Welcome Message Welcome to Warwick 2016 the 4

P164

Mr Zan Hua

University of Warwick

Living Micelles with Tuneable Morphologies through Interactions between Nucleobase-Containing Synthetic Polymers in Aqueous Solution

Herein, we report the preparation of nucleobase-containing synthetic amphiphilic diblock copolymers using RAFT polymerization. Well-defined spherical micelles can be formed in aqueous solutions through the self-assembly of amphiphilic nuceleobase-containing copolymers. Following assembly, copolymers with complementary nucleobases were introduced into the micellar solutions. The effect of such complementary nucleobase polymer was explored by DLS, SLS, SAXS and TEM. Depending on the length of the hydrophobic segment, a change in particle morphology could be observed. Nucleobase-containing copolymer interactions present a new and versatile method to access various self-assembled nanostructures.

P165

Mr Zhanyao Hou

Ghent University

Anthracene-based Hydrogels: From Supramolecular to Covalent Conversion via Photo-irradiation

Generally, Hydrogels can be classified into covalent and supramolecular hydrogels. In supramolecular hydrogels, a sol-gel transition can occur, which expanded their applications. However, poor non-covalent bonds are not stable against dilution, which limited their applications. We designed a new hydrogel that can undergo the conversion of non-covalent to covalent crosslinking based on anthracene group. Anthracene-containing poly(N-acryloylmorpholine) copolymers which form hydrogels were prepared by RAFT polymerization followed by a nucleophilic substitution reaction. Upon the addition of CB[8], a supramolecular hydrogel should be formed by host-guest interaction between CB[8] and two anthracene groups. Such a supramolecular hydrogel can be further converted into its corresponding covalently crosslinked hydrogel upon the irradiation at 365 nm. The studies of the formation of supramolecular hydrogel and the conversion between non-covalent and covalent crosslinking are currently ongoing.

P166

Miss Zoe Roberts

University of Warwick

Preparation and Characterisation of Thermoplastic Elastomers Containing Biodegradable Hard Segments

The use of a wide range of degradable hard segments of polyurethanes, including those derived from amino acids, has been of great interest as a result of their susceptibility to degradation but also because of their non-toxic byproducts. Variation in the hard segment composition, opens up greater control over the degradation and mechanical properties. A series of thermoplastic polyurethane elastomers with degradable hard and soft segments were synthesised. The incorporation of degradable linkages within the hard segment enables the more complete breakdown of the material. The resultant properties of these materials were studied, including mechanical analysis, contact angle analysis and hydrolytic degradability and in turn were correlated to polymer structure and composition which provided a greater understanding of the structure-function relationship of these materials.

P167

Dr Ignacio Martín-Fabiani

University of Surrey

Water Barrier Properties of Films Made from Particles Using a Modified Polymerisation-Induced Self-Assembly (PISA) Process

The presence of surfactants in latex films causes detrimental effects on water permeability and adhesion. Here, we report the synthesis of surfactant-free latex particles, using hydrophilic macromolecular RAFT agents (macroRAFTs) in water. In a Polymerization-Induced Self-Assembly (PISA) process, macroRAFTs can act as stabilizers during emulsion of acrylic monomers to obtain self-stabilized particles. Our results show that films made from these particles have lower water vapour sorption and liquid water uptake than conventional latex films made via conventional emulsion polymerization. NMR relaxometry allowed us to determine the degree of water confinement within soaked coatings. Notably, both the use of a less hydrophilic macroRAFT and a slight reduction in its content have a strong and positive impact on the barrier properties. The results presented here provide evidence for the potential of self-stabilized latex particles for the development of new waterborne protective coatings.

P168

Miss Elizabeth Jones

The University of Sheffield

How do Spherical Diblock Copolymer Nanoparticles Grow during RAFT Alcoholic Dispersion Polymerisation?

