BonLab does PISA with RAFT-agent version 0.1

Call them plastics, polymers, elastomers, thermoplasts, thermosets, or macromolecules. What’s in the name? Despite the current negative press in view of considerable environmental concerns on how we deal with polymer materials post-use, it cannot be denied that polymers have been a catalyst in the evolution of human society in the 20st century, and continue to do so.

One of the synthetic pathways toward polymer molecules is free radical polymerization, a process known since the late 1800s and conceptually developed from the 1920s-1930s onwards. Since the 1980s it gradually became possible to tailor the chemical composition and chain architecture of a macromolecule. The process is called reversible deactivation radical polymerization (RDRP), also known as controlled or living radical polymerization. By grabbing control on how individual polymer chains are made, with the ability to control the sequencing of its building blocks, known as monomers, true man-made design of large functional molecules has become reality. This architectural control of polymer molecules allows for materials to be formulated with unprecedented physical and mechanical properties.

One interesting phenomenon is that when we carry out an RDRP reaction using a “living” polymer (a first block) dissolved in for example water and try to extend the macromolecule by growing a second block that does not dissolve in water, it is possible to arrange the blockcopolymer molecules by grouping them together into a variety of small (colloidal) structures dispersed in water. More interestingly, these assembled suprastructures have the ability to dynamically change shape throughout the polymerization process, for example to transform from spherical, to cylindrical, to vesicle type objects. This Polymerization Induced Self-Assembly process has been given the acronym PISA.

One way to carry out the synthesis of macromolecules by reversible deactivation radical polymerization is to make use of the concept of Reversible Addition-Fragmentation chain-Transfer, known as RAFT. This polymerization process has conventionally now uses sulfur-chemistry in the synthesis of RAFT-agents (versions 1.0 and up so to say), which efficiently controlled the growth of macromolecules. It is based on an invention from the mid 1990s, but more interestingly came to fruition by the realization that methacrylate-based macromonomers acted as RAFT-agents (here version 0.1). These latter compounds were, however, not very efficient, and abandoned.

We now show in the BonLab’s latest paper published in ACS Macro Letters that methacrylate-based macromonomers can be used successfully as RAFT-agents in Polymerization Induced Self-Assembly (PISA) processes by carefully considering the mechanistic aspects.

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Prof.dr.ir. Stefan Bon says: “Our team is delighted with the results and we are happy the paper features in ACS Macro Letters. RAFT-ing the classic way will for sure get more than a 2nd try! To show that PISA with version 0.1 RAFT-agents is indeed possible, was an excellent team effort by PhD researcher Andrea Lotierzo, and 2nd year undergraduate Warwick Chemistry student (now 3rd year) Ryan Schofield.”

The use of this class of "primitive" RAFT-agents in heterogeneous polymerizations is however not trivial, because of their inherent low reactivity. In our 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 presence of poly(glycerol methacrylate) macromonomers in water showed limited control of chain-growth. Semi-continuous 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 thermo-responsive diblock copolymer, already “phase-separated” from solution. TEM analysis showed that PISA was successful and that different consecutive particle morphologies were obtained throughout the polymerization process.

The paper can be downloaded from ACS Macro Letters.  DOI: 10.1021/acsmacrolett.7b00857

BonLab makes hydrogel beads communicate

Hydrogels are soft objects that are mainly composed of water. The water is held together by a 3D cross-linked mesh. In our latest work we show that hydrogel beads made from the bio-sustainable polymer alginate can be loaded up with different types of molecules so that the beads can communicate via chemistry. 

Chemical communication underpins a plethora of biological functions and behaviours. Plants, animals and insects rely on it for cooperative action, your body uses it to moderate its internal environment and your cells require it to survive.

A key goal of materials science is to mimic this biological behaviour, and synthetic objects that are able to communicate with one another by the sending and receiving of chemical messengers are of great interest at a range of length scales. The most widely explored platform for this kind of communication is between nanoparticles, and to a lesser extent, vesicles, but to date, very little work explores communication between large (millimetre-sized), soft objects, such as hydrogels.

