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Mark Barrow from Warwick Chemistry in Collaboration with Bruker Daltonic and the Aquatic Ecosystem Protection Research Division of Environment Canada have studied the potential evironmental impact of oil exploration from the Athabasca oil sands in Canada.  There are concerns with particular respect to components in oil sands process water which may enter the aquatic ecosystem. Naphthenic acids have been previously targeted for study, due to their implications in toxicity toward aquatic wildlife, but it is believed that other components, too, contribute toward the potential toxicity of the oil sands process water. When mass spectrometry is used, it is necessary to use instrumentation with a high resolving power and mass accuracy when studying complex mixtures, but the technique has previously been hindered by the range of compounds that have been accessible via common ionization techniques, such as electrospray ionization. The research described here applied Fourier transform ion cyclotron resonance mass spectrometry in conjunction with electrospray ionization and atmospheric pressure photoionization, in both positive-ion and negative-ion modes, to the characterization of oil sands process water for the first time. The results highlight the need for broader characterization when investigating toxic components within oil sands process water. http://dx.doi.org/10.1021/ac100103y

The fate of nanoparticles used as stabilizers in solids-stabilized, or Pickering, emulsion polymerization for the formation of armored hybrid polymer latexes was studied. We showed that disk centrifugation can be used as a powerful quantitative tool to analyze and determine the concentration of nanoparticles in the water phase throughout solids-stabilized emulsion polymerizations. We performed a series of emulsion polymerizations using vinyl acetate, vinyl pivalate, methyl methacrylate, or butyl acrylate in presence of silica nanoparticles (Ludox TM-40, ca. 25 nm in diameter). The developed method to quantify the number of silica nanoparticles in the water phase proved to be an invaluable tool for determining key features of the polymerization process. The obtained concentration profiles versus monomer conversion explained the existence of limited coalescence of armored particles in the later stages of the solids-stabilized emulsion polymerization process of vinyl acetate, leading to nonspherical structures. Moreover, we demonstrated that the correlation of the measured number of silica nanoparticles present in the water phase with the average particle sizes of the latex particles provided excellent predictions for the coverage of the armored layer of nanoparticles on the surfaces of the polymer particles, corresponding to observed packing patterns. http://dx.doi.org/10.1021/la904817f

Ann Dixon and her group report the strong interaction of the platelet-derived growth factor beta-receptor (PDGF beta), which represents an important subclass of receptor tyrosine kinase (RTK) thought to be activated by ligand-induced dimerization. Interestingly, the receptor is also activated by the bovine papillomavirus E5 oncoprotein, an interaction involving the transmembrane domains of both proteins and resulting in constitutive downstream signalling. This unique mode of activation along with emerging data for other RTKs raises important questions about the role of the PDGF beta transmembrane domain in signalling. To address this, we have investigated the murine PDGF beta transmembrane and juxtamembrane domains. We show for the first time the strong oligomerization behavior of PDGF beta transmembrane domain, forming dimers and trimers in natural membranes and detergents; and that these self-interactions are mediated by a leucine-zipper-like motif. The juxtamembrane regions are found to regulate these helix-helix interactions and select specifically for dimer formation. These data provide evidence that PDGF beta is able to form ligand-independent dimers, supporting similar observations in a number of other RTK's. A point mutant in the PDGF beta juxtamembrane domain previously shown to cause receptor activation was studied and yielded no change in oligomerization or folding, suggesting (in-line with observations of the c-Kit receptor) that it may moderate interactions with other regions of PDGF beta.  http://dx.doi.org/10.1016/j.bbamem.2009.12.016

Dave Haddleton and collaborators report on the Antibacterial Effects of Poly(2-(dimethylamino ethyl)methacrylate) against Selected Gram-Positive and Gram-Negative Bacteria in Biomacromolecules. Antimicrobial coatings can reduce the occurrence of medical device-related bacterial infections. Poly(2-(dimethylamino ethyl)methacrylate) (pDMAEMA) is one such polymer that is being researched in this regard. The aims of this study were to (1) elucidate pDMAEMA’s antimicrobial activity against a range of Gram-positive and Gram-negative bacteria and (2) to investigate its antimicrobial mode of action. The methods used include determination of minimum inhibitory concentration (MIC) values against various bacteria and the effect of pH and temperature on antimicrobial activity. The ability of pDMAEMA to permeabilise bacterial membranes was determined using the dyes 1-N-phenyl-naphthylamine and calcein-AM. Flow cytometry was used to investigate pDMAEMA’s capacity to be internalized by bacteria and to determine effects on bacterial cell cycling. pDMAEMA was bacteriostatic against Gram-negative bacteria with MIC values between 0.1−1 mg/mL. MIC values against Gram-positive bacteria were variable. pDMAEMA was active against Gram-positive bacteria around its pK_a and at lower pH values, while it was active against Gram-negative bacteria around its pK_a and at higher pH values. pDMAEMA inhibited bacterial growth by binding to the outside of the bacteria, permeabilizing the outer membrane and disrupting the cytoplasmic membrane. By incorporating pDMAEMA with erythromycin, it was found that the efficacy of the latter was increased against Gram-negative bacteria. Together, the results illustrate that pDMAEMA acts in a similar fashion to other cationic biocides. http://dx.doi.org/10.1021/bm901166y