A poly(2-(dimethylamino)ethyl methacrylate) (PDMA) chain transfer agent was used for the RAFT dispersion polymerisation of benzyl methacrylate (BzMA) in ethanol. GPC analysis indicated a well-controlled polymerisation. The PBzMA block becomes insoluble as it grows, leading to the in situ formation of diblock copolymer nanoparticles via polymerisation-induced self-assembly. Varying the DP of the PBzMA block while using a given PDMA block produced a series of spherical nanoparticles with mean diameters ranging from 35 to 100 nm diameter. These nanoparticles were characterised by TEM, DLS, MALLS and SAXS. Mean aggregation numbers calculated from SAXS and MALLS are in good agreement and scale approximately linearly with PBzMA DP. This suggests that spherical micelles grow in size not only as a result of the increase in copolymer molecular weight during the PISA synthesis, but also by exchange of individual copolymer chains between micelles and/or by sphere-sphere fusion events.

P169

Mr Abdessamad Kaassis

UCL

Pulsatile drugs release from electrospun poly(ethylene oxide)–sodium alginate blend nanofibres

Novel and highly tuneable pulsatile drug delivery systems have been prepared through the electrospinning of a blend of poly(ethylene oxide) (PEO), sodium alginate (SA), and drugs. Fibres were prepared with a range of loadings of drugs and SA. The resultant fibres formed novel three dimensional structures contain crystalline drugs. It was found that at pH 6.8 (reminiscent of the intestinal tract) the fibres dissolve very rapidly, freeing all the embedded drugs quickly. However, at condition that mimic the gastrointestinal transit an unusual two stage release mechanism is seen. This comprises a rapid burst release, followed by a period where no further drug is released, and then a final stage of release freeing the remainder of the drug into solution. The amount of release in the initial stage, and the length of time between the first and final drug release stages, can be controlled by adjusting the drugs and/or SA contents. This results in highly tunable pulsatile release materials.

P170

Mr Adrian Williams

PSS Polymer Standards Service GmbH

Characterization of poly (methyl methacrylate)-graft-poly (styrene)s using various chromatographic techniques.

Two graft copolymer samples of identical average composition were synthesized by grafting polystyrene onto a broadly distributed PMMA backbone. GPC with viscometry and light scattering detection, GPC with UV and RI dual detection, gradient chromatography and 2D chromatography were applied to determine sample heterogeneity. While only limited information was retrieved by conventional GPC or GPC with molar mass sensitive detection, GPC with UV and RI revealed different chemical heterogeneity of the samples. Using gradient chromatography and 2D chromatography it was possible to identify non-grafted side chains and unreacted parent PMMA as well as the actual graft copolymer molecules. While in one sample, a heavily grafted product was formed in addition to non-grafted PMMA, the second sample did not contain any non-grafted PMMA but a graft product of lower grafting density. The different product distributions were explained by the different synthetic procedures.

P171

Miss Alaa Kadhim

One pot synthesis of star-shaped copolymers based on poly (e-caprolactone) and Polyglycerol for hydrophobic drug carriers

One pot synthesis of star-shaped copolymers based on poly (e-caprolactone) and Polyglycerol for hydrophobic drug carriers

Amphiphilic star shaped poly(e-caprolactone)-b-hyperbranched polyglycidol (sPCL-b-HPG) was successfully synthesized and used to deliver a verity of hydrophobic drug molecules. The first step of the synthesis involved the polymerization of e-caprolactone (CL) from a multifunctional core (trimethylolpropane (TMP)) to give the initial star polymer (SPCL) via ring opening polymerization. Then, glycidol was polymerized directly from the SPCL-HPG. The structure of SPCL-HPG was characterized by 1H-NMR, FTIR and GPC. TMP cored SPCL-HPG was used to encapsulate hydrophobic drugs: tetrakis 3,5-dihydroxyphenyl porphyrin (TDHPP, M_n=743) and 3,5-diacetoxyphenyl Porphyrin cored Hyperbranched Polymer (3,5-diacetoxybenzoic acid) (P-HBP, Mn=3000) respectively. The results showed that the drugs solubility in SPCL40-HPG60 were enhanced significantly. SPCL-HPG provide an alternative choice of drug carriers for different size of poorly soluble drugs.

