Nanostructured Polymeric Materials

Lead Research Organisation: University of Reading
Department Name: Chemistry

Abstract

Key scientific/technological challenges facing mankind at the opening of the 21st Century include the sustainable provision of both energy and water, a situation requiring a rapid shift away from technologies which consume resources without replenishment and which result in progressive degradation of the environment. The development of a sustainable approach to energy-generation, conversion and storage is recognised as one the highest priority areas in all of science. This is a field to which the Reading Polymer Group will make a substantial contribution through our work on low-cost polymer membranes for catalytic fuel cells, which generate electricity from hydrogen with very high efficiency and with only water as a by-product. Similarly, population growth and economic development across the planet is leading to rapidly increasing demands for clean drinking water, with even the prospect of water wars between nations which are constrained to share water resources. Here too, membrane science is key to meeting the challenge, with our own work focusing on the the development of membranes for the recycling of drinking water by low-pressure nanofiltration and ultrafiltration techniques. In this context we will also explore the potential of dispersed copolymer adsorbents as a novel approach to the removal of hazardous organic compounds from recycled water. A further global challenge results from the worldwide improvement in life expectancy, which is leading to increased incidence of age-related degenerative conditions such as Alzheimer's disease and CJD. These result from the misfolding, aggregation and precipitation of proteins in the form of amyloid plaques and fibrils in the brain. Our work in this field will involve the design, synthesis and detailed structural characterisation of amyloid-forming protein fragments and derivatives of these in which the fragments are linked to synthetic polymers. These latter materials will be designed to inhibit protein aggregation and precipitation, so that the work will be crucial in determining how such degenerative diseases can be controlled at the molecular level. The performance characteristics of polymeric materials are often crucially dependent on their detailed structure at the nanoscale. A fundamental aim of our research is to achieve specified polymer nanostructures through the self-assembly of polymer chains, with the assembly process itself being governed by the chain-sequences of the polymers involved. Synthetic methods providing unprecedented control over monomer sequences will be developed in the new research made possible by the Platform grant. This design-approach, underpinned by insights resulting from high-level theoretical studies and state-of-the-art structural analyses, will be followed in nearly all our work - from the study of membrane ionomers and amyloid-forming copolymers to new, exploratory work on self-repairing polymers and on polymer brushes as potentially responsive and biocompatible surfaces.The Reading Polymer Group (H.M. Colquhoun, I.W. Hamley, W. Hayes and M.W. Matsen) is involved in numerous international collaborations, including current EPSRC-funded programmes with groups at Case Western Reserve, the University of Michigan, the California Institute of Technology, and Northwestern University, Illinois. The Group's areas of expertise, in polymer theory (Matsen), synthesis (Colquhoun, Hayes and Hamley), characterisation (Hamley) and technological application (Colquhoun and Hayes) are highly complementary. The Group is funded from a wide range of sources and currently holds grants and external studentship-funding to a total value of 3.36M, including active EPSRC grants of 2.64M. Platform funding will enable a number of outstandingly gifted research staff to be supported flexibly over the next five years, and will allow the Reading Polymer Group to move rapidly into new fields of developing science.

Publications

10 25 50
 
Description Our work on this grant focused on issues of major importance to society - specifically the sustainable provision of energy, drinking water, health in old age, and information - through the targeted design and development of functional, nanostructured, polymeric materials. Key materials developed during the project included low-cost ionomers for proton transport in fuel cells and membrane electrolysers, new membrane polymers for nano/ultra-filtration of recycled water, peptides and peptide-polymer conjugates for the control of amyloid diseases and for tissue-regeneration. Self-assembling polymer systems were developed for application as structural materials, adhesives, biocompatible/ responsive surface coatings, and as media for information-storage and information processing at the molecular level.
Exploitation Route Our work on peptide chemistry for healthcare applications has potential applications in tissue regeneration (skin, cornea) and in the development of treatments for neurodegenerative amyloid diseases such as Parkinson's, Alzheimer's and CJD.

Our work on self-healing polymeric materials has potential applications in composite structures for automotive and aerospace applications. Also for damage-resistant cable coatings, self-repairing surface coatings, and structural adhesives.

Our work on ionomer membranes has potential applications in fuel cells (with either hydrogen or aqueous methanol as fuel), and in electrolysers for generating hydrogen from renewable energy sources such as wind and solar.

