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Port Glasgow, United Kingdom

Nelson D.J.,University of St. Andrews | Queval P.,National Graduate School of Chemistry, Rennes | Rouen M.,National Graduate School of Chemistry, Rennes | Magrez M.,National Graduate School of Chemistry, Rennes | And 8 more authors.
ACS Catalysis | Year: 2013

Synergic effects between ancillary N-heterocyclic carbenes [(1,3-bis(2,4,6-trimethylphenyl)-1,3-imidazoline-2-ylidene or 1,3-bis(2,6-diisopropylphenyl)-1,3-imidazoline-2-ylidene] and chelating benzylidene-ether ligands were investigated by studying initiation rates and kinetic profiles of Hoveyda-Grubbs (HG) type Ru complexes. A newly designed Ru-benzylidene-oxazinone precatalyst 4 was compared with Grela and Blechert complexes bearing modified isopropyloxy chelating leaving groups and with the standard HG complex to understand how the ancillary and the leaving ligands interact and influence the catalytic activity. © 2013 American Chemical Society. Source


Hillier I.H.,University of Manchester | Pandian S.,University of Manchester | Percy J.M.,WestCHEM | Vincent M.A.,University of Manchester
Dalton Transactions | Year: 2011

The potential energy surfaces for ring-closing metathesis reactions of a series of simple α,ω-dienes which lead to 5-10 membered ring products, have been explored using density functional theory methods. We have investigated both the conformational aspects of the hydrocarbon chain during the course of the reactions, as well as the stationary structures on the corresponding potential energy surfaces. Extensive conformational searches reveal that the reaction proceeds via the conformation that would be expected for the cycloalkene product, though most unexpectedly, cyclohexene forms via complexes in boat-like conformations. The M06-L density functional has been used to map out the potential energy surfaces, and has identified metallocyclobutane fragmentation as being generally the highest barrier along the pathway. The structural variations along the pathway have been discussed for the reactant hydrocarbons of differing chain length to identify points at which cyclisation events may begin to affect reaction rates. Our study provides an excellent starting point from which to begin to learn about the way RCM reaction outcomes are controlled by diene structure. © 2011 The Royal Society of Chemistry. Source


Jones S.,University of Glasgow | Asokanathan C.,UK National Institute for Biological Standards and Control | Kmiec D.,UK National Institute for Biological Standards and Control | Irvine J.,University of Glasgow | And 6 more authors.
Vaccine | Year: 2014

Protein-coated microcrystals (PCMCs) were investigated as potential vaccine formulations for a range of model antigens. Presentation of antigens as PCMCs increased the antigen-specific IgG responses for all antigens tested, compared to soluble antigens. When compared to conventional aluminium-adjuvanted formulations, PCMCs modified with calcium phosphate (CaP) showed enhanced antigen-specific IgG responses and a decreased antigen-specific IgG1:IgG2a ratio, indicating the induction of a more balanced Th1/Th2 response. The rate of antigen release from CaP PCMCs, in vitro, decreased strongly with increasing CaP loading but their immunogenicity in vivo was not significantly different, suggesting the adjuvanticity was not due to a depot effect. Notably, it was found that CaP modification enhanced the phagocytosis of fluorescent antigen-PCMC particles by J774.2 murine monocyte/macrophage cells compared to soluble antigen or soluble PCMCs. Thus, CaP PCMCs may provide an alternative to conventional aluminium-based acellular vaccines to provide a more balanced Th1/Th2 immune response. © 2014 The Authors. Source


Pappas C.G.,WestCHEM | Pappas C.G.,City University of New York | Mutasa T.,University of Strathclyde | Frederix P.W.J.M.,WestCHEM | And 8 more authors.
Materials Horizons | Year: 2015

Ultrasound, i.e. high frequency oscillating pressure waves, is commonly used to overcome kinetic barriers associated with dissolution, assembly and gelation. We demonstrate that ultrasound energy may also be used to achieve transient reorganization of supramolecular nanostructures, which revert back to the original state when sound is switched off. Aromatic peptide amphiphiles, Fmoc-FL and -YL were used to study the transient acoustic response. These systems showed temporary supramolecular transitions that were sequence dependent. The changes observed were due to an altered balance between H-bonding and π-stacking, giving rise in changes in chiral organisation of peptide building blocks. Transient reconfiguration was visualized by TEM and changes in supramolecular interactions characterized by fluorescence, FT-IR and CD. Remarkably, significant differences are observed when compared to thermal heating, which relates to the oscillating and directional characteristics of ultrasound when delivering heat to a system. © The Royal Society of Chemistry. Source


Zelzer M.,WestCHEM | Zelzer M.,TU Eindhoven | Todd S.J.,Renephra Ltd | Hirst A.R.,University of Leeds | And 2 more authors.
Biomaterials Science | Year: 2013

Enzyme responsive materials (ERMs) are a class of stimuli responsive materials with broad application potential in biological settings. This review highlights current and potential future design strategies for ERMs and provides an overview of the present state of the art in the area. © 2013 The Royal Society of Chemistry. Source

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