplets with δ g 0.7 were stable to coalescence, whereas droplets with δ < 0.7 were prone to coalescence when collected at the exit of the microfluidic droplet generator. The attachment of particles from the droplet phase to the liquid-liquid interface and the formation of the close-packed crystalline shell occurred within several seconds and was assisted by the hydrodynamic flow. 14 Owing to the very rapid particle jamming at the fluid interface, at high values of C p , we were able},
 bibtype = {article},
 author = {Nie, Zhihong and Jai, Il Park and Li, Wei and Bon, Stefan A F and Kumacheva, Eugenia},
 doi = {10.1021/ja807764m},
 journal = {Journal of the American Chemical Society},
 number = {49}
}

Particle-stabilized emulsions (Pickering emulsions) have recently seen a surge in interest, owing to their extremely high stability against coalescence and a broad range of applications in the fabrication of functional materials, for example, hollow permeable structures, 1 foams, 2,3 and hybrid supracolloidal assemblies. 4-6 Adsorption of colloidal particles to liquid-liquid interfaces occurs when they are not completely wetted by any of the phases. The attachment of a particle of radius a p to a water-oil interface is governed by a reduction of surface energy, E) πa p 2 γ(1 -|cos θ|) 2 , where γ is the interfacial tension between the two liquid phases and θ is the contact angle of the particle at the fluid interface. 7-10 Pickering emulsions are generated by injection methods or by the shearing of a mixture of two immiscible fluids with the solid particles present in excess, that is, in an amount that is significantly larger than is required for the complete coverage and stabilization of the droplets. Lower particle concentrations result in droplet coalescence 11 whereas an excess of particles in the system leads to their undesired loss and in principle, can affect the properties of the material derived from the Pickering emulsions. For a particular system, the concentration of particles required for the efficient stabilization of droplets depends on many factors, including the ratio between the dimensions of droplets and particles, and the number of particles. 9 Current methods for producing particle-coated emulsions generate droplets with a broad distribution of sizes, which complicates the rationalization of the amount of particles introduced in the system. Recently, microfluidic emulsi-fication has provided a means for the formation of highly mono-disperse droplets. 12,13 Furthermore, Subramaniam et al. 14 have shown that the deposition of microbeads from the continuous phase to the bubble-liquid interface is greatly assisted by hydrodynamic flow. Herein, we describe a microfluidic " inside-out " approach to the generation of monodisperse water-in-oil and oil-in-water Pickering emulsions, as well as the supracolloidal polymer microspheres. Our strategy has the following new features: the microfluidic emulsifica-tion of a dispersion of colloidal particles in the particle-free continuous phase and a rationalized, based on geometric consid-erations, approach to controlling the coverage of the droplets with a layer of solid particles. Emulsification was conducted in a microfluidic flow-focusing droplet generator. 13 A dispersion of 3.5 µm-diameter poly(divinyl-benzene-methacrylic acid) (poly(DVB-MAA)) particles in the water-ethanol (85/15 v/v) mixture was emulsified in hexadecane. The value of θ between the polymer film derived from the particles and the water-ethanol mixture was 82.2 (2.1°. Upon the formation of droplets with polydispersity below 5%, the microbeads rapidly migrated from the interior of the droplets to the droplet surface. Since the diameter of the particles used in the present work was significantly smaller than the diameter of the droplets, the surface coverage of the droplets, δ, was estimated as δ) A p /A d) C p F d a d / (4F p a p) (eq 1), where A d and A p are the surface area of the droplet and the area of the droplet coated with particles, respectively; F d is the density of the droplet phase, and C p and F p are the concentration and the density of particles, respectively. In Figure 1 the broken line shows the estimated variation in the concentration of particles required to achieve complete coverage of the droplets with varying size with a colloidal monolayer, with the assumptions that (i) all particles migrate from the droplet interior to the droplet surface and (ii) at the interface the particles form a hexagonal lattice with a packing density of 0.906. Below the line, the amount of particles is not sufficient for the complete coverage of the droplets; whereas above the line, the microbeads present in excess form a multilayer shell or remain in the droplet interior. Since the number of particles is proportional to the droplet volume (∼a d 3) and A d ≈ a d 2 , complete coverage of droplets with larger radii requires a lower concentration of the particles. In the experiments, we controlled the surface coverage of the droplets by varying independently the value of C p from 4 to 16 wt % and the values of a d from 40 to 100 µm (by tuning the ratio of flow rates of the droplet-to-continuous phases. 14 Filled symbols in Figure 1 show the experimental results. Droplets with δ g 0.7 were stable to coalescence, whereas droplets with δ < 0.7 were prone to coalescence when collected at the exit of the microfluidic droplet generator. The attachment of particles from the droplet phase to the liquid-liquid interface and the formation of the close-packed crystalline shell occurred within several seconds and was assisted by the hydrodynamic flow. 14 Owing to the very rapid particle jamming at the fluid interface, at high values of C p , we were able

@article{
 title = {Multilayered nanocomposite polymer colloids using emulsion polymerization stabilized by solid particles},
 type = {article},
 year = {2008},
 pages = {16850-16851},
 volume = {130},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ja807242k},
 month = {12},
 id = {86dc4c3a-706c-351a-8f27-2afbcdc57fc5},
 created = {2024-01-02T14:09:48.882Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:48.882Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000263320400013},
 source_type = {article},
 private_publication = {false},
 abstract = {We report a versatile emulsion polymerization process in which solid nanoparticles are used as stabilizer, thereby replacing the role of surfactants, allowing for simple fabrication of armored nanocomposite polymer latexes. Use of a second conventional seeded emulsion polymerization step provides a straightforward route to more complex multilayered nanocomposite polymer colloids.},
 bibtype = {article},
 author = {Colver, Patrick J. and Colard, Catheline A L and Bon, Stefan A F},
 doi = {10.1021/ja807242k},
 journal = {Journal of the American Chemical Society},
 number = {50}
}

We report a versatile emulsion polymerization process in which solid nanoparticles are used as stabilizer, thereby replacing the role of surfactants, allowing for simple fabrication of armored nanocomposite polymer latexes. Use of a second conventional seeded emulsion polymerization step provides a straightforward route to more complex multilayered nanocomposite polymer colloids.

@article{
 title = {Cellular polymer monoliths made via pickering high internal phase emulsions},
 type = {article},
 year = {2007},
 pages = {1537-1539},
 volume = {19},
 websites = {http://pubs.acs.org/doi/abs/10.1021/cm0628810},
 publisher = {ACS Publications},
 id = {ab7e337a-6b3a-3310-818d-dd8fe5a7b7f5},
 created = {2024-01-02T14:09:42.874Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:42.874Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {colver2007cellular},
 source_type = {article},
 private_publication = {false},
 abstract = {The prodn. of poly(divinylbenzene) poly(HIPE)s, high internal phase emulsions (HIPE), using pickering stabilization was demonstrated. The individual cells of the poly(HIPE)s are covered with particles and a variety of poly(HIPE)s can be designed by using two types of polymethacrylate-based particle stabilizers. [on SciFinder(R)]},
 bibtype = {article},
 author = {Colver, Patrick J. and Bon, S. A F},
 doi = {10.1021/cm0628810},
 journal = {Chemistry of Materials},
 number = {7}
}

The prodn. of poly(divinylbenzene) poly(HIPE)s, high internal phase emulsions (HIPE), using pickering stabilization was demonstrated. The individual cells of the poly(HIPE)s are covered with particles and a variety of poly(HIPE)s can be designed by using two types of polymethacrylate-based particle stabilizers. [on SciFinder(R)]

@article{
 title = {Pickering stabilization as a tool in the fabrication of complex nanopatterned silica microcapsules},
 type = {article},
 year = {2007},
 pages = {9527-9530},
 volume = {23},
 websites = {http://dx.doi.org/10.1021/la7016769},
 month = {9},
 publisher = {American Chemical Society},
 day = {11},
 id = {20b30592-aff3-3638-b0d2-8fa9f9d2155b},
 created = {2024-01-02T14:09:47.153Z},
 accessed = {2014-01-26},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:47.153Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Bon2007},
 private_publication = {false},
 abstract = {Complex silica-based microcapsules with nanopatterned features were made using Pickering stabilization as a fabrication tool. A sequential two-step liquid-liquid interface-driven assembly process was employed using Laponite clay discs and Laponite armored polystyrene latex particles as solids to stabilize emulsion droplets on two different length scales. The discotic Laponite particles and poly(diethoxysiloxane) were used as silica sources. The ethoxy groups of the poly(diethoxysiloxane) were removed via a triethylamine-catalyzed interfacial hydrolysis and sol-gel reaction. The organic components were removed via a calcination step. The two-stage templating route provided siliceous microcapsules of which the capsule walls were decorated on either the outside or inside with nanocapsules composed of Laponite clay.},
 bibtype = {article},
 author = {Bon, Stefan A F and Chen, Tao},
 doi = {10.1021/la7016769},
 journal = {Langmuir},
 number = {19}
}

Complex silica-based microcapsules with nanopatterned features were made using Pickering stabilization as a fabrication tool. A sequential two-step liquid-liquid interface-driven assembly process was employed using Laponite clay discs and Laponite armored polystyrene latex particles as solids to stabilize emulsion droplets on two different length scales. The discotic Laponite particles and poly(diethoxysiloxane) were used as silica sources. The ethoxy groups of the poly(diethoxysiloxane) were removed via a triethylamine-catalyzed interfacial hydrolysis and sol-gel reaction. The organic components were removed via a calcination step. The two-stage templating route provided siliceous microcapsules of which the capsule walls were decorated on either the outside or inside with nanocapsules composed of Laponite clay.