Our work on information-processing at the molecular level has potential applications in high-density data storage and in understanding the molecular origins of biological information.
Sectors Aerospace, Defence and Marine,Agriculture, Food and Drink,Chemicals,Construction,Electronics,Energy,Environment,Healthcare,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology,Transport

URL http://blogs.reading.ac.uk/chemistry/2013/03/06/miracle-ingredient-in-wrinkle-cream-revealed-by-professor-ian-hamley/
 
Description The work of Professor Hamley on Matrixyl (a peptide that he has shown promotes collagen production) has recently featured in the New Scientist, the Sunday Times and on BBC Radio 4. This work has led to the development and marketing of skincare products by Proctor and Gamble and by Forme Laboratories Ltd (to whom Professor Hamley is an advisor). In an extension of our research on membranes for sustainable energy and for water purification (Professors Colquhoun and Hayes) we have been awarded a three-year KTP project with BioInteractions Ltd. Here, membrane technology is used in a device to relieve the conditon of oedema by osmotic removal of excess fluid from the affected tissues. Many other industrial beneficiaries of our research were engaged during the period of the current Platform grant, including Novozymes, PharMaterials, Johnson Matthey, Domino Printing Sciences, AWE, DuPont-Teijin Films, BAE Systems, Cytec Engineered Materials, Henkel and DSTL. Such engagement is often achieved through interest generated by conference presentations, by press releases and news stories in the science media, and through personal research networks. The work with DuPont-Teijin Films has been especially noteworthy, resulting some 6 international patent filings on novel high-temperature polyester-imide films that extend the working temperature of such films well above those of existing polyesters. This work is currently being pursued to semi-technical scale by the company.
Sector Aerospace, Defence and Marine,Chemicals,Energy,Healthcare,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology,Retail
Impact Types Societal,Economic

 
Description BBSRC: Smart Materials for Wound Healing: A New Fast Acting in situ Method to Treat Skin and Eye wounds
Amount £122,470 (GBP)
Funding ID BB/J019836/1 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 01/2013 
End 12/2013
 
Description Collaborative MSc studenship: New polymer cross-linking systems
Amount £24,000 (GBP)
Organisation BAE Systems 
Sector Academic/University
Country United Kingdom
Start 01/2012 
End 12/2012
 
Description Collaborative PhD studentship: Healable polymers in power distribution networks
Amount £40,000 (GBP)
Organisation Gnosys Global 
Sector Private
Country United Kingdom
Start 01/2014 
End 12/2016
 
Description Collaborative PhD studentship: High strength supramolecular polymers
Amount £40,000 (GBP)
Organisation Atomic Weapons Establishment 
Sector Private
Country United Kingdom
Start 10/2010 
End 03/2014
 
Description Collaborative PhD studentship: High-Tg polyester-imides
Amount £68,000 (GBP)
Organisation DuPont Teijin Films 
Sector Private
Country Global
Start 10/2012 
End 09/2015
 
Description Collaborative PhD studentship: High-acidity fuel cell membranes
Amount £30,000 (GBP)
Organisation Johnson Matthey 
Sector Private
Country United Kingdom
Start 10/2011 
End 09/2014
 
Description Collaborative PhD studentship: New composite materials
Amount £83,910 (GBP)
Organisation BAE Systems 
Sector Academic/University
Country United Kingdom
Start 01/2013 
End 12/2016
 
Description Collaborative PhD studentship: Polymeric Fuel and Lubricant Additives
Amount £36,000 (GBP)
Organisation BP (British Petroleum) 
Sector Private
Country United Kingdom
Start 10/2012 
End 09/2015
 
Description Collaborative PhD studentship: Use of weak non-covalent interactions in novel adhesives
Amount £30,000 (GBP)
Organisation Henkel 
Sector Private
Country Germany
Start 01/2011 
End 12/2014
 
Description Direct Industrial funding
Amount £85,000 (GBP)
Organisation BAE Systems 
Sector Academic/University
Country United Kingdom
Start 10/2012 
End 09/2015
 
Description EPSRC Jumpstart grant
Amount £62,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 07/2014 
End 12/2014
 
Description EPSRC responsive mode: A Small-Angle Scattering Study of the Self-Assembly of Amyloid Peptides
Amount £143,407 (GBP)
Funding ID EP/G067538/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 05/2010 
End 10/2014
 
Description EPSRC responsive mode: Supramolecular Polyurethanes and their Composites: Properties and Engineering Performance
Amount £387,021 (GBP)
Funding ID EP/J010715/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 11/2012 
End 11/2015
 
Description EU FP7 Joint Undertaking: "Next Generation Polymer Membrane Electrolyser"
Amount € 28,000 (EUR)
Funding ID 245262 
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 01/2010 
End 12/2012
 