P172

Mr Alan Rigoussen

Luxembourg Institute of Science and Technology (LIST)

Investigation on the compatibilization of immiscible polymers blends

Polylactide (PLA), a bio-based polymer with interesting properties, has limited applications according to its brittleness and poor thermal stability. Polymer blending of PLA with acrylonitrile-butadiene-styrene (ABS), a petroleum based thermoplastic with interesting thermal and mechanical properties, is an effective method to enhance the properties of PLA aiming at extending its applications. However, the incompatibility between PLA and ABS remains a challenge to obtain a polymer blend with tailored properties. Compatibilization of PLA and ABS using cardanol, a naturally occurring phenolic compound, has been implemented by reactive extrusion. In this presentation, we will highlight the efficiency of cardanol as compatibilizer and the compatibilization mechanisms based on the reaction of cardanol with the polymers.

P173

Miss Alba Castañon

The University of Nottingham

Synthesis of CO2-soluble hydrocarbon based stabilisers by RAFT/MADIX polymerisation

Carbon capture is now a major global process and our aim is to make positive use of the captured CO2 as an alternative and clean solvent for polymer synthesis. We report the synthesis of hydrocarbon based CO2-soluble polymers that work as surfactants in dispersion polymerisation and overcome the limitations requiring fluorinated or siloxane materials that are expensive and not environmentally acceptable and can be used in a wider variety of monomers than the previous ones reported.1

A range of P(VAc-s-VPi)-b-PNVP block copolymers with different molecular weight and molar ratios were synthesized using controlled radical polymerisation techniques (RAFT/MADIX) and analysed by NMR (1D and 2D), GPC (in THF) and DSC. Solubility of the samples in scCO₂ was determined using a variable volume view cell designed at The University of Nottingham.

P174

Ms Alessia Weiss

ARC Centre of Excellence in Convergent Bio-Nano Science and Technology, and the Department of Chemical and Biomolecular Engineering, The University of Melbourne, Parkville, Victoria 3010, Australia

Controlled Protein Adsorption on Zwitterionic Replica Particles

There is mounting evidence that the formation of a protein corona around drug delivery vehicles is the primary determinant of their biological behaviour in vitro and in vivo, as this changes the particle’s ‘synthetic identity’ to a ‘biological identity’. Therefore, it is crucial to understand how particle design parameters such as size and surface chemistry as well as the biological milieu which includes protein solution composition and adsorption conditions influence this process. This understanding will assist in the design of smarter drug carriers, which either diminish protein adsorption or take advantage of the adsorbed corona. Furthermore, it will facilitate predicting protein corona formation and therefore bio-nano interactions. In this study, we investigate the adsorption of proteins around zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine) replica particles under varying conditions as well as the impact of flow by using defined microfluidic systems.

P175

Mr Alex Oliver

University of Bristol

Patchy Micelles via the “Living” Crystallization-Driven Self-Assembly of Polyferrocenylsilane Triblock Terpolymers

Living crystallization-driven self-assembly of crystalline-coil diblock copolymers allows the formation of well-defined micellar architectures with controlled size and dimensionality.1 Although a variety of architectures are possible through this route, there are several limitations towards preparing materials with distinct microphase coronal structures.2 ABC triblock terpolymers, with two chemically different polymers attached to a central core-forming block, can open new routes to polymer nanostructures within the corona of micelles.3 Herein, we will report the synthesis of a variety of PFS-containing ABC triblock terpolymers and the solution-phase self-assembly of these materials towards the formation of “patchy” structures.

1. Z. M. Hudson, I. Manners et al., Nat. Chem., 2014, 6, 893-898. 2. J. Schmelz, H. Schmalz et al., Soft Matter, 2013, 9, 2101-2107. 3. J. Schmelz, H. Schmalz et al., J. Am. Chem. Soc., 2012, 134, 14217-14225.

P176

Dr Alexander Ilchev

Department of Chemical and Environmental Engineering at the University of Nottingham

Poly(D,L-Lactide) Star Polymers as Dispersants for Hydroxyapatite Nanoparticles during Nanocomposite Manufacturing

Star polymers of rac-poly(lactic acid) (s-PLA) were prepared for use as dispersants for hydroxyapatite nanoparticles in a polymer matrix. Better control of the stars’ molecular weight and dispersity was achieved in all polymerisations relative to similarly prepared linear PLA. This was attributed to the degenerative chain transfer process between the star polymer’s arms causing a greater probability of transfer relative to propagation during polymerisation. The reaction temperature was optimized to allow for the shortest reaction times while keeping the catalyst concentration below the limits for biomedical materials and minimizing the rates of degradation reactions to below detectable levels. All reactions were carried out to over 90% conversion. The residual lactide was efficiently removed by vacuum distillation. The poor thermal diffusivity of PLA coupled to an exothermic enthalpy of polymerisation may result in a thermal runaway for larger scale polymerisations.