@article{
 title = {Organic–Inorganic Hybrid Hollow Spheres Prepared from TiO2-Stabilized Pickering Emulsion Polymerization},
 type = {article},
 year = {2007},
 pages = {2286-2289},
 volume = {19},
 websites = {http://doi.wiley.com/10.1002/adma.200602447},
 month = {9},
 day = {3},
 id = {f282e845-a5c8-3f6f-a8e8-eab0d6b14685},
 created = {2024-01-02T14:09:47.346Z},
 accessed = {2014-01-26},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:47.346Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Chen2007},
 private_publication = {false},
 abstract = {When organic–inorganic hybrid hollow microspheres (capsules) are composed of nanometer-sized colloidal building blocks a synergetic combination of excellent properties may be achieved that cannot be obtained from the individual components. Because of this synergy these organic–inorganic hybrid hollow spheres could exhibit particular properties and applications, ranging from drug release systems to “containers” for catalytic materials.},
 bibtype = {article},
 author = {Chen, T. and Colver, P. J. and Bon, S. A. F.},
 doi = {10.1002/adma.200602447},
 journal = {Advanced Materials},
 number = {17}
}

When organic–inorganic hybrid hollow microspheres (capsules) are composed of nanometer-sized colloidal building blocks a synergetic combination of excellent properties may be achieved that cannot be obtained from the individual components. Because of this synergy these organic–inorganic hybrid hollow spheres could exhibit particular properties and applications, ranging from drug release systems to “containers” for catalytic materials.

@article{
 title = {Pickering miniemulsion polymerization using laponite clay as a stabilizer},
 type = {article},
 year = {2007},
 pages = {8316-8322},
 volume = {23},
 websites = {http://pubs.acs.org/doi/abs/10.1021/la701150q},
 month = {7},
 id = {76a138d9-f4b7-3558-b704-dc73afb42c23},
 created = {2024-01-02T14:09:47.733Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:47.733Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000248229900008},
 source_type = {article},
 private_publication = {false},
 abstract = {Solid-stabilized, or Pickering, miniemulsion polymerizations using Laponite clay discs as stabilizer are investigated. Free radical polymerizations are carried out using a variety of hydrophobic monomers (i.e., styrene, lauryl (meth)acrylate, butyl (meth)acrylate, octyl acrylate, and 2-ethyl hexyl acrylate). Armored latexes, of which the surfaces of the particles are covered with clay discs, are obtained, as confirmed by scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Overall polymerization kinetics of the Pickering miniemulsion polymerizations of styrene were investigated via gravimetry. Comparison with the bulk polymerization analogue clearly shows compartmentalization. Moreover, retardation effects up to intermediate monomer conversions are observed; they are more prominent for the smaller particles and are ascribed to the Laponite clay. A model is presented that allows for the prediction of the average particle size of the latexes produced as a function of the amounts of monomer and Pickering stabilizers used. It shows that under specific generic conditions the number of clay discs used correlates in a linear fashion with the total surface area of the latex particles. This is a direct result of the reversibility of the Laponite clay disc adhesion process under the emulsification conditions (i.e., sonication) used.},
 bibtype = {article},
 author = {Bon, Stefan A.F. and Colver, Patrick J.},
 doi = {10.1021/la701150q},
 journal = {Langmuir},
 number = {16}
}

Solid-stabilized, or Pickering, miniemulsion polymerizations using Laponite clay discs as stabilizer are investigated. Free radical polymerizations are carried out using a variety of hydrophobic monomers (i.e., styrene, lauryl (meth)acrylate, butyl (meth)acrylate, octyl acrylate, and 2-ethyl hexyl acrylate). Armored latexes, of which the surfaces of the particles are covered with clay discs, are obtained, as confirmed by scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Overall polymerization kinetics of the Pickering miniemulsion polymerizations of styrene were investigated via gravimetry. Comparison with the bulk polymerization analogue clearly shows compartmentalization. Moreover, retardation effects up to intermediate monomer conversions are observed; they are more prominent for the smaller particles and are ascribed to the Laponite clay. A model is presented that allows for the prediction of the average particle size of the latexes produced as a function of the amounts of monomer and Pickering stabilizers used. It shows that under specific generic conditions the number of clay discs used correlates in a linear fashion with the total surface area of the latex particles. This is a direct result of the reversibility of the Laponite clay disc adhesion process under the emulsification conditions (i.e., sonication) used.

@article{
 title = {Route to stable non-spherical emulsion droplets},
 type = {article},
 year = {2007},
 keywords = {Assembly,Droplets,Emulsion,Non-spherical,Pickering stabilization,Polymerization},
 pages = {4839-4842},
 volume = {43},
 websites = {http://www.sciencedirect.com/science/article/pii/S0014305707004934},
 month = {11},
 id = {6aa286be-28cb-3744-a681-08c3eefd0ac4},
 created = {2024-01-02T14:09:48.481Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:48.481Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000251625700026},
 source_type = {article},
 private_publication = {false},
 abstract = {A route to the production of stable non-spherical emulsion droplets has been developed by pushing millimeter-sized liquid droplets stabilized by an excess amount of solid Pickering particles through a narrow capillary. This excess amount allows for the full coverage of the newly created droplets' interface during deformation. Upon exiting the capillary the adhered particles wedge, or "jam", on the surface preserving the non-spherical shape. Stable millimeter-sized non-spherical liquid droplets with aspect ratios exceeding 10 and cross-sections in line with capillary dimensions are easily obtained. Post-modification can be performed in conventional reactors. The ability to fabricate non-spherical droplets creates exciting opportunities in areas such as self-healing polymer composites. ?? 2007 Elsevier Ltd. All rights reserved.},
 bibtype = {article},
 author = {Bon, Stefan A F and Mookhoek, Steven D. and Colver, Patrick J. and Fischer, Hartmut R. and van der Zwaag, Sybrand},
 doi = {10.1016/j.eurpolymj.2007.09.001},
 journal = {European Polymer Journal},
 number = {11}
}

A route to the production of stable non-spherical emulsion droplets has been developed by pushing millimeter-sized liquid droplets stabilized by an excess amount of solid Pickering particles through a narrow capillary. This excess amount allows for the full coverage of the newly created droplets' interface during deformation. Upon exiting the capillary the adhered particles wedge, or "jam", on the surface preserving the non-spherical shape. Stable millimeter-sized non-spherical liquid droplets with aspect ratios exceeding 10 and cross-sections in line with capillary dimensions are easily obtained. Post-modification can be performed in conventional reactors. The ability to fabricate non-spherical droplets creates exciting opportunities in areas such as self-healing polymer composites. ?? 2007 Elsevier Ltd. All rights reserved.

@article{
 title = {Colloidosomes as micron-sized polymerisation vessels to create supracolloidal interpenetrating polymer network reinforced capsules},
 type = {article},
 year = {2007},
 pages = {194-199},
 volume = {3},
 websites = {http://xlink.rsc.org/?DOI=B612066K},
 id = {de0bdc03-6b40-3f56-8825-abc601f2f133},
 created = {2024-01-02T14:09:49.779Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:49.779Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000246006600008},
 source_type = {article},
 private_publication = {false},
 abstract = {Supracolloidal interpenetrating polymer network reinforced capsules are prepared by using micron-sized colloidosomes of poly(methyl methacrylate-co-divinylbenzene) microgels as reaction vessels. An interpenetrating polymer network as scaffold is generated via radical polymerisation of the interior phase to produce hollow supracolloidal structures with a raspberry core–shell morphology. Their flexibility is tailored by variation of the monomer feed composition.},
 bibtype = {article},
 author = {Bon, Stefan A. F. and Cauvin, Séverine and Colver, Patrick J.},
 doi = {10.1039/B612066K},
 journal = {Soft Matter},
 number = {2}
}

Supracolloidal interpenetrating polymer network reinforced capsules are prepared by using micron-sized colloidosomes of poly(methyl methacrylate-co-divinylbenzene) microgels as reaction vessels. An interpenetrating polymer network as scaffold is generated via radical polymerisation of the interior phase to produce hollow supracolloidal structures with a raspberry core–shell morphology. Their flexibility is tailored by variation of the monomer feed composition.

@article{
 title = {Supracolloidal structures through liquid-liquid interface driven assembly and polymerization},
 type = {article},
 year = {2006},
 keywords = {Colloids,Emulsions,Pickering,Polymerization,Self-assembly},
 pages = {34-41},
 volume = {245-246},
 websites = {http://doi.wiley.com/10.1002/masy.200651306},
 month = {12},
 id = {b1cb4b13-1b43-38a7-928d-ee9276489941},
 created = {2024-01-02T14:09:47.532Z},
 accessed = {2014-01-26},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:47.532Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Colver2006},
 private_publication = {false},
 abstract = {Solid particles can adhere to liquid-liquid interfaces. When emulsion droplets are stabilized in such a way one speaks of a Pickering emulsion. The supracolloidal structures formed by this interface driven assembly process can be referred to as colloidosomes. Herein we explain the concept of colloidosome formation, their deformation behavior upon evaporation of their inner phase. Moreover, we describe Pickering miniemulsion and suspension polymerization processes, both yielding armored raspberry-type core-shell composite polymer particles.},
 bibtype = {article},
 author = {Colver, Patrick J. and Chen, Tao and Bon, Stefan A F},
 doi = {10.1002/masy.200651306},
 journal = {Macromolecular Symposia},
 number = {1}
}

Solid particles can adhere to liquid-liquid interfaces. When emulsion droplets are stabilized in such a way one speaks of a Pickering emulsion. The supracolloidal structures formed by this interface driven assembly process can be referred to as colloidosomes. Herein we explain the concept of colloidosome formation, their deformation behavior upon evaporation of their inner phase. Moreover, we describe Pickering miniemulsion and suspension polymerization processes, both yielding armored raspberry-type core-shell composite polymer particles.