Dave Haddleton and collaborators report on Modification of Thiol Functionalized Aptamers by Conjugation of Synthetic Polymers in Bioconjugate Chemistry. Aptamers are known for their short in vivo circulating half-life and rapid renal clearance. Their conjugation to poly(ethylene glycol) (PEG) is a way to improve their residence in the body. Two aptamers (AptD and AptF), having a disulfide protected thiol modification on the 3′ end, have been conjugated to maleimide activated PEGs of various molecular weights and structures (linear PEG20; branched PEG20 and 40; PolyPEG17, 40, and 60 kDa). The high yield coupling (70−80% in most of the cases) could be achieved using immobilized tris[2-carboxyethyl]phosphine hydrochloride (TCEP) as reducing agent at pH 4. The affinity of PEGylated AptD for its target was reduced by conjugation to linear PEG20 and branched PEG40, but not to branched PEG20 and PolyPEGs. This work demonstrates an alternative approach to PEGylation of aptamers, and that the effect of PEG on the affinity for the target varies according to the structure and conformation of the synthetic polymer. http://dx.doi.org/10.1021/bc900397s

The team of Richard Walton and his collaborators (contact: Franck Millange, Institut Lavoisier, Université de Versailles, UMR 8180, 78035 Versailles (France)) esed high intensiity synchrotron X-rays in situ diffraction observations of the solvothermal crystallisation of metal-organic frameworks (MOFs) constructed from transition- metals and carboxylate ligands. The study reveals that while some show classical nucleation-growth crystallisation, others are formed via metastable transient phases. These are among the first experimental data concerning the crystallisation mechanism of porous MOFs, materials currently at the focus of intense research activity for applications in separation and catalysis.http://dx.doi.org/10.1002/anie.200905627

The team studied the binding mode adopted by picolinamide derivatives in organometallic Os^II and Ru^II half-sandwich complexes and showed that it can lead to contrasting cancer cell cytotoxicity. N-Phenyl picolinamide derivatives (XY) in Os^II (1, 3−5, 7, 9) and Ru^II (2, 6, 8, 10) complexes [(η⁶-arene)(Os/Ru)(XY)Cl]ⁿ⁺, where arene = p-cymene (1−8, 10) or biphenyl (9), can act as N,N- or N,O-donors. Electron-withdrawing substituents on the phenyl ring resulted in N,N-coordination and electron-donating substituents in N,O-coordination. Dynamic interconversion between N,O and N,N configurations can occur in solution and is time- and temperature- (irreversible) as well as pH-dependent (reversible). The neutral N,N-coordinated compounds (1−5 and 9) hydrolyzed rapidly (t_1/2 ≤ min), exhibited significant (32−70%) and rapid binding to guanine, but no binding to adenine. The N,N-coordinated compounds 1, 3, 4, and 9 exhibited significant activity against colon, ovarian, and cisplatin-resistant ovarian human cancer cell lines (3 4 > 1 > 9). In contrast, N,O-coordinated complexes 7 and 8 hydrolyzed slowly, did not bind to guanine or adenine, and were nontoxic. http://dx.doi.org/10.1021/jm900731j

Final year PhD student Julie Ann Lough (Prof. Sadler's group) won Best Female at this year's BBC Radio 1 Student Radio Awards (www.studentradioawards.co.uk). She was shorlisted to the final 6 from hundreds of entries nationwide in October and on Tuesday the 24th of November in a lavish event with many of the countries top radio personalities she received the award of Best Female Presenter. The award was presented by Huw Stephens and the event hosted by Fearne Cotton and Scott Mills  (BBC Radio 1 presenters). Julie Ann has only being doing student radio for a year and so winning an award of this prestige is a massive achievement. Her regular show "Late Night Chat with Julie Ann" can be heard on Sundays from 9 - 11pm on RaW-1251AM (radio.warwick.ac.uk). This award entitles Julie Ann to present a show on BBC Radio1 and a weeks work experience in a GLOBAL Radio station.