In our work published in the Journal of Materials Chemistry B, we present combinations of large, soft hydrogel objects containing different signalling and receiving molecules, can exchange chemical signals. Beads encapsulating one of three species, namely the enzyme urease, the enzyme inhibitor silver (Ag+), or the Ag+ chelator dithiothreitol (DTT), are shown to interact when placed in contact with one another. By exploiting the interplay between the enzyme, its reversible inhibitor, and this inhibitor’s chelator, we demonstrate a series of ‘conversations’ between the beads. 

The movie shows two different scenario's:

 

Scenario 1: When a bead containing both urease, at a concentration of 5 g/L, and silver, at a concentration of 0.2 mmol/L, is immersed in a 0.1 mol/L solution of urea, no pH increase is observed (left bead). If an identical bead (middle bead) makes contact with one containing 0.52 mol/L DTT (right bead), the contained DTT diffuses into the silver-bound ‘enzyme’ bead. This results in the chelation of silver ions from the urease and thus its reactivation. Scale bar = 5 mm. 

Scenario 2: a 1 mmol/L ‘silver’ bead sits next to a 0.125 g/L ‘urease’ bead (far left and the top middle bead, respectively) in an aqueous solution of 0.1 mol/L urea. In this case, however, a third bead is introduced, namely a 0.52 mol/L ‘DTT’ bead (bottom middle). The far-right bead, containing 0.125 g/L urease, undergoes its colour and pH change as expected (onset at 214 seconds). As the left-hand ‘enzyme’ bead makes contact with a ‘silver’ bead, a pH increase after this time period is not observed, as the silver binds to the enzyme active site. After a longer delay (420 seconds), a pH increase is observed. Scale bar = 5 mm. 

Details of the study can be found in our paper "communication between hydrogel beads via chemical signalling" which was published in the Journal of Materials Chemistry B (DOI:10.1039/C7TB02278F).

The study forms part of a wider program to develop technology to design hydrogels that can be programmed and communicate. As part of this series we reported earlier in 2017 in Materials Horizons a study on the design of hydrogel fibres and beads with autonomous independent responsive behaviour and have the ability to communicate (DOI: 10.1039/C7MH00033B) and in Journal of Materials Chemistry B technology to program hydrogels.

 

BonLab develops technology to program hydrogels

A hydrogel is a solid object predominantly composed of water. The water is held together by a cross-linked 3D mesh, which is formed from components such as polymer molecules or colloidal particles. Hydrogels can be found in a wide range of application areas, for example food (think of agar, gelatine, tapioca, alginate containing products), and health (wound dressing, contact lenses, hygiene products, tissue engineering scaffolds, and drug delivery systems).  

In Nature hydrogels can be found widely in soft organisms. Jellyfish spring to mind. These are intriguing creatures and form an inspiration for an area called soft robotics, a discipline seek to fabricate soft structures capable of adaptation, ultimately superseding mechanical hard-robots. Hydrogels are an ideal building block for the design of soft robots as their material characteristics can be tailored. It is however, challenging to introduce and program responsive autonomous behaviour and complex functions into man-made hydrogel objects.

 

Ross Jaggers and prof.dr.ir. Stefan Bon at BonLab have now developed technology that allows for temporal and spatial programming of hydrogel objects, which we made from the biopolymer sodium alginate. Key to its design was the combined use of enzyme and metal-chelation know-how.