@article{
 title = {Pickering stabilized miniemulsion polymerization: Preparation of clay armored latexes},
 type = {article},
 year = {2005},
 pages = {7887-7889},
 volume = {38},
 websites = {http://dx.doi.org/10.1021/ma051070z},
 month = {9},
 publisher = {American Chemical Society},
 id = {119af17a-269f-3afa-8ab3-981fef35ffbc},
 created = {2024-01-02T14:09:46.936Z},
 accessed = {2014-01-26},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:46.936Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {Cauvin2005},
 private_publication = {false},
 abstract = {Laponite clay armored latex particles of polystyrene made via a Pickering\nstabilized miniemulsion polymerization of monomer filled Laponite\ncolloidosomes of submicron dimensions were prepared. Relatively stable\nPickering emulsions were obtained when styrene was replaced by methyl\nor ethyl methacrylate and when 16.7% of 4-vinylpyridine was added\nas cationic comonomer. Polystyrene latex particles with an approximate\naverage diameter of 145 nm, armored with Laponite RD clay particles,\nwere successfully prepared. It was shown that aqueous phase polymerization\nevents should be kept to a minimum, since both the use of water-soluble\ninitiators and more polar monomers resulted in partial conversion\nand coagulation.},
 bibtype = {article},
 author = {Cauvin, Séverine and Colver, Patrick J. and Bon, Stefan A F},
 doi = {10.1021/ma051070z},
 journal = {Macromolecules},
 number = {19}
}

Laponite clay armored latex particles of polystyrene made via a Pickering\nstabilized miniemulsion polymerization of monomer filled Laponite\ncolloidosomes of submicron dimensions were prepared. Relatively stable\nPickering emulsions were obtained when styrene was replaced by methyl\nor ethyl methacrylate and when 16.7% of 4-vinylpyridine was added\nas cationic comonomer. Polystyrene latex particles with an approximate\naverage diameter of 145 nm, armored with Laponite RD clay particles,\nwere successfully prepared. It was shown that aqueous phase polymerization\nevents should be kept to a minimum, since both the use of water-soluble\ninitiators and more polar monomers resulted in partial conversion\nand coagulation.

@article{
 title = {Atom transfer radical polymerization of 1-ethoxyethyl (Meth)acrylate: Facile route toward near-monodisperse poly((meth)acrylic acid)},
 type = {article},
 year = {2004},
 pages = {6673-6675},
 volume = {37},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma0491208?journalCode=mamobx},
 publisher = {[Easton, Pa.]: American Chemical Society.},
 id = {ceb50d86-d351-3c2c-aa6e-fa03b6a4954b},
 created = {2024-01-02T14:09:35.501Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:35.501Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {van2004atom},
 source_type = {article},
 private_publication = {false},
 abstract = {ATRP was shown to be a suitable technique for the polymn. of 1-ethoxyethyl (meth)acrylate. Well-defined homopolymers and block copolymers were prepd. which can be deprotected to give the corresponding polyacids or polyacid segments by simple heating. [on SciFinder (R)]},
 bibtype = {article},
 author = {Van Camp, Wim and Du Prez, Filip E. and Bon, Stefan A F},
 doi = {10.1021/ma0491208},
 journal = {Macromolecules},
 number = {18}
}

ATRP was shown to be a suitable technique for the polymn. of 1-ethoxyethyl (meth)acrylate. Well-defined homopolymers and block copolymers were prepd. which can be deprotected to give the corresponding polyacids or polyacid segments by simple heating. [on SciFinder (R)]

@article{
 title = {A simple method to convert atom transfer radical polymerization (ATRP) initiators into reversible addition fragmentation chain-transfer (RAFT) mediators},
 type = {article},
 year = {2004},
 keywords = {ATRP,Initiator,Living radical polymerization,Mediator,RAFT},
 pages = {641-645},
 volume = {40},
 websites = {http://www.sciencedirect.com/science/article/pii/S0014305703002817},
 publisher = {Elsevier},
 id = {fd4c0e53-d5ea-39d6-a226-54063dbd9bc2},
 created = {2024-01-02T14:09:40.971Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:40.971Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {wager2004simple},
 source_type = {article},
 private_publication = {false},
 abstract = {A simple method to convert atom transfer radical polymerization (ATRP) initiators into reversible addition fragmentation chain-transfer (RAFT) mediators is reported. Poly(methylmethacrylate) (PMMA), poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and poly(ethylene glycol) (PEG) ATRP initiators were converted into their corresponding RAFT analogues using modified ATRP conditions for polymer chain activation in presence of bis(thiobenzoyl) disulphide. ?? 2003 Elsevier Ltd. All rights reserved.},
 bibtype = {article},
 author = {Wager, Charlene M. and Haddleton, David M. and Bon, Stefan A F},
 doi = {10.1016/j.eurpolymj.2003.10.025},
 journal = {European Polymer Journal},
 number = {3}
}

A simple method to convert atom transfer radical polymerization (ATRP) initiators into reversible addition fragmentation chain-transfer (RAFT) mediators is reported. Poly(methylmethacrylate) (PMMA), poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and poly(ethylene glycol) (PEG) ATRP initiators were converted into their corresponding RAFT analogues using modified ATRP conditions for polymer chain activation in presence of bis(thiobenzoyl) disulphide. ?? 2003 Elsevier Ltd. All rights reserved.

@inbook{
 type = {inbook},
 year = {2002},
 pages = {845-893},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/0471220450.ch15/summary},
 publisher = {John Wiley & Sons, Inc.},
 chapter = {Experimental procedures and techniques for radical polymerization},
 id = {04be03dd-945a-3d64-a427-dd3e269dcb5f},
 created = {2024-01-02T14:09:44.033Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:44.033Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon200215},
 source_type = {book chapter},
 private_publication = {false},
 abstract = {The goal of this chapter is to present a number of radical polymerization experiments, both traditional and novel. The experimental procedures will be helpful to both experienced people in the field and people who are at the dawn of their interest in radical polymer chemistry. The authors describe extensive processes that cover bulk, solution, emulsion, and suspension as well as a wide range of different chemistry. The chapter concludes with examples that illustrate the many types of polymerization processes.},
 bibtype = {inbook},
 author = {Bon, Stefan A F and Haddleton, David M},
 editor = {Matyjaszewski, Krzystztof and Warner, J C and Davis, Thomas P},
 doi = {10.1002/0471220450.ch15},
 title = {Handbook of Radical Polymerization}
}

The goal of this chapter is to present a number of radical polymerization experiments, both traditional and novel. The experimental procedures will be helpful to both experienced people in the field and people who are at the dawn of their interest in radical polymer chemistry. The authors describe extensive processes that cover bulk, solution, emulsion, and suspension as well as a wide range of different chemistry. The chapter concludes with examples that illustrate the many types of polymerization processes.

@article{
 title = {Living radical polymerization immobilized on Wang resins: Synthesis and harvest of narrow polydispersity poly(methacrylate)s},
 type = {article},
 year = {2001},
 pages = {768-774},
 volume = {34},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma0011690},
 publisher = {ACS Publications},
 id = {b5dcdde7-7ea2-3b43-976b-966eec1cb49b},
 created = {2024-01-02T14:09:35.139Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:35.139Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {angot2001living},
 source_type = {article},
 private_publication = {false},
 abstract = {Wang resin has been transformed into an initiator for copper(I)-mediated living radical polymerization of methacrylates at initiator loading of 0.9 and 3.5 mmol g(-1). The immobilized initiator was characterized by ATR FTIR, gel phase C-13 NMR, and solid-state CP/MAS C-13 NMR using two different spinning frequencies as well as a TOSS pulse sequence. The immobilized initiator has been used to prepare poly(methyl methacrylate), PMMA, homopolymer, and poly(methyl methacrylate)-block-poly(benzyl methacrylate-co-methyl methacrylate), P(MMA)-block-P(BzMA-co-MMA), block copolymers. The poly(methacrylate)s have been harvested from the insoluble resin by a simple trifluoroacetic acid, TFA, wash which selectively cleaved the activated benzyl ester linkage, so as to facilitate analysis. At an initiator loading of 0.9 mmol g(-1) the M-n increases linearly with conversion with kinetics following first-order behavior in monomer as would be expected for living polymerization. After 3 h a 61.9% conversion of MMA is reached, with the isolated polymer chains having an average number molar mass, M-n, of 8200 and a polydispersity, PDI, of 1.18. High conversions, >90%, lead to considerable increases in M-n and PDI. Moreover, small amounts of "free" chains present in the supernatant, ca. 5-8% after 4 h of reaction time, were found. The morphology of the beads was monitored by SEM with the integrity being maintained throughout the transformations. Attempts to prepare true block copolymers via a two-stage process involving isolation of the Wang resins with the first block and subsequent reuse to attach the second block were not satisfactory. However, a one-shot addition of BzMA at high conversion of MMA allowed the synthesis of P(MMA)-block-P(BzMA-co-MMA) with a narrow molar mass distribution, as confirmed with SEC, DSC, and NMR. The paper demonstrates that Wang immobilized chemistry can be used to prepare excellent polymers maintaining the characteristics of analogous homogeneous living radical polymerizations while allowing for catalyst removal by simple washing procedures. The potential for automation of this chemistry for high throughput synthesis has been demonstrated.},
 bibtype = {article},
 author = {Angot, Stephanie and Ayres, Neil and Bon, Stefan A F and Haddleton, David M.},
 doi = {10.1021/ma0011690},
 journal = {Macromolecules},
 number = {4}
}