P177

Dr Amanda K. Pearce

University of Nottingham/University of Queensland

Localised delivery of doxorubicin to prostate cancer cells through a PSMA-targeted hyperbranched polymer theranostic

The therapeutic potential of hyperbranched polymers targeted to prostate cancer was investigated. PEGMA hyperbranched polymers were synthesised via RAFT polymerisation to feature targeting ligands for PSMA on the periphery, with doxorubicin attached through hydrazone formation, which allowed controlled release of the drug from the polymers in in vitro endosomal conditions. The polymers could target PSMA-expressing prostate cancer cells in vitro and facilitate transport of doxorubicin into the cells as confirmed by live cell confocal imaging. Finally, the ability of the complex to induce a therapeutic effect on prostate cancer cells was investigated through a tumour regression study, which confirmed that the DOX-loaded polymers could significantly reduce the volume of prostate tumours in vivo in comparison to free drug and a polymer control, with no adverse toxicity to the animals. This work therefore demonstrates the potential of this system for prostate cancer theranostics.

P178

Dr Alexandra Gower

University of Nottingham

Accelerated Synthesis of Polymers via Electromagnetically Heated Catalytic Chain Transfer Polymerization Using Cobalt and Iron Catalysts

This paper reports work to improve the CCTP of acrylates via the use of electromagnetic heating/excitation and chain transfer agents (CTA) which are more sustainable than the benchmark cobalt centered CCTP catalysts. These CTAs are based on iron and exhibit greater activity with acrylates than the cobalt centered species. By comparison with cobalt, iron is more toxicologically acceptable for use in catalyst systems that are intended for applications in biomedical devices. The synthesis of a range of Fe CTAs is detailed, as is a comparison of their performance with methyl methacrylate and methyl acrylate. In the case of the acrylate monomer, when CCT was conducted using Fe CTAs and conventional heating, the polymerization was inhibited. By adopting MWH, previously reported to promote FRP propagation over termination, it is demonstrated the inhibition can be overcome. This demonstrates improved CCTP with acrylates and supports the proposal that MWH can increase the rate of propagation.

P179

Dr Ana Sousa-Herves

Glycosystems Laboratory, Instituto de Investigaciones Químicas (IIQ).

Polymeric Glyconanogels as Inhibitors of Lectin-Mediated Viral Infections

Carbohydrate-protein interactions mediate many biological processes including tumour progression, inflammation, and viral infection. These interactions are typically characterized by a high selectivity and a low affinity, which is compensated in Nature by multivalency.

In this communication, we will report the synthesis and characterization of multivalent glyconanogels prepared from FDA-approved Poly(ethylene glycol) (PEG). The nanogels display multiple mannose moieties and have been designed to interact with the cellular receptor DC-SIGN by mimicking viral structures. DC-SIGN is a lectin that recognizes highly mannosylated glycoproteins, and is known to play a key role in the initial stages of many viral infections, including HIV and Ebola virus. Finally, infection assays performed with an artificial Ebola virus demonstrated the potent antiviral activity through specific DC-SIGN recognition of the glyconanogels.

P180

Miss Anna P. Constantinou

Imperial College London

Thermoresponsive Gels Based on Multiblock Copolymers

Triblock and tetrablock copolymers were synthesised using Group Transfer Polymerisation (GTP). These polymers were based on poly(ethylene glycol) (PEG) based methacrylates, the hydrophobic n-butyl methacrylate (BuMA) and the hydrophilic, pH-responsive as well as thermoresponsive 2-(dimethylamino)ethyl methacrylate (DMAEMA). Several structural polymeric characteristics were varied like the length of the PEG group for the triblock copolymers and the position of the blocks for tetrablock copolymers. The influence of these structural characteristics on the polymers self-assembly ability and their thermoresponsive properties with emphasis on their ability to form injectable gels was investigated.