Description EU H2020 Marie Curie ETN: "EURO-SEQUENCES"
Amount € 273,288 (EUR)
Funding ID 642083 
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 01/2015 
End 12/2018
 
Description Healable composites
Amount £60,000 (GBP)
Organisation Cytec Industries 
Sector Private
Country United States
Start 01/2013 
End 12/2015
 
Description KTP: Membrane device for the treatment of oedema
Amount £205,729 (GBP)
Organisation TSB Bank plc 
Sector Private
Country United Kingdom
Start 01/2014 
End 12/2016
 
Description Platform Grant Renewal: Nanostructured Polymers for Healthcare
Amount £1,185,824 (GBP)
Funding ID EP/L020599/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 06/2014 
End 05/2019
 
Description Royal Society Brian Mercer Feasibility Award
Amount £30,000 (GBP)
Organisation The Royal Society 
Sector Charity/Non Profit
Country United Kingdom
Start 06/2013 
End 06/2014
 
Description STFC Futures studentship: Enzyme-responsive hydrogels for diagnostics, delivery and regenerative medicine
Amount £35,244 (GBP)
Funding ID ST/L502480/1 
Organisation STFC Laboratories 
Sector Public
Country United Kingdom
Start 06/2013 
End 05/2017
 
Description Supramolecular polymers for ink-jet printing
Amount £88,000 (GBP)
Funding ID IC/10002591 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 10/2010 
End 03/2014
 
Description Surfaces for Molecular Recognition at the Atomic Level ("SMALL")
Amount € 404,000 (EUR)
Funding ID 238804 
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 10/2010 
End 09/2013
 
Description Domino 
Organisation Domino (UK)
Country United Kingdom 
Sector Private 
PI Contribution Industrial CASE award (EPSRC). PhD student developed new supramolecular polymers for application in industrial inkjet printing.
Collaborator Contribution Domino provided facilities for evaluating the new materials under actual inject printing conditions, including accommodation and travel for the PhD student working at Domino.
Impact Further PhD funding (2015-2017) following the success of the Industrial Case project. Patent filings by Domino in this field.
Start Year 2010
 
Description EuroSequences 
Organisation Charles Sadron Institute
Department Precision Macromolecular Chemistry
Country France 
Sector Public 
PI Contribution The collaboration is an EU Horizon-2020 Marie Sklodowska-Curie ITN, which funds 15 PhD studentships in Universities across a range of EU countries. The network is coordinated by J-F Lutz of the Institut Charles Sadron in Strasbourg, France. One such studentship is held in my own group at Reading. The project is entitled Euro-Sequences and is aimed at writing and reading comonomer sequence information at the level of individual polymer molecules. Our contribution is to develop small molecules that recognise specific sequences in polymer chains and so enable such sequences to be read out via NMR spectroscopy. Also to develop methods for exchanging sequences between polymer chains (as occurs in DNA) as a primitive method of "writing" new information into the chains.
Collaborator Contribution Objective 1 (Polymer Chemistry): an important goal of the project is the development of new synthetic routes for preparing sequence-controlled copolymers. One important target is the development of high-molecular weight sequence-defined polymers using fast and easy chemical protocols. In order to reach that goal, automatized chemical protocols will be used in several individual sub-projects. Objective 2 (Self-assembly and folding): As learned from biopolymers such as proteins, the primary structure of synthetic macromolecules has a direct influence on their folding and supramolecular selforganization. Hence, an important objective of the project is to use controlled comonomer sequences for preparing folded macromolecular origami. Objective 4 (Materials and properties): The correlation between primary structure and materials properties, in particular, the influence of ordered monomer sequences on thermal and mechanical properties (e.g. tensile strength, rupture) of synthetic polymer materials is examined in detail. The ultimate objective is the development of precision polymer materials for the plastics industry.
Impact Research lectures at consortium meetings in Strasbourg (Jan. 2015) and Ghent (Oct. 2015). Collaboration is mainly chemistry, including organic, analytical, polymer and supramolecular chemistry.
Start Year 2015
 
Description Johnson Matthey plc 
Organisation Johnson Matthey
Country United Kingdom 
Sector Private 
PI Contribution Collaboration on fuel-cell membranes in which Reading developed new ionic polymers and developed methods for casting membranes.
Collaborator Contribution Johnson Matthey were able to fabricate our membranes into membrane-electrode assemblies and evaluate these under actual fuel-cell operating conditions.
Impact Patents and publications. Funding for PhD studentships. Collaborative TSB projects. See relevant sections.
 