Wang resin has been transformed into an initiator for copper(I)-mediated living radical polymerization of methacrylates at initiator loading of 0.9 and 3.5 mmol g(-1). The immobilized initiator was characterized by ATR FTIR, gel phase C-13 NMR, and solid-state CP/MAS C-13 NMR using two different spinning frequencies as well as a TOSS pulse sequence. The immobilized initiator has been used to prepare poly(methyl methacrylate), PMMA, homopolymer, and poly(methyl methacrylate)-block-poly(benzyl methacrylate-co-methyl methacrylate), P(MMA)-block-P(BzMA-co-MMA), block copolymers. The poly(methacrylate)s have been harvested from the insoluble resin by a simple trifluoroacetic acid, TFA, wash which selectively cleaved the activated benzyl ester linkage, so as to facilitate analysis. At an initiator loading of 0.9 mmol g(-1) the M-n increases linearly with conversion with kinetics following first-order behavior in monomer as would be expected for living polymerization. After 3 h a 61.9% conversion of MMA is reached, with the isolated polymer chains having an average number molar mass, M-n, of 8200 and a polydispersity, PDI, of 1.18. High conversions, >90%, lead to considerable increases in M-n and PDI. Moreover, small amounts of "free" chains present in the supernatant, ca. 5-8% after 4 h of reaction time, were found. The morphology of the beads was monitored by SEM with the integrity being maintained throughout the transformations. Attempts to prepare true block copolymers via a two-stage process involving isolation of the Wang resins with the first block and subsequent reuse to attach the second block were not satisfactory. However, a one-shot addition of BzMA at high conversion of MMA allowed the synthesis of P(MMA)-block-P(BzMA-co-MMA) with a narrow molar mass distribution, as confirmed with SEC, DSC, and NMR. The paper demonstrates that Wang immobilized chemistry can be used to prepare excellent polymers maintaining the characteristics of analogous homogeneous living radical polymerizations while allowing for catalyst removal by simple washing procedures. The potential for automation of this chemistry for high throughput synthesis has been demonstrated.

@article{
 title = {Advances in catalytic chain transfer polymerisation mediated by cobaloximes},
 type = {article},
 year = {2001},
 pages = {29-42},
 volume = {165},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/1521-3900(200103)165:1%3C29::AID-MASY29%3E3.0.CO;2-5/abstract},
 publisher = {Basel; Oxford, CT: Huthig & Wepf, 1994-},
 id = {971bfe77-46d7-32c5-af9d-aaaa22e2c3e9},
 created = {2024-01-02T14:09:37.761Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:37.761Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon2001advances},
 source_type = {article},
 private_publication = {false},
 abstract = {Catalytic chain transfer copolymerisation of MMA and HEMA (70:30) has been carried out under semi-continuous emulsion polymerisation conditions, using CoBF as catalyst. It has been shown that macromonomers of low molar mass can be synthesised with an apparent chain transfer constant, C-S(E), of ca. 1300 down to a threshold value of Ca. 20 ppm of CoBF. Below this value an initial 20% shot of monomer/catalyst mixture was necessary to prevent events involved in the catalytic chain transfer process becoming diffusion controlled and to prevent the reaction to proceed under monomer starved conditions. Analysis of the Co(II) species by SQUID has been carried out. CoBF shows a value for its effective magnetic susceptibility of 1.77 mu (B). It was found that a correction for the response of the sample container is essential for reliable data to be achieved. Diffusion ordered 2D-NMR spectroscopy (DOSY) has been used as a method to study the catalyst diffusion dependence for the rate coefficient of chain transfer. However, the apparent values of the found diffusion coefficients are an order of magnitude above the natural limit for center of mass diffusion.},
 bibtype = {article},
 author = {Bon, Stefan A.F. and Morsley, David R. and Waterson, Jennifer and Haddleton, David M. and Lees, Martin R. and Horne, Tim},
 doi = {10.1002/1521-3900(200103)165:1<29::AID-MASY29>3.0.CO;2-5},
 journal = {Macromolecular Symposia},
 number = {1}
}

Catalytic chain transfer copolymerisation of MMA and HEMA (70:30) has been carried out under semi-continuous emulsion polymerisation conditions, using CoBF as catalyst. It has been shown that macromonomers of low molar mass can be synthesised with an apparent chain transfer constant, C-S(E), of ca. 1300 down to a threshold value of Ca. 20 ppm of CoBF. Below this value an initial 20% shot of monomer/catalyst mixture was necessary to prevent events involved in the catalytic chain transfer process becoming diffusion controlled and to prevent the reaction to proceed under monomer starved conditions. Analysis of the Co(II) species by SQUID has been carried out. CoBF shows a value for its effective magnetic susceptibility of 1.77 mu (B). It was found that a correction for the response of the sample container is essential for reliable data to be achieved. Diffusion ordered 2D-NMR spectroscopy (DOSY) has been used as a method to study the catalyst diffusion dependence for the rate coefficient of chain transfer. However, the apparent values of the found diffusion coefficients are an order of magnitude above the natural limit for center of mass diffusion.

@article{
 title = {Cobalt-mediated catalytic chain-transfer polymerization (CCTP) in water and water/alcohol solution},
 type = {article},
 year = {2001},
 keywords = {Catalytic chain transfer,Cobalt,Hydrophilic,Macromonomer,Methacrylate},
 pages = {2378-2384},
 volume = {39},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/pola.1214/full},
 publisher = {John Wiley & Sons, Inc.},
 id = {61542520-0c0a-3e29-9b13-554b251a6619},
 created = {2024-01-02T14:09:43.144Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:43.144Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton2001cobalt},
 source_type = {article},
 private_publication = {false},
 abstract = {This article describes the use of cobalt-mediated catalytic chain transfer in aqueous solution under fed conditions for the preparation of macromonomers of acidic, hydroxy, and zwitterionic functional monomers. Use of a batch reaction leads to hydrolysis of catalyst, a mixture of mechanisms and poor control of the reaction. A feed process is described that adds catalyst as a solution in monomer over the course of the reaction. The feed process is applied to a range of monomers of methacrylic acid (2), 2-aminoethyl methacrylate hydrochloride (3), 2-hydroxyethyl methacrylate (4), 2-methacryloxyethyl phosphoryl choline (5), glycerol monomethyl methacrylate (6), and 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-D-glucofuranose (7). Use of the feed process for water-soluble monomers in conjunction with 1 as a catalytic chain-transfer agent gives high-conversion, > 90%, water-soluble macromonomers. The number-average molecular mass (Mn was determined by integration of the 1H NMR spectrum comparing the vinylic end group with the remainder of the backbone. Pseudo-Mayo plots were constructed by measuring the Mn at high conversion as a function of [monomer]/[catalyst] to give observed chain-transfer constants of 1120, 958, and 1058 for 4, 6, and 2, respectively. All products were obtained as relatively high-solid, homogeneous, low-viscosity aqueous solutions.},
 bibtype = {article},
 author = {Haddleton, David M. and Depaquis, Estelle and Kelly, Elizabeth J. and Kukulj, Dax and Morsley, Stuart R. and Bon, Stefan A.F. and Eason, Michael D. and Steward, Andrew G.},
 doi = {10.1002/pola.1214},
 journal = {Journal of Polymer Science, Part A: Polymer Chemistry},
 number = {14}
}

This article describes the use of cobalt-mediated catalytic chain transfer in aqueous solution under fed conditions for the preparation of macromonomers of acidic, hydroxy, and zwitterionic functional monomers. Use of a batch reaction leads to hydrolysis of catalyst, a mixture of mechanisms and poor control of the reaction. A feed process is described that adds catalyst as a solution in monomer over the course of the reaction. The feed process is applied to a range of monomers of methacrylic acid (2), 2-aminoethyl methacrylate hydrochloride (3), 2-hydroxyethyl methacrylate (4), 2-methacryloxyethyl phosphoryl choline (5), glycerol monomethyl methacrylate (6), and 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-D-glucofuranose (7). Use of the feed process for water-soluble monomers in conjunction with 1 as a catalytic chain-transfer agent gives high-conversion, > 90%, water-soluble macromonomers. The number-average molecular mass (Mn was determined by integration of the 1H NMR spectrum comparing the vinylic end group with the remainder of the backbone. Pseudo-Mayo plots were constructed by measuring the Mn at high conversion as a function of [monomer]/[catalyst] to give observed chain-transfer constants of 1120, 958, and 1058 for 4, 6, and 2, respectively. All products were obtained as relatively high-solid, homogeneous, low-viscosity aqueous solutions.

@inbook{
 type = {inbook},
 year = {2000},
 pages = {148-161},
 websites = {http://pubs.acs.org/doi/abs/10.1021/bk-2001-0780.ch009},
 month = {11},
 day = {28},
 id = {32b07c8e-7cf8-3eff-b07c-556de254957b},
 created = {2024-01-02T14:09:31.160Z},
 accessed = {2018-07-26},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:31.160Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 abstract = {An overview of recent advances in living radical polymerisation under aqueous conditions and the synthesis of water-soluble and dispersible polymers by living radical polymerisation techniques is given. Living radical polymerisation involving nitroxide stabilised radicals, transition metal mediated and reversible addition fragmentation (RAFT) is covered. This overview is followed by some specific examples of the use of copper(I) mediated living radical polymerisation for the synthesis of some water soluble/dispersible polymers. Firstly the use of a modified SPAN surfactant to polymerise 2-(dimethylamino)ethyl methacrylate (DMAEMA) producing polymers with narrow polydispersity and controlled Mn is described (Mn = 6700, PDI = 1.27). These polymers disperse in acidic aqueous media with a CAC of 0.16 gL-1. Derivatised solketal is described as an initator for sequential atom transfer polymerisation of methyl methacrylate (MMA) and DMAEMA to give Y-shaped water soluble polymers. These two examples serve to illustrate the range of topology and hydrophilic functionality which can easily be incorporated into vinyl polymers through living radical methodology.},
 bibtype = {inbook},
 author = {Bon, Stefan A.F. and Ohno, Kohji and Haddleton, David M.},
 doi = {10.1021/bk-2001-0780.ch009},
 chapter = {Water-Soluble and Water Dispersible Polymers by Living Radical Polymerisation},
 title = {ACS Symposium Series (vol 780)}
}

An overview of recent advances in living radical polymerisation under aqueous conditions and the synthesis of water-soluble and dispersible polymers by living radical polymerisation techniques is given. Living radical polymerisation involving nitroxide stabilised radicals, transition metal mediated and reversible addition fragmentation (RAFT) is covered. This overview is followed by some specific examples of the use of copper(I) mediated living radical polymerisation for the synthesis of some water soluble/dispersible polymers. Firstly the use of a modified SPAN surfactant to polymerise 2-(dimethylamino)ethyl methacrylate (DMAEMA) producing polymers with narrow polydispersity and controlled Mn is described (Mn = 6700, PDI = 1.27). These polymers disperse in acidic aqueous media with a CAC of 0.16 gL-1. Derivatised solketal is described as an initator for sequential atom transfer polymerisation of methyl methacrylate (MMA) and DMAEMA to give Y-shaped water soluble polymers. These two examples serve to illustrate the range of topology and hydrophilic functionality which can easily be incorporated into vinyl polymers through living radical methodology.