P181

Miss Anne Fuhrmann

Laboratory of Organic Chemistry and Functional Materials, Department of Chemistry, Humboldt-Universität zu Berlin

Switching the healing capability of dynamic covalent polymers by light

The reversible thermoresponsive crosslinking of polymers contributes significantly to the field of smart, self-healing materials [1]. A prominent motif is the Diels-Alder reaction in which the pair of maleimide and furan is the most reliable [2,3]. Herein, we apply our concept of photocontrolling a reversible reaction [4] to polymer networks consisting of thermo- and photoresponsive furyl-substituted diarylethene crosslinkers and maleimide-containing copolymers. By turning the Diels-Alder crosslinking reaction ON or OFF with light, we demonstrate a control of the local healing of scratches in thin films. We envision a use of these responsive polymers in coating applications where the healing ability of the films can be controlled by irradiation with light of different wavelengths.

[1] Tasdelen, Polym. Chem. 2011, 2133.

[2] Syrett, Becer, Haddleton, Polym. Chem. 2010, 978.

[3] Asadirad et. al., J. Am. Chem. Soc. 2014, 3024.

[4] Göstl, Hecht, Angew. Chem. Int. Ed. 2014, 8784.

P182

Ms Anne-Kristin Trützschler

Friedrich-Schiller Universität Jena, Laboratory of Organic and Macromolecular Chemistry/JCSM

Entering the Brain: Glutathione modified polyethylenimin derivative for brain delivery

The controlled delivery of genetic material into cells is more topical than ever. Besides viral transfection, non-viral delivery is of high interest, reflected in the large number of transfection agents being proposed. Thereby, poly(ethylene imine) (PEI) represents the gold standard for in vitro applications. While the transfection of cells in vitro is established, the delivery in vivo is demanding. Due to the blood-brain barrier (BBB), the targeting of cells in the brain without active transporters is limited. Recently, the application of glutathione (GSH) as targeting molecule for nanoparticle coating was reported. With this study we show the route to a GSH connected PEI copolymer. Using two synthesis routes, differences in complexation efficiency and cellular interaction of amines placed in the backbone and side chain were studied. With that approach polymers with GSH have been synthesized and the ability of crossing the BBB was investigated in a dynamic cell culture model.

P183

Dr Antonio Ruiz-Sanchez

Newcastle University

Zwitterionic-Fluoro Hydrogels as Anti-Biofouling Coatings.

The unwanted fouling of surfaces by organisms presents a huge and largely unsolved problem. From medical implants to the hulls of ships, fouling leads to reduced performance and increased costs. For example, fouling of ship hulls increases fuel consumption up to 40%. Considering there are over 90,000 vessels in the world fleet, with the largest ships consuming over 350 tonnes of fuel per day, the fuel savings and the reduction in greenhouse gas emissions would be considerable if biofouling were eliminated. Fluoropolymers and zwitterionic polymers individually make platforms for achieving fouling deterrence but have never been studied as a conjugate system. We report the copolymerization of fluoropolymers end-terminated with methacrylate functions with methacrylate-based zwitterion monomers to produce polymer coatings in a way which allows control of surface properties. Their antifouling behaviour was assessed and found to relate to coating composition and method of preparation.

P184

Miss Ariane PEYRET

Laboratoire de Chimie des Polymères Organiques

Photon-triggered cargo release from polymersomes under temporal, spatial and spectral control

Polymersomes are robust self-assembled vesicular structures that are employed in many domains. Control over their membrane properties is crucial, in particular in drug delivery applications. Here, we present a method allowing programmed vesicle rupture with full control in time, space and excitation wavelength for selective cargo-release.

We designed a tunable protocol for light-driven polymersome rupture, which combines the advantages of utilizing light as a trigger and the fast release of components from bursting vesicles. Our system is based on laser excitation of hydrophilic dyes encapsulated in the lumen of distinct giant poly(butadiene)-b-poly(ethylene oxide) polymersomes. Upon excitation, the fast generation of reactive oxygen species leads to an increase of the internal osmotic pressure that can not be compensated fast enough, resulting in vesicle rupture. We show that we can rupture polymersomes with high precision, and even to deliver small polymersomes and liposomes.