Her award winning entry can be heard here 

Ioana Dumitrescu, Patrick R. Unwin and Julie V. Macpherson make the cover of Chem.Commun with their feature article on Electrochemistry at carbon nanotubes (CNTs): It is a large and growing field, but one in which there is still uncertainty about the fundamental activity of CNTs as electrode materials. On the one hand, there are many reports which focus on the favourable electrochemical properties of CNT electrodes, such as enhanced detection sensitivity, electrocatalytic effects and reduced fouling. On the other hand, other studies suggest that CNTs may be no more electroactive than graphitic powder. Furthermore, it has been proposed that the catalytic nanoparticles from which CNTs are formed may dominate the electrochemical characteristics in some instances. A considerable body of the literature presumes that the CNT sidewall is inert and that edge-plane-graphite-like open ends and defect sites are responsible for the electron transfer activity observed. In contrast, studies of well characterised single-walled nanotube (SWNT) electrodes, either as individual tubes or as two-dimensional networks, suggest sidewall activity. This review highlights how the various discrepancies in CNT electrochemistry may have arisen, by taking a historical view of the field and identifying crucial issues that still need to be solved. When assessing the behaviour of CNT electrodes, it is vitally important that careful consideration is given to the type of CNT used (SWNT or multi-walled), the quality of the material (presence of impurities), the effect of chemical processing steps in the fabrication of electrodes and the experimental arrangements adopted. Understanding these key features is an essential requirement to develop a fundamental understanding of CNT electrochemistry, to allow a wide range of electroanalytical applications, and to move the field forward rationally. As part of this process, high resolution electrochemical and electrical imaging techniques are expected to play a significant role in the future, as well as theoretical developments which examine the fundamentals of electron transfer at different types of CNTs and their characteristic surface sites. http://dx.doi.org/10.1039/b909734a

The fabrication of micrometer-sized monodisperse highly porous polymer particles, of both spherical and rodlike shapes, using a simple microfluidic setup is demonstrated. Droplets were generated in a coflow device from a water-in-oil high internal phase emulsion (HIPE), hereby creating a water-in-oil-in-water (W/O/W) emulsion. The individual droplets of monomer HIPE were polymerized downstream in the channel through photopolymerization. The polymer particles produced via this strategy possess very large macropores in comparison with the more conventional porous polymer beads synthesized by inducing in situ phase separation throughout the polymerization process through the use of porogenic solvents. Epoxy-functionalized porous particles made using the HIPE microfluidic method showed superior performance in a consecutive azide and cycloaddition “click”−“click” modification procedure monitored by IR. Our microfluidic approach led to the successful miniaturization of monodisperse submillimeter spherical poly(HIPE) beads, down to diameters of 400 μm. More strikingly is the production of poly(HIPE) rods, which were obtained by using a viscous HIPE, which in coflow emulsification formed an unstable jet that broke up into rodlike sections. These rodlike droplets maintained their shapes throughout the microfluidic channel and did not relax back into spherical droplets, allowing for production of poly(HIPE) rods upon photopolymerization. The nonspherical shape in this case is not determined by confined channel geometries, which to the best of our knowledge is unprecedented as a strategy to produce nonspherical polymer particles with microfluidics.

The work was carried out in collaboration with prof. Filip du Prez's research team (University of Ghent, Belgium). First author and PhD student M. Talha Gokmen visited Stefan Bon's team at Warwick for a number of weeks to found the basis for the work reported.

 http://dx.doi.org/10.1021/ma9018679

Alzheimer's Peptide Aβ1-42, an amyoid beta peptide, is found in plagues in the brains of Alzheimer's disease patients, and accumulation of this very hydrophobic peptide is thought to be the direct cause of the disease. However, the reason for accumulation is not clear. A common theory is that the balance between production and degradation of this peptide is disrupted in the disease. One method whereby degradation of the peptide can be inhibited is by modification into a form which is resistant to enzymatic degradation (proteolysis). In peptides, isomerization of aspartic acid into isoaspartic acid (where the peptide bond is via the side-chain beta carbon rather than the normal backbone alpha carbon) is known to inhibit enzymatic degradation, and may be the elusive Alzheimer's "trigger", which results in decreased degradation and therefore accumulation of the peptide. Nadia Sargaeva of Prof.  Peter O'Connor's group has developed a new mass spectrometric method for detecting this isomerization and tested it out on the worst variant of the amyloid beta peptide, the full length version containing amino acids 1-42. 

Read the paper