@article{
 title = {Matrix-assisted laser desorption ionization time-of-flight mass spectroscopy of polydimethylsiloxanes prepared via anionic ring-opening polymerization},
 type = {article},
 year = {2000},
 keywords = {QD Chemistry},
 pages = {694-698},
 volume = {698},
 websites = {http://wrap.warwick.ac.uk/13454/},
 publisher = {Wiley Online Library},
 id = {159c7610-2f57-39ca-a1ec-a9c99a3ba6c7},
 created = {2024-01-02T14:09:36.286Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:36.286Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton2000matrix},
 source_type = {article},
 private_publication = {false},
 abstract = {Poly(dimethylsiloxane) prepared by the anionic ring-opening polymerization initiated by butyl-lithium in tetrahydrofuran has been examined by MALDI TOF mass spectrometry. The molecular weight distributions have been found to be different from those obtained by SEC, with the MALDI spectra underestimating the contribution of the higher mass macromolecules leading to an underestimation of the average molecular weights. Three distributions are observed in the mass spectra that correspond to the initiation and interchain-exchange mechanisms producing three different macromolecular species. The pre-dominant species is an integral sum of the repeat unit indicating that anionic ring-opening propagation is fast when compared to intermolecular chain transfer. This is in conflict with earlier studies and indicates that the relative rates of transfer by different processes are highly dependent upon reaction conditions.},
 bibtype = {article},
 author = {Haddleton, David M and Bon, Stefan A F and Robinson, Kay L and Emery, N Julian and Moss, Ian},
 doi = {10.1002/(SICI)1521-3935(20000301)201:6<694::AID-MACP694>3.0.CO;2-I},
 journal = {Macromolecular Chemistry and Physics},
 number = {6}
}

Poly(dimethylsiloxane) prepared by the anionic ring-opening polymerization initiated by butyl-lithium in tetrahydrofuran has been examined by MALDI TOF mass spectrometry. The molecular weight distributions have been found to be different from those obtained by SEC, with the MALDI spectra underestimating the contribution of the higher mass macromolecules leading to an underestimation of the average molecular weights. Three distributions are observed in the mass spectra that correspond to the initiation and interchain-exchange mechanisms producing three different macromolecular species. The pre-dominant species is an integral sum of the repeat unit indicating that anionic ring-opening propagation is fast when compared to intermolecular chain transfer. This is in conflict with earlier studies and indicates that the relative rates of transfer by different processes are highly dependent upon reaction conditions.

@article{
 title = {Studies on controlled radical polymerization using 5-membered cyclic PROXYL nitroxides and corresponding alkoxyamines},
 type = {article},
 year = {2000},
 keywords = {PROXYL,TEMPO,nitroxyl radicals,radical polymerization},
 pages = {2510-2518},
 volume = {201},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/1521-3935(20001101)201:17%3C2510::AID-MACP2510%3E3.0.CO;2-S/abstract},
 publisher = {WILEY-VCH Verlag GmbH},
 id = {28f0e182-25ae-3079-8cfd-02601ce744f5},
 created = {2024-01-02T14:09:36.650Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:36.650Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {cameron2000studies},
 source_type = {article},
 private_publication = {false},
 abstract = {2,2'5,5'-tetramethylpyrrolidine-N-oxyl (PROXYL) and derivatives bearing one a-aryl substituent (Ph, p-CF3Ph, p-Me2NPh) were prepared and converted to alkoxyamines by reaction with di-tert-butyl peroxalate (DTBPO) and excess styrene. Both the nitroxides (plus DTBPO as a radical source) and alkoxyamines were investigated in the controlled radical polymerization (CRP) of styrene, and their behavior was compared to that of TEMPO. Polymerization mediated by each nitroxide display a linear relationship between molecular weight and conversion, producing material of low polydispersity indicating a controlled process. However, a comparison of kinetic behavior was complicated by the unknown concentration of active species present. Polymerizations with preformed alkoxyamines at a known concentration also displayed controlled behavior (polydispersities 1.25-1.5), and an influence of nitroxide substituent on the overall rate of polymerization could be determined. PROXYL and the dimethylaniline-substituted nitroxide gave similar CRP rates to TEMPO, whereas a Ph or (to a lesser extent) p-CF3Ph substituent resulted in significantly faster reactions. These results are discessed in terms of the likely steric and electronic influence of substituents on the nitroxide radical center, and the resulting influence on polymerization rate. It is concluded that the steric bulk of the Ph substituent is the most likely cause of the rate enhancement displayed by the corresponding mediator.},
 bibtype = {article},
 author = {Cameron, N R and Reid, a J and Span, P and Bon, S a F and Steven van Es, J J G and German, a L},
 doi = {10.1002/1521-3935(20001101)201:17<2510::AID-MACP2510>3.3.CO;2-J},
 journal = {Macromol. Chem. Phys.},
 number = {17}
}

2,2'5,5'-tetramethylpyrrolidine-N-oxyl (PROXYL) and derivatives bearing one a-aryl substituent (Ph, p-CF3Ph, p-Me2NPh) were prepared and converted to alkoxyamines by reaction with di-tert-butyl peroxalate (DTBPO) and excess styrene. Both the nitroxides (plus DTBPO as a radical source) and alkoxyamines were investigated in the controlled radical polymerization (CRP) of styrene, and their behavior was compared to that of TEMPO. Polymerization mediated by each nitroxide display a linear relationship between molecular weight and conversion, producing material of low polydispersity indicating a controlled process. However, a comparison of kinetic behavior was complicated by the unknown concentration of active species present. Polymerizations with preformed alkoxyamines at a known concentration also displayed controlled behavior (polydispersities 1.25-1.5), and an influence of nitroxide substituent on the overall rate of polymerization could be determined. PROXYL and the dimethylaniline-substituted nitroxide gave similar CRP rates to TEMPO, whereas a Ph or (to a lesser extent) p-CF3Ph substituent resulted in significantly faster reactions. These results are discessed in terms of the likely steric and electronic influence of substituents on the nitroxide radical center, and the resulting influence on polymerization rate. It is concluded that the steric bulk of the Ph substituent is the most likely cause of the rate enhancement displayed by the corresponding mediator.

@article{
 title = {Copper(i) mediated living radical polymerisation in an ionic liquid},
 type = {article},
 year = {2000},
 pages = {1237-1238},
 websites = {http://xlink.rsc.org/?DOI=b003335i},
 publisher = {Royal Society of Chemistry},
 id = {894d2bf3-9508-34db-b608-719aaa60db24},
 created = {2024-01-02T14:09:37.127Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:37.127Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {carmichael2000copper},
 source_type = {article},
 private_publication = {false},
 abstract = {1-Butyl-3-methylimidazolium hexafluorophosphate, a room temperature ionic liquid, has been used as solvent for the copper(I) mediated living radical polymerisation of methyl methacrylate; the rate of reaction is enhanced and narrow polydispersity polymers are obtained which are easily isolated from the catalyst.},
 bibtype = {article},
 author = {Carmichael, Adrian J. and Haddleton, David M. and Bon, Stefan A. F. and Seddon, Kenneth R.},
 doi = {10.1039/b003335i},
 journal = {Chemical Communications},
 number = {14}
}

1-Butyl-3-methylimidazolium hexafluorophosphate, a room temperature ionic liquid, has been used as solvent for the copper(I) mediated living radical polymerisation of methyl methacrylate; the rate of reaction is enhanced and narrow polydispersity polymers are obtained which are easily isolated from the catalyst.

