We have collected a large portfolio of polymerisation protocols to make almost any type of macromolecule as well as characterising their molecular mass and composition. We focus most of our synthetic efforts to make either diblock or triblock amphiphilic copolymers and as showed in Fig.1, we have made them combining different chemistries. For many years, we did this in collaboration with other groups experts in polymer synthesis where our input was limited either to the physical and/or the biological characterisation of the final products. With Prof Anthony Ryan, we have had access to both hydrophilic and hydrophobic polyethers either combined with each other or with polybutadiene. With Prof Steve Armes we worked with several methacrylate copolymers of which poly(2-(methacryloyloxy) ethyl phosphorylcholine) – poly(2-(di-isopropylamino)ethyl methacrylate) (PMPC-PDPA) being the most studied. We have now learned to make polymers ourselves and expanded our synthetic protocols to involve ring opening polymerisation and solid-phase synthesis methods. Our aim is to create simple and scalable protocols focussing on chemistry that is already clinically used. Meanwhile, we still work with experts in polymer synthesis to explore future approaches. These include Prof Charlotte Williams with who we're learning how to upgrade our ring-opening synthesis using more complex architectures, with Dr Remzi Becer where we are looking at glycopolymers and controlled sequence polymers, with Prof Robert Luxenhofer who we are working with polypeptoids.
- G. Yilmaz, L. Messager, A. S. Gleinich, D. A. Mitchell, G. Battaglia, C. R. Becer Glyconanoparticles with controlled morphologies and their interactions with a dendritic cell lectin Polymer Chem. 2016, 7 (41), 6293-6296
- C. Fetsch, J. Gaitzsch, L. Messager, G. Battaglia, and R. Luxenhofer Self-Assembly of Amphiphilic Block Copolypeptoids for Drug Delivery Carriers - Micelles, Worms and Polymersomes Sci. Rep. 2016, 6:33491
- J Gaitzsch, V. Chudasama, E. Morecroft, L. Messager, G. Battaglia Synthesis of an Amphiphilic Miktoarm Star Terpolymer for Self-Assembly into Patchy Polymersomes ACS Macro Lett. 2016, 5, 351–354
- P. Chambon, A. Blanazs, G. Battaglia and S. Armes Facile Synthesis of Methacrylic ABC Triblock Copolymer Vesicles by RAFT Aqueous Dispersion Polymerization Macromolecules 2012, 45, 5081–5090
- E. Themistou, G. Battaglia, S.P. Armes Facile Synthesis of Thiol-Functionalized Amphiphilic Polylactide-Methacrylic Diblock Copolymers Polymer Chem. 2014,5, 1405-1417
- J. Gaitzsch, K. Keru, G. Battaglia Peptoidosomes as nanoparticles from amphiphilic block alpha-peptoids using solid-phase-synthesis Eur. Poly J., 2015, 73, 447–454.
- J. Rosselgong, A. Blanazs, P. Chambon, M. Williams, M. Semsarilar, J. Madsen, G. Battaglia and S. P. Armes* Thiol-Functionalized Block Copolymer Vesicles ACS Macro Lett. 2012, 1, 1041–1045
The chemical structure of a polymer backbone often requires further modification. This may it be for molecular recognition and targeting, imaging or tracking. Polymers often need to be conjugated with another substance. The latter may belong to a large variety of molecules, with proteins and contrast agents such as dyes and metal being the most prominent examples. We have thus developed several approaches to perform this process either by using the functional group as initiator for the polymerisation or modify it post-polymerisation. Recently, in collaboration with Prof Filip Du Prez, in a work led by our ex-member, Dr Jens Gaitzsch, we compared different conjugation reactions that do not rely on the use of a metal catalyst and in protic solvents. We observed that amine–NHS ester coupling is only possible in a non-ptotic solvents, thiol–maleimide click reaction yields a clean conjugated polymer even in a protic environment but the final link is rather labile, the ring-strain promoted azide–alkyne reagents are sensitive to the condition used during radical polymerisation. Finally, the 1,2,4-triazoline-3,5-dione (TAD) coupling provides a stable bond and works in additive-free conditions to give a complete conversion of the reactant.
- J. Gaitzsch, M. Delahaye, A. Poma, F. Du Prez and G. Battaglia Comparison of metal free polymer-dye conjugation strategies in protic solvents Polymer Chem. 2016 , 7, 3046 - 3055
- L. Ruiz-Perez, J. Madsen, E. Themistou, J. Gaitzsch, L. Messanger, S. Armes and G.Battaglia Nanoscale detection of metal-labeled copolymers in patchy polymersomes Polymer Chem. 2015, 6, 2065-2068
- J. Madsen, I. Canton, N. Warren, E. Themistou, A. Blanazs, B. Ustbas, X. Tian, R. Pearson, G. Battaglia, A. Lewis, S. P. Armes Nile blue-based nano-sized pH sensors for simultaneous far-red and near-infrared live bioimaging J. Am. Chem. Soc. 2013, 135, 14863–14870
- G. Battaglia, C. LoPresti, S. Forster M. Massignani, J. Madsen, N. J. Warren, S. P. Armes, C. Vasilev, J. K. Hobbs, S. Chirasatitsin, A. Engler Wet nano-scale imaging and testing of polymersomes Small 2011, 7, (14), 2010–2015
We combine polymer synthesis with self-assembly to create porous cross-linked materials with porosity, surface chemistry, surface topology, topography, mechanical properties is tuned by supramolecular interactions. We have adapted the synthesis of porous foams prepared by high internal phase emulsion (HIPE) using amphiphilic copolymers that act as surfactants during the HIPE process. We showed that the block copolymers anchor to the polymerised oil phase via the lipophilic block via chemical and/or physical entanglement. This results in the consequent presentation of the hydrophilic block on the pore surfaces which in turn controls its surface properties. The foam physical architecture can be tailored through controlling emulsion parameters such as the initiator, shear rate, and aqueous phase volume fraction. The pore surface chemistry and topography by the type of copolymer used. Finally, when we mix different copolymers together, they will undergo phase separation at the oil-water interface with consequent formation of different surface domains and hence achieving control of the control of the pore surface topology.
- P. Viswanathan, D. Johnson, C. Hurley, N. Cameron and G. Battaglia 3D Surface Functionalization of Emulsion-templated Polymeric Foams Macromolecules 2014, 47, 7091–7098
- C. Rodenburg, P. Viswanathan, M. A. E Jepson, X. Xiong, H. Jacksch, G. Battaglia Helium Ion Microscopy based wall thickness and surface roughness analysis of polymer foams obtained from high internal phase emulsion Ultramicroscopy, 2014, 139:13-9
- P. Viswanathan, S. Chirasatitsin, K. Ngamkham, A. Engler, and G. Battaglia, Cell instructive microporous scaffolds through interface engineering J. Am. Chem. Soc. 2012, 134 (49), 20103–20109