This video shows a programmed hydrogel tree. The hydrogel is made from sodium alginate and cross-linked with Calcium ions. Two scenarios are shown. In a tree of generation 1 the leaves contain a pH sensitive dye and the enzyme urease. The enzyme is trapped into the hydrogel leaves. The tree is floating in water of acidic pH. The water contains urea as trigger/fuel. After a dormant time period the leaves change colour from yellow to blue. This happens as the enzyme decomposes urea into ammonia and carbon dioxide. The bell-shaped activity curve of the enzyme is key to program the time delay in colour change. In a tree of generation 2, the leaves contain emulsion droplets of oil which are coloured red. Again they contain the enzyme urease. In this case, however, the system also contains the compound EDTA, which is a great calcium chelator at higher pH values. After a certain dormant time period, the pH in the leaves rises sufficiently (as a result of the enzymatic reaction decomposing urea into ammonia and carbon dioxide) that EDTA does its job. This results in spatial disintegration of the hydrogel leaves.

This video shows a programmed hydrogel object containing the numbers 1, 2 and 3. The hydrogel is made from sodium alginate and cross-linked with Calcium ions. The numbers contain emulsion droplets of oil which are coloured blue, red and yellow respectively. Each hydrogel number is loaded with a different amount of the enzyme urease. The enzyme is trapped into the gel. Number 1 contains the highest amount, number 3 the lowest. The hydrogel object is floating in water of acidic pH. The water contains urea as trigger/fuel. The system also contains the compound EDTA, which is a great calcium chelator at higher pH values. After a certain programmed dormant time period (dependent on enzyme loading), the pH in each of the numbers rises sufficiently (as a result of the enzymatic reaction decomposing urea into ammonia and carbon dioxide) that EDTA does its job. This results in spatial and temporal disintegration of the numbers.

Details of the study can be found in our paper "temporal and spatial programming in soft composite hydrogel objects" which was published in the Journal of Materials Chemistry B (DOI: 10.1039/C7TB02011B).

The study forms part of a wider program to develop technology to design hydrogels that can be programmed and communicate. As part of this series we reported earlier in 2017 in Materials Horizons a study on the design of hydrogel fibres and beads with autonomous independent responsive behaviour and have the ability to communicate (DOI: 10.1039/C7MH00033B).

 

 

Roughening up polymer microspheres and their diffusion in a liquid

Spherical microparticles that are roughened up, so that their surfaces are no longer smooth, are intriguing. You can wonder that when we place a large number of these particles in a liquid, it may show interesting rheological behaviour. For example, would they behave like cornstarch in that when we apply a lot of shear it thickens? You can imagine that spiky spheres can interlock and jam. Biologists are interested in how microparticles interact with cells and organisms, and have started to show that the shape of the particle can play an important role. Similarly, these small particles of intricate shape may show fascinating behavior at deformable surfaces, for example is there a cheerio effect?, and may show unexpected motion. This sounds all fun, but how do we make rough microparticles, as for polymer ones this is not easy?

Fig. 1 Transmission electron microscopy (TEM) images of poly(styrene) microspheres deformed at 110 °C within a dried colloidal inorganic matrix for approximate time periods of 10, 30, 60 and 120 min (a–d), (e–h), (i–l). The inorganic particles utilized were cigar-shaped calcium carbonate (a–d), large, rod-shaped calcium carbonate (e–h) and small, spherical/oblong-shaped zinc oxide (i–l). Scale bars = 1.0 μm.

Fig. 1 Transmission electron microscopy (TEM) images of poly(styrene) microspheres deformed at 110 °C within a dried colloidal inorganic matrix for approximate time periods of 10, 30, 60 and 120 min (a–d), (e–h), (i–l). The inorganic particles utilized were cigar-shaped calcium carbonate (a–d), large, rod-shaped calcium carbonate (e–h) and small, spherical/oblong-shaped zinc oxide (i–l). Scale bars = 1.0 μm.

In our paper published in Soft Matter we report an easy and versatile method to morph spherical microparticles into their rough surface textured analogues. For this, we embed the particles into an inorganic matrix of intricate shape and heat them up above the temperature at which the particles become a polymer melt. Capillary imbibition imprints the inorganic texture into the particles, turning them rough. We also look at how the particles move through a liquid, by tracking their motional behavior. Rough particles appear bigger, than their smooth precursors.  

