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41.
Kristina Hetherington Dr. Zsofia Hegedus Dr. Thomas A. Edwards Dr. Richard B. Sessions Prof. Adam Nelson Prof. Andrew J. Wilson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(34):7638-7646
Protein–protein interactions (PPIs) control virtually all cellular processes and have thus emerged as potential targets for development of molecular therapeutics. Peptide-based inhibitors of PPIs are attractive given that they offer recognition potency and selectivity features that are ideal for function, yet, they do not predominantly populate the bioactive conformation, frequently suffer from poor cellular uptake and are easily degraded, for example, by proteases. The constraint of peptides in a bioactive conformation has emerged as a promising strategy to mitigate against these liabilities. In this work, using peptides derived from hypoxia-inducible factor 1 (HIF-1α) together with dibromomaleimide stapling, we identify constrained peptide inhibitors of the HIF-1α/p300 interaction that are more potent than their unconstrained sequences. Contrary to expectation, the increased potency does not correlate with an increased population of an α-helical conformation in the unbound state as demonstrated by experimental circular dichroism analysis. Rather, the ability of the peptide to adopt a bioactive α-helical conformation in the p300 bound state is better supported in the constrained variant as demonstrated by molecular dynamics simulations and circular dichroism difference spectra. 相似文献
42.
We consider associated production of squarks and gluinos with the lightest supersymmetric particle (LSP), or states nearly degenerate in mass with it. Though sub-dominant to pair production of color SU(3)-charged superpartners, these processes are directly sensitive to the wavefunction composition of the lightest neutralinos. Exploiting event-shape variables - including some introduced here for the first time - we are able to identify the composition of the LSP by selecting events involving a single high-pT jet recoiling against missing transverse energy. We illustrate the proposed technique on a set of benchmark cases and propose methods for applying these results in more realistic experimental environments. 相似文献
43.
Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers 下载免费PDF全文
Samantha Staniland Bo Yuan Nelson Giménez‐Agulló Dr. Tommaso Marcelli Dr. Simon C. Willies Dr. Damian M. Grainger Prof. Nicholas J. Turner Prof. Jonathan Clayden 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13084-13088
Atropisomeric biaryls carrying ortho‐hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time‐dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme. 相似文献
44.
The study of the reaction of l-tyrosine or its tetrabutylammonium salt with formaldehyde was performed. The results established that this reaction does not lead to macrocyclic amino acid-type compounds, and in all cases, mixtures of linear oligomers of two or more l-tyrosine units bound by methylene groups were obtained. The formation of ion pair-type linear aggregates in the tetrabutylammonium salt hinders the oligomerization reaction, allowing the isolation of an l-tyrosine dimer, unlike the l-tyrosine reaction, in which a trimer could be isolated. 相似文献
45.
André L. Santos Regina M. Takeuchi Rodrigo A. A. Muñoz Lúcio Angnes Nelson R. Stradiotto 《Electroanalysis》2014,26(2):233-242
This article critically reviews the electroanalytical methods devoted for the determination of organic compounds in automotive fuels that can range from contaminants to additives typically introduced into liquid biofuels and liquid fossil fuels. Contaminants such as aldehydes and ketones in bioethanol, free fatty acids and glycerol in biodiesel, and sulfur and nitrogen organic compounds in gasoline and diesel fuel, and additives such as colour markers and antioxidants added to fuels were determined by electroanalytical methods. Special focus is given to electrodes, electrochemical techniques, and sample preparation strategies. Future directions of research on electroanalysis of liquid fuels are presented. 相似文献
46.
David Adeyemi Janes Mokgadi James Darkwa Chimezie Anyakora Grace Ukpo Charlotta Turner Nelson Torto 《Chromatographia》2011,73(9-10):1015-1020
Electrospun polystyrene (PS) nanofibers (130–500 nm) incorporating a potassium salt of imidazole-1-carbodithioate were evaluated as potential sorbents for the pre-concentration of a model organochlorine pesticide; 1,1-dichloro-2,2bis-(4-chlorophenyl)ethylene (DDE). The efficiencies of DDE (0.25–1.0 μg L?1) adsorption by the nanofiber sorbent followed by desorption employing pressurized hot water extraction (PHWE) were investigated and monitored using gas chromatography with electron capture detection (GC-ECD). Parameters such as time, temperature and pressure of extraction, sample volume, DDE concentration and sorbent mass were optimized. The maximum adsorption of DDE (0.50 μg L?1) on electrospun PS and carbodithioate incorporated PS nanofibers was at 43.7 and 94.6%, respectively, in 20 min. Incorporation of carbodithiote doubled the adsorption efficiency of PS and achieved LOD of 0.000234 μg L?1 for DDE. The optimal DDE desorption on the PHWE system was 93.8% in 10 min. It would seem that the use of electrospun nanofibers as sorbent material with subsequent desorption by PHWE has great potential and thus warrants further investigations. This approach as it uses water as an extraction solvent for an organochlorine pesticide provides an opportunity to eliminate organic solvents, especially for procedures aimed at monitoring organic pollutants in the environment. 相似文献
47.
