These authors contributed equally to this work An antiparallel strand arrangement in water-soluble helicates creates an amphipathic functional topology akin to that of host-defence peptides. High and selective cancer cell line toxicity is exhibited, causing dramatic changes in the cell cycle without DNA damage, and remarkably there is no significant toxicity to MRSA and E. coli.

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The ability to harness cellular redox processes for abiotic synthesis might allow the preparation of engineered hybrid living systems. Towards this goal we describe a new bacteria‐mediated iron‐catalysed reversible deactivation radical polymerisation (RDRP), with a range of metal‐chelating agents and monomers that can be used under ambient conditions with a bacterial redox initiation step to generate polymers. Cupriavidus metallidurans, Escherichia coli, and Clostridium sporogenes species were chosen for their redox enzyme systems and evaluated for their ability to induce polymer formation. Parameters including cell and catalyst concentration, initiator species, and monomer type were investigated. Water‐soluble synthetic polymers were produced in the presence of the bacteria with full preservation of cell viability. This method provides a means by which bacterial redox systems can be exploited to generate “unnatural” polymers in the presence of “host” cells, thus setting up the possibility of making natural–synthetic hybrid structures and conjugates.

Synthesis of long-chain hyperbranched poly(ethylenimine-co-oxazoline)s by AB2 thiol–yne chemistry is reported, and their application as pDNA transfection agents studied.

Heparin plays a significant role in wound healing and tissue regeneration applications, through stabilization of fibroblast growth factors (FGF). Risks associated with batch-to-batch variability and contamination from its biological sources have led to the development of synthetic, highly sulfonated polymers as promising heparin mimics. In this work, a systematic study of an aqueous polymerization-induced self-assembly (PISA) of styrene from poly(2-acrylamido-2-methylpropane sodium sulfonate) (P(AMPS)) macro reversible addition-fragmentation chain transfer (macro-RAFT) agents produced a variety of spherical heparin-mimicking nanoparticles, which were further characterized with light scattering and electron microscopy techniques. None of the nanoparticles tested showed toxicity against mammalian cells; however, significant hemolytic activity was observed. Nonetheless, the heparin-mimicking nanoparticles outperformed both heparin and linear P(AMPS) in cellular proliferation assays, suggesting increased bFGF stabilization efficiencies, possibly due to the high density of sulfonated moieties at the particle surface.

Breaking away from the linear structure of previously reported peptide‐based gelators, this study reports the first example of gel formation based on the use of cyclic peptides made of alternating d‐ and l‐amino acids, known to self‐assemble in solution to form long nanotubes. Herein, a library of cyclic peptides was systemically studied for their gelation properties in various solvents, uncovering key parameters driving both organogel and hydrogel formation. The hierarchical nature of the self‐assembly process in water was characterised by a combination of electron microscopy imaging and small‐angle X‐ray scattering, revealing a porous network of entangled nanofibres composed by the aggregation of several cyclic peptide nanotubes. Rheology measurements then confirmed the formation of soft hydrogels.

Sébastien. (2017) Self-assembly and dis-assembly of stimuli responsive tadpole-like single chain nanoparticles using a switchable hydrophilic/hydrophobic boronic acid cross-linker. Polymer Chemistry, 28 (8). pp. 4079-4087. Permanent WRAP URL:http://wrap.warwick.ac.uk/93551 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for-profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL' above for details on accessing the published version and note that access may require a subscription. Living systems are driven by molecular machines that are composed of folded polypeptide chains, which are assembled together to form a multimeric complex. Although replicating this type of systems is a long standing goal in polymer science, the complexity of the structures imposes is synthetically very challenging, and generating synthetic polymers to mimic the process of these assemblies appears to be a more appealing approach. To this end, we report a linear polymer programmable for stepwise folding and assembly to higher-order structures. To achieve this, a diblock copolymer composed of 4-Acryloylmorpholine and glycerol acrylate was synthesised with high precision via reversible addition fragmentation chain transfer polymerisation (Ð < 1.22). Both intramolecular folding and intermolecular assembly was driven by pH responsive cross-linker, benzene-1,4-diboronic acid. The resulting intramolecular folded single chain nanoparticles were well defined (Ð < 1.16) and successfully assembled into a multimeric structure (Dh = 245 nm) at neutral pH with no chain entanglement. The assembled multimer was observed with a spherical morphology as confirmed by TEM and AFM. These structures were capable of unfolding and disassembling either at low pH or in the presence of sugar. This work offers new perspective for the generation of adaptive smart materials.

Copies of full items can be used for personal research or study, educational, or not-for-profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription.For more information, please contact the WRAP Team at: wrap@warwick.ac.uk Synthesis of Mannosylated and PEGylated Nanoparticles via RAFT Emulsion Polymerisation, and Investigation of Particle-Lectin Aggregation using TOC Graphic and Graphical Abstract 1 Abstract: 2Recent developments in controlled radical polymerisation presents an attractive way of producing 3 biocompatible polymeric nanoparticles for a wide range of applications. With this motivation, well 4 defined P(ManAm) and P(PEGA) coated nanoparticles in a range of different sizes have been 5 synthesised via RAFT emulsion polymerisation. The particles were used to precisely investigate the 6 effect of particle size on lectin binding with Concanavalin A, and validate the use of online DLS 7 measurements for lectin-glycoparticle aggregation studies. Larger particles were found to have an 8 enhanced aggregation by both UV-Vis turbidimetric and DLS aggregation studies. The DLS technique 9 was shown to be robust up to an aggregate diameter of c.500nm for aggregation tests, and was not 10 affected by any dilution or light scattering effects that typically hinder the common use of turbidimetry 11 in particle aggregation studies.