You can read the paper here: DOI:10.1039/C7SM00589J

A mechanistic investigation of Pickering emulsion polymerization

Emulsion polymerization is an important industrial production method to prepare latexes. Polymer latex particles are typically 40-1000 nm and dispersed in water. The polymer dispersions find application in wide ranges of products, such as coatings and adhesives, gloves and condoms, paper textiles and carpets, concrete reinforcement, and so on.

Conventional emulsion polymerization processes make use of molecular surfactants, which aids the polymerization reaction during which the particles are made and keeps the polymer colloids dispersed in water.  We, and others, introduced Pickering emulsion polymerization a decade ago in which we replace common surfactants with inorganic nanoparticles.

In Pickering emulsion polymerization the polymer particles made are covered with an armor of the inorganic nanoparticles.  This offers a nanocomposite colloid which may have intriguing properties and features not present in conventional "naked" polymer latexes.

To fully exploit this innovation in emulsion polymers, a mechanistic understanding of the polymerization process is essential. Current understanding is limited which restricts the use of the technique in the fabrication of more complex, multilayered colloids.

In our paper, recently published in Polymer Chemistry, 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 to 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.

The paper can be read here: http://dx.doi.org/10.1039/C7PY00308K

Independent responsive behaviour and communication in hydrogel objects

Autonomous response mechanisms are vital to the survival of living organisms and play a key role in both biological function and independent behaviour. The design of artificial life, such as neural networks that model the human brain and robotic devices that can perform complex tasks, relies on programmed intelligence so that responses to stimuli are possible. Responsive synthetic materials can translate environmental stimuli into a direct material response, for example thermo-responsive shape change in polymer gels or light-triggered drug release from capsules. Materials that have the ability to moderate their own behaviour over time and selectively respond to their environment, however, display autonomy and more closely resemble those found in nature.

In our recent paper, published in Materials Horizons, we present soft hydrogel objects that possess 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 disintegration. This design allows for independent response behaviour of a collection of hydrogel fibers which contain coloured oil droplets in a single closed system. In addition, we show that hydrogel beads can communicate with one another, hereby influencing their pre-programmed individual behaviour. 

The incorporation of responsive time control directly into soft matter objects demonstrates an advance in the field of autonomous materials.

The paper can be read at http://dx.doi.org/10.1039/C7MH00033B

Join BonLab as a PhD student in 2017

We are looking for enthusiastic and dedicated people to join the BonLab as a PhD student in October 2017. Do you have what it takes to work at the forefront in supracolloidal chemical engineering? 

You will be working under guidance of prof.dr.ir. Stefan A. F. Bon on an exciting 4 year project in collaboration with industry in the area of polymer and colloid science.

Prof.dr.ir. Stefan A. F. Bon

Prof.dr.ir. Stefan A. F. Bon

 

We study the chemistry and physics of colloidal systems in which molecular and/or colloidal entities can be assembled into more complex supracolloidal structures, with the aim to produce innovative advanced materials . The project will span synthesis of particles and macromolecules with a design tailored to provide function, the development of methods to (self)-organise colloidal matter, and the fabrication and characterization of advanced colloidal materials of use in a variety of industrial applications.

Enquiries, which should include a CV with the names of two referees, should be made to prof.dr.ir. Stefan A. F Bon (s.bon@warwick.ac.uk)

Requirements:

An eligible student must hold, or be predicted to obtain, at least a 2.1 4-year degree in Chemistry, Chemical Engineering, Physics, or an equivalent scientific discipline. Exceptional students with a 3 year BSc degree only will be considered. This studentship is open to UK and EU nationals and those of equivalent status* (fees paid, plus annum stipend). Availability is for 4 years beginning on 1st October 2017.

*Please note - ELIGIBILITY - We can only offer the stipend to UK citizens who have lived in the UK for over 3 years (e.g. as a student), or EU nationals. Applicants from outside the EU are not eligible for this post due to restrictions on funding.