@article{
 title = {Modification of the ω-bromo end group of poly(methacrylate)s prepared by copper(I)-mediated living radical polymerization},
 type = {article},
 year = {2000},
 pages = {2678-2686},
 volume = {38},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/1099-0518(20000801)38:15%3C2678::AID-POLA70%3E3.0.CO;2-P/abstract},
 publisher = {John Wiley & Sons, Inc.},
 id = {e493647f-0101-3fd6-91a6-55f819730526},
 created = {2024-01-02T14:09:38.924Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:38.924Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon2000modification},
 source_type = {article},
 private_publication = {false},
 abstract = {Four different approaches to introduce a specific functional group at the terminus of poly(methacrylate)s (PMMAs) prepared via copper(I)bromide/pyridinali- mine-mediated atom transfer polymerization, under polymerization conditions, are reported. Method 1 involves the homolysis of the -COBr bond with a subsequent reaction, via coupling or disproportionation, with an external radical species. The reaction with 2,2,6,6-tetramethylpiperidin-N-oxyl shows a high conversion (78%) of the -bromoPMMAchains into their corresponding macromonomer analogues. Method 2 utilizes monomers that are able to undergo radical addition followed by subsequent fragmentation. Reactions with trimethyl[1-(trimethylsiloxy)phenylethenyloxy]silane and allyl bromide show quantitative and 57% transformation, respectively. Method 3 is the reaction of a monomer that yields a relatively more stable secondary, or primary, carbon–halogen bond. Reactions with divinylbenzene, n-butylacrylate, and ethylene showed quantitative, 62%, and quantitative additions, respectively. Method 4 is the addition of nonhomopropagating monomers, that is, maleic anhydride. This reaction proceeds quantitatively.},
 bibtype = {article},
 author = {Bon, Stefan A F and Steward, Andrew G. and Haddleton, David M.},
 doi = {10.1002/1099-0518(20000801)38:15<2678::AID-POLA70>3.0.CO;2-P},
 journal = {Journal of Polymer Science, Part A: Polymer Chemistry},
 number = {15}
}

Four different approaches to introduce a specific functional group at the terminus of poly(methacrylate)s (PMMAs) prepared via copper(I)bromide/pyridinali- mine-mediated atom transfer polymerization, under polymerization conditions, are reported. Method 1 involves the homolysis of the -COBr bond with a subsequent reaction, via coupling or disproportionation, with an external radical species. The reaction with 2,2,6,6-tetramethylpiperidin-N-oxyl shows a high conversion (78%) of the -bromoPMMAchains into their corresponding macromonomer analogues. Method 2 utilizes monomers that are able to undergo radical addition followed by subsequent fragmentation. Reactions with trimethyl[1-(trimethylsiloxy)phenylethenyloxy]silane and allyl bromide show quantitative and 57% transformation, respectively. Method 3 is the reaction of a monomer that yields a relatively more stable secondary, or primary, carbon–halogen bond. Reactions with divinylbenzene, n-butylacrylate, and ethylene showed quantitative, 62%, and quantitative additions, respectively. Method 4 is the addition of nonhomopropagating monomers, that is, maleic anhydride. This reaction proceeds quantitatively.

@article{
 title = {Copper(I)-Mediated Living Radical Polymerization in the Presence of Oxyethylene Groups: Online 1 H NMR Spectroscopy To Investigate Solvent Effects},
 type = {article},
 year = {2000},
 keywords = {QD Chemistry},
 pages = {8246-8251},
 volume = {33},
 websites = {http://wrap.warwick.ac.uk/12808/%5Cnhttp://pubs.acs.org/doi/abs/10.1021/ma001097c},
 publisher = {ACS Publications},
 id = {c5e9fef3-12dc-3661-b00d-db6be072d05f},
 created = {2024-01-02T14:09:39.100Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:39.100Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton2000copper},
 source_type = {article},
 private_publication = {false},
 abstract = {The use of oxyethylene methacrylate monomers, initiators, and 1,2-diethoxyethane as a cosolvent in the living radical polymerization mediated by copper(I) pyridylmethanimine complexes has been studied. Online H-1 NMR monitoring of the reaction has been used to investigate the living radical polymerizations. Polymerization of poly(ethylene glycol) methyl ether methacrylate macromonomer (MeO(PEG)MA; M-n = 480) was carried out in toluene mediated by a copper(I) bromide/N-(n-propyl)-2-pyridylmethanimine catalyst, using phenyl alpha -bromoisobutyrate (1) as initiator. The measured number-average molar mass, M-n, of the product increases linearly with monomer conversion in close agreement to the theoretical M-n, with low polydispersity products (PDI < 1.2) achieved in all cases, as expected for a living polymerization. The overall rate of polymerization was very fast (ca. 90% conversion after 1 h at 90 <degrees>C) when compared to polymerization of benzyl methacrylate (BzMA) under similar conditions, indicating high values for k(p)[R*], where R* = active propagating species. The origin of this dramatic rate enhancement was investigated by carrying out the polymerization of MeO(PEG)MA over a range of temperatures and by the polymerization of alkyl methacrylates with a MeO(PEG)-derived macroinitiator. Polymerization of BzMA was carried out in I,2-diethoxyethane as solvent, which showed an enhanced rate when compared to polymerization in nonpolar/noncoordinating solvents. The high value of k(p)[R*] is ascribed to complexation of the oxyethylene groups at the copper in a dynamic state with the pyridylmethanime ligand complexation, which results in a more active catalyst.},
 bibtype = {article},
 author = {Haddleton, David M and Perrier, Sébastien and Bon, Stefan A F},
 doi = {10.1021/ma001097c},
 journal = {Macromolecules},
 number = {22}
}

The use of oxyethylene methacrylate monomers, initiators, and 1,2-diethoxyethane as a cosolvent in the living radical polymerization mediated by copper(I) pyridylmethanimine complexes has been studied. Online H-1 NMR monitoring of the reaction has been used to investigate the living radical polymerizations. Polymerization of poly(ethylene glycol) methyl ether methacrylate macromonomer (MeO(PEG)MA; M-n = 480) was carried out in toluene mediated by a copper(I) bromide/N-(n-propyl)-2-pyridylmethanimine catalyst, using phenyl alpha -bromoisobutyrate (1) as initiator. The measured number-average molar mass, M-n, of the product increases linearly with monomer conversion in close agreement to the theoretical M-n, with low polydispersity products (PDI < 1.2) achieved in all cases, as expected for a living polymerization. The overall rate of polymerization was very fast (ca. 90% conversion after 1 h at 90 C) when compared to polymerization of benzyl methacrylate (BzMA) under similar conditions, indicating high values for k(p)[R*], where R* = active propagating species. The origin of this dramatic rate enhancement was investigated by carrying out the polymerization of MeO(PEG)MA over a range of temperatures and by the polymerization of alkyl methacrylates with a MeO(PEG)-derived macroinitiator. Polymerization of BzMA was carried out in I,2-diethoxyethane as solvent, which showed an enhanced rate when compared to polymerization in nonpolar/noncoordinating solvents. The high value of k(p)[R*] is ascribed to complexation of the oxyethylene groups at the copper in a dynamic state with the pyridylmethanime ligand complexation, which results in a more active catalyst.

@article{
 title = {Copper(I) bromide/N-(n-Octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate using carbosilane dendritic initiators},
 type = {article},
 year = {2000},
 pages = {4048-4052},
 volume = {33},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma991908g},
 publisher = {ACS Publications},
 id = {b09644f0-89f8-384c-9c62-ef3acf77f16d},
 created = {2024-01-02T14:09:39.876Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:39.876Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {hovestad2000copper},
 source_type = {article},
 private_publication = {false},
 abstract = {The zeroth (Si(CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br)(4)), 2, and first (Si(CH2)(3)Si((CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br))(3)(4)), 3, generation of 2-bromoisobutyryl functionalized carbosilane dendrimers have been successfully applied as initiators for the copper(I) bromide/N-(n-octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate. The overall rate of polymerization are comparable for the two dendritic initiators studied, 2 (3.4 x 10(-5) mol L-1 s(-1)) and 3 (4.8 x 10(-5) mol L-1 s(-1)) with the benzylic model compound C6H5CH2OC(O)CMe2Br (1) showing a lower rate of polymerization for both dendritic initiators, (7.3 x 10(-5) mol L-1 s(-1)) where [initiator sites] = 1.87 x 10(-2) mol L-1. We postulate that this is caused by initial intramolecular termination. The molecular weight distribution is less than 1.3 after 3 h reaction time. Initiator 3, however, produces star-star coupling throughout the polymerization. When the dendritic periphery is partialy functionalized (statistically two and six arms of the first generation dendrimer, respectively, 4 and 5) the control of the molecular weight distribution was lost (PDI > 3) for 4 as a result of too low of a value for [initiator site], i.e., 3.12 x 10(-3) mol L-1.},
 bibtype = {article},
 author = {Hovestad, Neldes J. and Van Koten, Gerard and Bon, Stefan A.F. and Haddleton, David M.},
 doi = {10.1021/ma991908g},
 journal = {Macromolecules},
 number = {11}
}

The zeroth (Si(CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br)(4)), 2, and first (Si(CH2)(3)Si((CH2)(3)SiMe2(C6H4CH2OC(O)CMe2Br))(3)(4)), 3, generation of 2-bromoisobutyryl functionalized carbosilane dendrimers have been successfully applied as initiators for the copper(I) bromide/N-(n-octyl)-2-pyridylmethanimine-mediated living-radical polymerization of methyl methacrylate. The overall rate of polymerization are comparable for the two dendritic initiators studied, 2 (3.4 x 10(-5) mol L-1 s(-1)) and 3 (4.8 x 10(-5) mol L-1 s(-1)) with the benzylic model compound C6H5CH2OC(O)CMe2Br (1) showing a lower rate of polymerization for both dendritic initiators, (7.3 x 10(-5) mol L-1 s(-1)) where [initiator sites] = 1.87 x 10(-2) mol L-1. We postulate that this is caused by initial intramolecular termination. The molecular weight distribution is less than 1.3 after 3 h reaction time. Initiator 3, however, produces star-star coupling throughout the polymerization. When the dendritic periphery is partialy functionalized (statistically two and six arms of the first generation dendrimer, respectively, 4 and 5) the control of the molecular weight distribution was lost (PDI > 3) for 4 as a result of too low of a value for [initiator site], i.e., 3.12 x 10(-3) mol L-1.