Nicole A.S. White Henry A. Ellis Peter N. Nelson Paul T. Maragh 《The Journal of chemical thermodynamics》2011,43(4):584-590
Thermotropic phase transition temperatures, enthalpies and entropies of phase changes and odd–even alternation, in a homologous series of anhydrous lithium n-alkanoates, LiCnH2n?1O2 (LiC8–19 inclusive), have been investigated by differential scanning calorimetry (d.s.c.), hot stage polarizing microscopy and solid state 13C NMR spectroscopy. The number of phases observed, between the room temperature microcrystalline solid and isotropic melt, shows a clear dependence on chain length. For LiC8–13, only one intermediate lamellar II crystalline phase is observed. For LiC14–19, a lamellar II and high temperature phase are evident. The high temperature phase is characterized by pre-melting and disordering of hydrocarbon chains as they change from nearly all-trans to one with increased gauche conformers. It is probably a solid rotator phase. Odd–even alternation in melting temperature, density and some thermodynamic data result from the relative distance between methyl groups, from opposite layers in a bi-layer. Molecular models indicate that the methyl groups in odd chains are more favourably orientated which lead to a more energetically favoured staggered conformer. As a consequence, the methyl groups, for odd chains, are in closer proximity than even chains. This subtle change in the molecular lattice could account for the presence of polymorphic structures on cooling from the melt. 相似文献
48.
The glassy carbon electrode was modified with a nickel pentacyanonitrosylferrate film by electrodeposition of Ni and subsequent derivatization with NaPCNF. The film was characterized by XPS and electrochemical methods. Cyclic voltammetry of the NiPCNF onto the GC shows a redox couple (FeIII/FeII) with E°′ of 538 mV (Ipa/Ipc around 1) and ΔEp of 93 mV in 0.5 mol L?1 KNO3, with a diffusion‐controlled process. There was a decrease of anodic peak currents of the film in the presence of sulfide and 2‐propanethiol due to a precipitation reaction on the film surface by nucleophilic attack. 相似文献
49.
Min Tian Sapanbir S. Thind Shuai Chen Nelson Matyasovzsky Aicheng Chen 《Electrochemistry communications》2011,13(11):1186-1189
In the present work, we report on a facile and effective approach to significantly enhance the photocatalytic activity of TiO2 nanotubes. The TiO2 nanotubes prepared by the electrochemical oxidation of titanium in dimethyl sulfoxide (DMSO) with 2% HF were treated in a methanol solution under UV light irradiation. In comparison with the untreated TiO2 nanotubes, the treatment resulted in a dramatic increase in the donor density of the TiO2 nanotubes by approximately 3 orders of magnitude. The treated TiO2 nanotubes exhibited a 15-fold enhancement in photocurrent and a 6.8-fold increase in the photoelectrochemical degradation of 4-nitrophenol, significant for hydrogen generation and wastewater treatment. 相似文献
50.
Nelson M. Larocca Edson N. Ito Carlos Triveño Rios Luiz A. Pessan Rosario E. S. Bretas Elias Hage Jr. 《Journal of Polymer Science.Polymer Physics》2010,48(21):2274-2287
Poly(butylene terephthalate) (PBT)/styrene‐acrylonitrile copolymer (SAN) blends were investigated with respect to their phase morphology. The SAN component was kept as dispersed phase and PBT as matrix phase and the PBT/SAN viscosity ratio was changed by using different PBT molecular weights. PBT/SAN blends were also compatibilized by adding methyl methacrylate‐co‐glycidyl methacrylate‐co‐ethyl acrylate terpolymer, MGE, which is an in situ reactive compatibilizer for melt blending. In noncompatibilized blends, the dispersed phase particle size increased with SAN concentration due to coalescence effects. Static coalescence experiments showed evidence of greater coalescence in blends with higher viscosity ratios. For noncompatibilized PBT/SAN/MGE blends with high molecular weight PBT as matrix phase, the average particle size of SAN phase does not depend on the SAN concentration in the blends. However noncompatibilized blends with low molecular weight PBT showed a significant increase in SAN particle size with the SAN concentration. The effect of MGE epoxy content and MGE molecular weight on the morphology of the PBT/SAN blend was also investigated. As the MGE epoxy content increased, the average particle size of SAN initially decreased with both high and low molecular weight PBT phase, thereafter leveling off with a critical content of epoxy groups in the blend. This critical content was higher in the blends containing low molecular weight PBT than in those with high molecular weight PBT. At a fixed MGE epoxy content, a decrease in MGE molecular weight yielded PBT/SAN blends with dispersed nanoparticles with an average size of about 40 nm. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010 相似文献