 

BonLab will be at the 2017 International Polymer Colloids Group conference this summer

We at BonLab are excited and looking forward to the 2017 IPCG meeting, this time organised by prof. Prof. Jose R. Leiza from the University of the Basque Country (Spain) and Dr. Willie Lau from Oriental Yuhong (China). Prof.dr.ir. Stefan Bon will give a masterclass on polymer colloids in the preceeding Gordon Research Seminar to an international audience of postgraduate students. He will also give an invited talk in the main conference with the tentative title: Dynamic Supracolloidal Engineered Materials

The International Polymer Colloids GroupConference (IPCG2017) will bring together world leading scientists to discuss the latest developments in the area of colloidal polymer science. The talks of the invited speakers will feature a balance of traditional and emerging applications for polymer colloids, including advanced colloid monitoring techniques, morphology and film formation, hybrid colloids, colloids for life and biotechnological applications, and engineering colloids.

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The conference will take place in Arantzazu, which is a Sanctuary located in the town of Oñati in the Basque Country Region (Spain). The place benefits from the highland silence and peaceful atmosphere of the Aizkorri mountain range. The place is frequently visited by devotees (Virgin of Arantzazu) and tourists. Arantzazu is also a starting point for several mountains trails and circuits for hikers that provide access to the meadows of Urbia and on to the mountain range Aizkorri.

Stefan Bon previously chaired the 2015 IPCG meeting in New Hampshire, USA. More in this in one of our blog entries

Stefan Bon interviewed by freelance writer Chris Woolston for Nature

Prof.dr.ir. Stefan Bon had a pleasant conversation with freelance writer Chris Woolston on the UK visa and immigration policy of the UK and the impact on his research team. Stefan stressed that "the changing landscape of the UK with respect to immigration and work permits is of great concern and highly worrying. The UK is increasingly fast squandering its international reputation."

An article written by Chris was published in the scientific leading journal Nature today (02 March 2017, 543, 139–141) containing an excerpt of the discussion: "Long waits for English-proficiency tests have also vexed Stefan Bon, a chemical engineer at the University of Warwick in Coventry, UK. Last year, one of his postdocs had to travel from Germany to the Netherlands to take the test, and the whole process — scheduling it, taking it and waiting for the results — took almost six months. Bon says that principal investigators (PIs) should expect delays, and that all prospective lab members should take the test as early as possible."

 

Stefan Bon invited by ESC2017 - 16th European Student Colloid Conference

Prof.dr.ir. Stefan Bon has been invited to participate and talk at the European Students Colloid Conference, sponsored by ECIS (European Colloid & Interface Society) that will be held in Florence on June 19 - 22, 2017 (ESC2017).

He said: "I am absolutely delighted with the invitation. I am excited to participate and interact with students from all over Europe and discuss aspects of colloid science. I am very much looking forward to, what promises to be, an outstanding conference."

Prof.dr.ir. Stefan A. F. Bon 

Prof.dr.ir. Stefan A. F. Bon 

The meeting will be devoted to young physicists/chemists in the field of colloid science, and it will be a great opportunity for PhD students to present their research results and to meet their peers from different research units. 

The topics of the conference range from adsorption and interfacial phenomena, to biomaterials, to micro- and nano-structured materials... and much more. The conference program consists of oral and poster sessions, with many social events. Seven outstanding invited speakers have already confirmed their attendance.

Several prizes will be awarded for the best presentations, including the ECIS/ACIS prize for student exchange.

Abstract submission: February 1 - March 15, 2017

Notification of acceptance: April 15, 2017

Early bird registration deadline: May 15, 2017

Regular registration and bursary travel application deadline: May 29, 2017

For more information:

please visit: http://www.esc2017.it/

or email the ESC 2017 Organizing Committee: esc2017@csgi.unifi.it