@article{
 title = {Novel polymers from atom transfer polymerisation mediated by copper (I) Schiff base complexes},
 type = {article},
 year = {2000},
 pages = {201-208},
 volume = {157},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/1521-3900(200007)157:1%3C201::AID-MASY201%3E3.0.CO;2-P/abstract},
 publisher = {WILEY-VCH Verlag},
 id = {3bb70760-e8c0-3fb4-bcc2-8739eaa9190e},
 created = {2024-01-02T14:09:40.050Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:40.050Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton2000novel},
 source_type = {article},
 private_publication = {false},
 abstract = {The use of copper(I) Schiff base complex catalysed atom transfer polymerisation of methacrylates is described. The use of a range of functional and multi-functional initiators enables the synthesis of a range of functional and star polymers to be prepared under undemanding synthetic conditions. End capping with silyl enol ethers allows for ω-functional polymers. The combination of novel initiators, functional monomers and end capping allows an unprecedented array of macromolecular structures to be produced with limited need for protecting group chemistry.},
 bibtype = {article},
 author = {Haddleton, David M and Heming, Alex M and Jarvis, Adam P and Khan, Afzal and Marsh, Andrew and Perrier, Sebastien and Bon, Stefan A F and Jackson, Stuart G and Edmonds, Ryan and Kelly, Elizabeth and others, undefined},
 doi = {10.1002/1521-3900(200007)157:1<201::AID-MASY201>3.0.CO;2-P},
 journal = {Macromolecular Symposia},
 number = {1}
}

The use of copper(I) Schiff base complex catalysed atom transfer polymerisation of methacrylates is described. The use of a range of functional and multi-functional initiators enables the synthesis of a range of functional and star polymers to be prepared under undemanding synthetic conditions. End capping with silyl enol ethers allows for ω-functional polymers. The combination of novel initiators, functional monomers and end capping allows an unprecedented array of macromolecular structures to be produced with limited need for protecting group chemistry.

@article{
 title = {Copper(I)-mediated living radical polymerization under fluorous biphasic conditions},
 type = {article},
 year = {2000},
 pages = {1542-1543},
 volume = {122},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ja993478f?journalCode=jacsat},
 publisher = {the American Chemical Society},
 id = {f7420166-dbf0-3784-89c9-286866139ec7},
 created = {2024-01-02T14:09:40.264Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:40.264Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton2000copper},
 source_type = {article},
 private_publication = {false},
 abstract = {The title process as applied to methacrylates involves the use of the fluorous biphase as a medium for atom-transfer polymn. that would allow for the recovery of catalyst-free product and for reuse of catalyst. Atom-transfer living polymn. of Me methacrylate in perfluoromethylcyclohexane contg. CuBr and ligand pentakis-N-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl)-1,4,7-triazaheptane proceeds very effectively, allowing sepn. of product from catalyst, leaving the catalyst in a reusable state, which gives very reproducible results after repeated uses. [on SciFinder (R)]},
 bibtype = {article},
 author = {Haddleton, David M. and Jackson, Stuart G. and Bon, Stefan A F},
 doi = {10.1021/ja993478f},
 journal = {Journal of the American Chemical Society},
 number = {7}
}

The title process as applied to methacrylates involves the use of the fluorous biphase as a medium for atom-transfer polymn. that would allow for the recovery of catalyst-free product and for reuse of catalyst. Atom-transfer living polymn. of Me methacrylate in perfluoromethylcyclohexane contg. CuBr and ligand pentakis-N-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl)-1,4,7-triazaheptane proceeds very effectively, allowing sepn. of product from catalyst, leaving the catalyst in a reusable state, which gives very reproducible results after repeated uses. [on SciFinder (R)]

@article{
 title = {Use of methyl 2-(bromomethyl)acrylate as a chain-transfer agent to yield functionalized macromonomers via conventional and living radical polymerizations},
 type = {article},
 year = {2000},
 pages = {5819-5824},
 volume = {33},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma991922t},
 publisher = {ACS Publications},
 id = {97066e92-b3da-3dae-826d-569fc61774a1},
 created = {2024-01-02T14:09:40.443Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:40.443Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon2000use},
 source_type = {article},
 private_publication = {false},
 abstract = {The chain-transfer constants of methyl (2-bromomethyl)acrylate (MBrMA) in bulk polymerizations of methyl methacrylate (MMA) and styrene were determined at 70 degrees C using both the Mayo method (1/DPn as well as 2/DPw) and the chain-length-distribution procedure (Lambda). The C(MBrMA)values using 2/DPw and Lambda were consistent, i.e., 1.28 and 1.20 for MMA and 11.44 and 10.92 for styrene, respectively. MBrMA was used as a chain-transfer agent in the emulsion polymerization of MMA to yield an a-bromo-functionalized macromonomeric latex ([M-n] = 9.6 x 10(3) g mol(-1); PDI = 1.80), which was subsequently copolymerized with styrene to yield the corresponding poly(styrene-graft-MMA) copolymer. MBrMA was used as an addition-fragmentation agent in the living radical polymerization of MMA mediated by copper(I) bromide/N-(n-octyl)-2-pyridylmethanimine In situ addition of a 5-fold equivalent of MBrMA and Cu(0) to this polymerization quenched the reaction and transformed the omega-bromide into the methacrylate-based macromonomer quantitatively.},
 bibtype = {article},
 author = {Bon, Stefan A.F. and Morsley, Stuart R. and Waterson, Carl and Haddleton, David M.},
 doi = {10.1021/ma991922t},
 journal = {Macromolecules},
 number = {16}
}

The chain-transfer constants of methyl (2-bromomethyl)acrylate (MBrMA) in bulk polymerizations of methyl methacrylate (MMA) and styrene were determined at 70 degrees C using both the Mayo method (1/DPn as well as 2/DPw) and the chain-length-distribution procedure (Lambda). The C(MBrMA)values using 2/DPw and Lambda were consistent, i.e., 1.28 and 1.20 for MMA and 11.44 and 10.92 for styrene, respectively. MBrMA was used as a chain-transfer agent in the emulsion polymerization of MMA to yield an a-bromo-functionalized macromonomeric latex ([M-n] = 9.6 x 10(3) g mol(-1); PDI = 1.80), which was subsequently copolymerized with styrene to yield the corresponding poly(styrene-graft-MMA) copolymer. MBrMA was used as an addition-fragmentation agent in the living radical polymerization of MMA mediated by copper(I) bromide/N-(n-octyl)-2-pyridylmethanimine In situ addition of a 5-fold equivalent of MBrMA and Cu(0) to this polymerization quenched the reaction and transformed the omega-bromide into the methacrylate-based macromonomer quantitatively.

@article{
 title = {Copper-mediated living radical polymerization utilizing biological and end group modified poly(ethylene-co-butylene) macroinitiators},
 type = {article},
 year = {2000},
 pages = {182-196},
 volume = {768},
 websites = {http://pubs.acs.org/doi/abs/10.1021/bk-2000-0768.ch013},
 publisher = {ACS Publications},
 id = {6156a6d7-2d89-3b5c-9a35-531214462d97},
 created = {2024-01-02T14:09:43.840Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:43.840Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton2000copper},
 source_type = {article},
 private_publication = {false},
 abstract = {Copper mediated living radical polymerization can be used with a wide range of functional initiators to produce functional polymers. Block copolymers may be efficiently prepared using macroinitiators. This is demonstrated in this paper by synthesis and characterisation of a cholestrol based initiator and macroinitiators based on mono and difunctional polymers of ethylene and butylène. Polymerization of styrene and methacrylates using Schiff base ligands in conjunction with Cu(I)Br proceeds in a controlled manner yielding homopolymers, A-B diblock and A-BA triblock (co)polymers of defined molecular weight and low polydispersity. Polymers based on methacrylic acid, 2-dimethylaminoethyl methacrylate and a random copolymer of methacrylic acid and methyl methacrylate have been synthesized by use of the cholestrol initiator to give resulting water soluble/dispersible polymers.},
 bibtype = {article},
 author = {Haddleton, David M and Jarvis, Adam P and Waterson, Carl and Bon, Stefan A F and Heming, Alex M},
 doi = {10.1021/bk-2000-0768.ch013},
 journal = {ACS Symposium Series}
}

Copper mediated living radical polymerization can be used with a wide range of functional initiators to produce functional polymers. Block copolymers may be efficiently prepared using macroinitiators. This is demonstrated in this paper by synthesis and characterisation of a cholestrol based initiator and macroinitiators based on mono and difunctional polymers of ethylene and butylène. Polymerization of styrene and methacrylates using Schiff base ligands in conjunction with Cu(I)Br proceeds in a controlled manner yielding homopolymers, A-B diblock and A-BA triblock (co)polymers of defined molecular weight and low polydispersity. Polymers based on methacrylic acid, 2-dimethylaminoethyl methacrylate and a random copolymer of methacrylic acid and methyl methacrylate have been synthesized by use of the cholestrol initiator to give resulting water soluble/dispersible polymers.