Description University of Delaware 
Organisation University of Delaware
Country United States 
Sector Academic/University 
Start Year 2006
 
Title COPOLYESTERIMIDES COMPRISING BIS(2-HYDROXYALKYL)-2,2'-(1,4-PHENYLENE)BIS(1,3-DIOXOISOINDOLINE-5-CARBOXYLATE) AND ARTICLES MADE THEREFROM 
Description A copolyester comprising repeating units derived from an aliphatic glycol, an aromatic dicarboxylic acid, and the monomer of formula (I): (Formula (I)) wherein n = 2, 3or 4, and wherein comonomer (I) constitutes a proportion of the glycol fraction of the copolyester; and a film,fibre or moulding composition or moulded article comprising said copolyester. 
IP Reference WO2015193682 
Protection Patent application published
Year Protection Granted 2015
Licensed Yes
Impact None as yet.
 
Title COPOLYESTERIMIDES OF POLY(ALKYLENE TEREPHTHALATE)S HAVING HIGH GLASS TRANSITION TEMPERATURE AND FILM MADE THEREFROM 
Description A copolyester comprising repeating units derived from an aliphatic glycol, terephthalic acid, and the monomer of formula (I): wherein n = 2, 3 or 4, and films, fibres, moulding compositions and moulded articles made therefrom. 
IP Reference WO2013093446 
Protection Patent application published
Year Protection Granted 2013
Licensed Commercial In Confidence
Impact Impact on development programme of DuPont Teijin Films.
 
Title COPOLYESTERIMIDES OF POLY(ALKYLENE TEREPHTHALATE)S HAVING HIGH TG AND HIGH MONOMER CONTENT AND FILM MADE THEREFROM 
Description A copolyester comprising repeating units derived from an aliphatic glycol, terephthalic acid, and the monomer of formula (I): wherein n = 2, 3 or 4, wherein comonomer (I) constitutes a proportion of the glycol fraction of the copolyester, and wherein the comonomer (I) is present in amounts of greater than 10 mol% of the glycol fraction of the copolyester, and films and articles made therefrom. 
IP Reference WO2014096763 
Protection Patent application published
Year Protection Granted 2014
Licensed Commercial In Confidence
Impact Impact on development programme of DuPont Teijin Films. Fully-funded (by DTF) PhD student following up this work at Reading. Royal Society Brian Mercer Feasibility Award received to help progress commercialisation.
 
Title Inkjet composition 
Description A printed deposit comprising a self-assembled supramolecular polymer formed by Ï - Ï stacking interactions between at least a portion of a first polymer (preferably an electron-rich chromophore comprising an aromatic or heteroaromatic ring, such as pyrenyl or naphthyl) and at least a portion of a second polymer (preferably an electron-deficient chromophore comprising an alkene or an aromatic or heteroaromatic moiety, such as a naphthalene diimide or a dinitrofluorenone). An ink composition suitable for forming the deposit of the self-assembled supramolecular polymer comprising a solvent and a first and a second polymer, wherein at least a portion of the first polymer is capable of forming Ï - Ï stacking interactions with at least a portion of the second polymer to form the self-assembled supramolecule. 
IP Reference GB2511623 
Protection Patent application published
Year Protection Granted 2014
Licensed Commercial In Confidence
Impact Impact on development programme of Domino Printing Sciences Ltd (Cambridge UK).
 
Title LOW VISCOSITY SUSPENDING VINYL COPOLYMERS 
Description A rheology modifier copolymer of formula (I), wherein A is a macromonomer; B is an acrylic or methacrylic acid or salt thereof; C is a polyacidic vinyl monomer selected from maleic, fumaric, itaconic, citraconic and acids combinations thereof and anhydrides and salts thereof; and D optionally when present is a crosslinking monomer. 
IP Reference US2014256897 
Protection Patent granted
Year Protection Granted 2014
Licensed Commercial In Confidence
Impact Significant impacts on the product development programme of DuPont Teijin Films.
 
Description Public lecture at the RSC in London: Our Light Materials 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact Lots of questions and discussion afterwards. I had mentioned the materials issues with the early Comet airliner, and one member of the audience wanted to talk specifically about this as her father had been involved in investigating the problem.

Several invitations (subsequently taken up) to give the lecture to A-level students in schools.
Year(s) Of Engagement Activity 2012
URL http://www.youtube.com/watch?v=M_REbBFj_x8
 
Description Royal Society Summer Science Exhibition 2015 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Public/other audiences
Results and Impact In the summer of 2014 my PhD student Kate Lim mentioned to me that she had just been to the Royal Society Summer Exhibition in London, and that she thought it was a really great way for scientists to get their research in front of the public. Well, that would be one way of putting it. What she actually said was "We could do that!"