@article{
 title = {Nitroxide-mediated living radical polymerization: Determination of the rate coefficient for alkoxyamine C-O bond homolysis by quantitative ESR},
 type = {article},
 year = {1999},
 pages = {8269-8276},
 volume = {32},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma990771r},
 publisher = {American Chemical Society},
 id = {0c623c85-fc2d-3065-ac59-a3ab83722aae},
 created = {2024-01-02T14:09:44.218Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:44.218Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon1999nitroxide},
 source_type = {article},
 private_publication = {false},
 abstract = {The rate coefficient for alkoxyamine C−O bond homolysis has been determined over a range of temperatures for both 2-tert-butoxy-1-phenyl-1-(1-oxy-2,2,6,6-tetramethylpiperidinyl)ethane (1) and a polystyrene−TEMPO (approximately 75 units) adduct using quantitative ESR. In },
 bibtype = {article},
 author = {Bon, Stefan A.F. and Chambard, Grégory and German, Anton L.},
 doi = {10.1021/ma990771r},
 journal = {Macromolecules},
 number = {25}
}

The rate coefficient for alkoxyamine C−O bond homolysis has been determined over a range of temperatures for both 2-tert-butoxy-1-phenyl-1-(1-oxy-2,2,6,6-tetramethylpiperidinyl)ethane (1) and a polystyrene−TEMPO (approximately 75 units) adduct using quantitative ESR. In

@phdthesis{
 title = {Collected studies on nitroxide-mediated controlled radical polymerisation},
 type = {phdthesis},
 year = {1998},
 pages = {160},
 websites = {http://repository.tue.nl/509300,https://pure.tue.nl/ws/files/1598297/9800899.pdf},
 publisher = {Technische Universiteit Eindhoven},
 institution = {Eindhoven University of Technology},
 department = {Chemical Engineering},
 id = {ee644f03-48f9-3692-8072-f2793b982871},
 created = {2024-01-02T14:09:34.396Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:34.396Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon1998debut},
 source_type = {PhD Thesis},
 private_publication = {false},
 bibtype = {phdthesis},
 author = {Bon, Stefan A F},
 doi = {10.6100/IR509300}
}

@article{
 title = {Nitroxide-Mediated Controlled Radical Polymerization: Toward Control of Molar Mass},
 type = {article},
 year = {1998},
 pages = {236-257},
 volume = {685},
 websites = {http://pubs.acs.org/doi/abs/10.1021/bk-1998-0685.ch015},
 publisher = {AMERICAN CHEMICAL SOCIETY},
 id = {3db92445-f794-3edb-8922-753dadaf0794},
 created = {2024-01-02T14:09:41.761Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:41.761Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon1998nitroxide},
 source_type = {article},
 private_publication = {false},
 abstract = {The mechanism of the TEMPO-mediated controlled radical polymerization of styrene in bulk is discussed. It is shown that the isotropic correlation time (τc) of a nitroxide can be used as a measure of the diffusive rate coefficient of trapping (ketD). A general empirical relationship for the density of polystyrene as a function of molar mass and temperature is established to correct concentration data obtained from CRP experiments for volume contraction. It is demonstrated that the overall rates of polymerization of styrene in bulk do not show a dependence upon alkoxyamine concentration. Broadening of the molar mass distribution in a CRP experiment is ascribed to a low rate of alkoxyamine C-O bond homolysis and permanent chain-stopping reactions, e.g. bimolecular termination.},
 bibtype = {article},
 author = {Bon, Stefan A F and Bergman, Frank A C and Van Es, JJGS and Klumperman, Bert and German, Anton L},
 doi = {10.1021/bk-1998-0685.ch015},
 journal = {ACS Symposium Series}
}

The mechanism of the TEMPO-mediated controlled radical polymerization of styrene in bulk is discussed. It is shown that the isotropic correlation time (τc) of a nitroxide can be used as a measure of the diffusive rate coefficient of trapping (ketD). A general empirical relationship for the density of polystyrene as a function of molar mass and temperature is established to correct concentration data obtained from CRP experiments for volume contraction. It is demonstrated that the overall rates of polymerization of styrene in bulk do not show a dependence upon alkoxyamine concentration. Broadening of the molar mass distribution in a CRP experiment is ascribed to a low rate of alkoxyamine C-O bond homolysis and permanent chain-stopping reactions, e.g. bimolecular termination.

@article{
 title = {[N-Alkyl-(2-pyridyl) methanimine] copper (I) complexes: Characterisation and application as catalysts for atom-transfer polymerisation},
 type = {article},
 year = {1998},
 pages = {1799-1806},
 volume = {1998},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/(SICI)1099-0682(199811)1998:11%3C1799::AID-EJIC1799%3E3.0.CO;2-6/abstract},
 publisher = {WILEY-VCH Verlag GmbH},
 id = {fa9cf1b7-7c3d-3f9c-bb6c-a8ff27e26e85},
 created = {2024-01-02T14:09:42.330Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:42.330Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton1998n},
 source_type = {article},
 private_publication = {false},
 abstract = {The synthesis and characterisation of a series of novel bis(imine)copper(I) complexes and their use in atom-transfer polymerisation of methyl methacrylate is described. Several N-alkyl-(2-pyridyl)methanimines (alkyl = n-butyl, isobutyl, sec-butyl, n-propyl) and N-(n-propyl)-1-(2-pyridyl)ethanimine as ligands have been fully characterised. Three bis[N-alkyl-(2-pyridyl)methanimine]copper(I) complexes, [Cu(C5H4N)CH=N(iBu)2][BF4], [Cu(C5H4N)C(CH3)=N(nPr)2][PF6], and [Cu(C5H4N)CH=N(sBu)2][BF4] have been structurally characterised; all having a distorted tetrahedral arrangement of co-ordinating nitrogen atoms surrounding the metal centre. All of the catalysts were found to be effective atom-transfer polymerisation catalysts for the polymerisation of MMA in hydrocarbon solution. However, it was discovered that the performance of the catalysts containing n-alkyl substituents was superior to those containing branched alkyl substituents. The presence of branching in the alkyl substituent results in a reduction of reaction rate and a corresponding broadening of the polydispersity index.},
 bibtype = {article},
 author = {Haddleton, David M and Duncalf, David J and Kukulj, Dax and Crossman, Martin C and Jackson, Stuart G and Bon, Stefan A F and Clark, Andrew J and Shooter, Andrew J},
 doi = {10.1002/(SICI)1099-0682(199811)1998:11<1799::AID-EJIC1799>3.0.CO;2-6},
 journal = {European Journal of Inorganic Chemistry},
 number = {11}
}

The synthesis and characterisation of a series of novel bis(imine)copper(I) complexes and their use in atom-transfer polymerisation of methyl methacrylate is described. Several N-alkyl-(2-pyridyl)methanimines (alkyl = n-butyl, isobutyl, sec-butyl, n-propyl) and N-(n-propyl)-1-(2-pyridyl)ethanimine as ligands have been fully characterised. Three bis[N-alkyl-(2-pyridyl)methanimine]copper(I) complexes, [Cu(C5H4N)CH=N(iBu)2][BF4], [Cu(C5H4N)C(CH3)=N(nPr)2][PF6], and [Cu(C5H4N)CH=N(sBu)2][BF4] have been structurally characterised; all having a distorted tetrahedral arrangement of co-ordinating nitrogen atoms surrounding the metal centre. All of the catalysts were found to be effective atom-transfer polymerisation catalysts for the polymerisation of MMA in hydrocarbon solution. However, it was discovered that the performance of the catalysts containing n-alkyl substituents was superior to those containing branched alkyl substituents. The presence of branching in the alkyl substituent results in a reduction of reaction rate and a corresponding broadening of the polydispersity index.

@article{
 title = {Controlled radical polymerization in emulsion},
 type = {article},
 year = {1997},
 pages = {324-326},
 volume = {30},
 websites = {http://pubs.acs.org/doi/abs/10.1021/ma961003s?journalCode=mamobx},
 publisher = {[Easton, Pa.]: American Chemical Society.},
 id = {2a824e14-e026-3a92-9fba-e41daf222f60},
 created = {2024-01-02T14:09:36.832Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:36.832Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon1997controlled},
 source_type = {article},
 private_publication = {false},
 bibtype = {article},
 author = {Bon, Stefan A F and Bosveld, Michiel and Klumperman, Bert and German, Anton L.},
 doi = {10.1021/ma961003s},
 journal = {Macromolecules},
 number = {2}
}

@article{
 title = {Emulsifier-free synthesis of monodisperse core-shell polymer colloids containing chloromethyl groups},
 type = {article},
 year = {1995},
 pages = {19-29},
 volume = {58},
 websites = {http://onlinelibrary.wiley.com/doi/10.1002/app.1995.070580103/abstract},
 publisher = {Wiley Online Library},
 id = {7614996b-65c4-37aa-9c21-036a7e34a574},
 created = {2024-01-02T14:09:41.962Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:41.962Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {bon1995emulsifier},
 source_type = {article},
 private_publication = {false},
 abstract = {Both the synthesis of m,p-trimethyl(vinylbenzyl) ammonium chloride (TMVBAC) and the synthesis of polymer colloids consisting of a shell of poly(vinylbenzyl chloride) grafted onto a well-defined, monodisperse poly(styrene–divinylbenzene) core are described. The preparation of the polymer latices consists of a sequence of different emulsifier-free emulsion polymerizations. First, monodisperse poly(styrene–divinylbenzene) seed latices, with 2,2′-azobis(2-amidinopropane) hydrochloride (AIBA·2HCl) as cationic initiator, are prepared under batch conditions. These latices are used for the seeded polymerization of divinylbenzene (DVB), in order to synthesize monodisperse particles, with a well-defined spherical shape, which contain a sufficient amount of pendant vinyl groups for grafting of the vinylbenzyl chloride (VBC) monomer. After the graft polymerization, the chloromethyl groups can easily be modified with a postpolymerization reaction. As an example, the amination with trimethylamine (TMA) is described.},
 bibtype = {article},
 author = {Bon, Stefan A F and Van Beek, Henno and Piet, Pieter and German, Anton L.},
 doi = {10.1002/app.1995.070580103},
 journal = {Journal of Applied Polymer Science},
 number = {1}
}

Both the synthesis of m,p-trimethyl(vinylbenzyl) ammonium chloride (TMVBAC) and the synthesis of polymer colloids consisting of a shell of poly(vinylbenzyl chloride) grafted onto a well-defined, monodisperse poly(styrene–divinylbenzene) core are described. The preparation of the polymer latices consists of a sequence of different emulsifier-free emulsion polymerizations. First, monodisperse poly(styrene–divinylbenzene) seed latices, with 2,2′-azobis(2-amidinopropane) hydrochloride (AIBA·2HCl) as cationic initiator, are prepared under batch conditions. These latices are used for the seeded polymerization of divinylbenzene (DVB), in order to synthesize monodisperse particles, with a well-defined spherical shape, which contain a sufficient amount of pendant vinyl groups for grafting of the vinylbenzyl chloride (VBC) monomer. After the graft polymerization, the chloromethyl groups can easily be modified with a postpolymerization reaction. As an example, the amination with trimethylamine (TMA) is described.