In fact, thinking about it later, our work on self-healing polymeric materials did seem like something a lot of people might be interested in, and we managed to persuade my colleague and collaborator in this field, Wayne Hayes, and his collaborator Clive Siviour in the Oxford University Engineering Department to go along with the idea. Our subsequent joint proposal to the Royal Society for an exhibit at their 2015 exhibition, to be called "Materials that Repair Themselves", was accepted as one of only two chemistry exhibits that year.

We were then faced with the problems of designing, building, and of course funding the exhibit. In the end, the Universities of Reading and Oxford put up most of the money, and colleagues from industry generously loaned us various items to enhance our exhibition stand. These included the front end of an only slightly damaged Formula 1 car, built from high-performance composite materials, and an ultra-high-speed camera that showed how materials fail in real time. Visitors could puncture a balloon and then watch the details of their balloon imploding in very..... slow..... motion.

Colleagues in the Events Department at Reading, notably Ellie Gotay, helped us design the actual stand, which took the form of a backdrop showing a chemistry research lab, with exhibition tables and computer displays in front. One computer showed continuous molecular simulations of polymer chains breaking apart from one another and then re-assembling through hydrogen bonding and p-p-stacking. This reflected the actual mechanisms by which are own recently-published materials repaired themselves after mechanical damage. Samples of a new commercial polymer of this type were also exhibited, and we delighted in slicing through samples of this material with special cutters and handing the pieces to our visitors. They would then watch in disbelief as the fragments in their hands grew back together again. "It's not magic" we would say, "it's chemistry".

We used classical molecular models to show how the basic polymer molecules were constructed and how they interacted with one another. However, to illustrate one of the key mechanisms behind polymer self-healing, Kate also built a special set of models using polystyrene spheres and carefully-positioned Velcro patches to simulate hydrogen bonds. When the initially-separated "molecules" were shaken together (simulating random thermal motion) in a large polyethylene box, they reversibly assembled into a flexible, coherent mass - a visual simulation of polymer self-repair.

The exhibition ran for seven days in early July 2015. It was the hottest July week on record, and more than 2000 visitors a day piled through the doors of the Royal Society in Carlton House Terrace. We were able to explain and demonstrate our story to nearly all these visitors, who ranged from madly keen schoolchildren, to enthusiastic adults, unexpected experts ("I used to work for NASA") and passing Fellows of the Royal Society. Exhibitors on the stand from Reading were: Professors Howard Colquhoun and Wayne Hayes; Drs Ben Littlefield, Lewis Hart and Antonio Feula; research students Kate Lim, Corinne McEwan, Ben Baker and Tahkur Singh Babra; and events organiser Ellie Gotay. Exhibitors from Oxford were: Professor Clive Siviour; Dr Xuegang Tang and research students Heather Wilson and Sung-Ho Yoon.

In order to preserve our voices - and our sanity - Kate had to run a military-style operation, with four or five staff and research students manning the stand at any one time and being relieved at half-day intervals by incoming teams from Reading and Oxford. The afternoon teams would stay overnight in a student hall in Bloomsbury before taking on the next morning shift and being relieved in their turn at lunchtime. It was exhausting but massively enjoyable work, and we all felt afterwards that we had made a real contribution to public engagement with the science of advanced materials. Several visitors subsequently contacted us to ask for lectures, magazine articles, television and newspaper interviews (all of which were duly provided), and a year after the event we are still getting hits on our exhibition Facebook and Twitter pages.
Year(s) Of Engagement Activity 2015
URL http://sse.royalsociety.org/2015/mending-materials/
 
Description School Visit (Charterhouse) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact Lecture on "Our Light Materials" for students aged 14-18, from a number of schools, given at Charterhouse in October 2013. About 70 students took part in the lecture with lively discussions afterwards. The talk covered the science behind modern high-performance composite materials and their applications in medicine, aerospace, and automotive technologies.
Year(s) Of Engagement Activity 2013
URL http://www.charterhouse.org.uk/chemistry-lecture
 
Description School Visit (Eltham) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact Presentation of sixth-form lecture "Our Light Materials" at Eltham College (South London) describing the science behind the development of lightweight polymeric materials, including carbon fibre composites, and the applications of these materials in the modern world.
Year(s) Of Engagement Activity 2017
URL https://www.elthamcollege.london/school-calendar/sixth-form-talk-professor-howard-colquhoun-universi...