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891.
John K. Fincham Michael B. Hursthouse Harold G. Parkes Leylacaron S. Shaw Robert A. Shaw 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):185-194
Abstract Based on its reactions with various nucleophiles both geminal and non-geminal structures have been earlier proposed for N3P3Cl4(NH2)2, although its geminal structure is now considered established. The reactions of this compound with alcohols have been investigated and the products examined by NMR spectroscopy and X-ray crystallography. Evidence for both unrearranged as well as geminal → non-geminal rearranged alcoholysis products is presented. 相似文献
892.
893.
Adriana Reyes‐Mayer Bonifacio Alvarado‐Tenorio Angel Romo‐Uribe Michael Jaffe 《先进技术聚合物》2013,24(12):1029-1039
The influence of heat treatment on the texture, microstructure and tensile mechanical properties of extruded thin films of a series of high‐performance thermotropic liquid crystal polymers (LCPs) was investigated. LCPs based on random units of hydroxybenzoic acid (B), hydroxynaphthoic acid (N), terephthalic acid (TA) and biphenol (BP) were kindly supplied by the former Hoechst Celanese Corp as 50 µm thick extruded tapes. The LCPs, denoted B‐N, COTBP and RD1000, have B and N as common comonomers and vary the other comonomers. Thus, this study also enables the investigation of the influence of monomer composition on microstructure and mechanical properties. Heat treatments were carried out at temperatures close to the solid‐to‐nematic transition (Ts→n) for periods up to 5 h, under dry air conditions. The thermal treatment produced either two endotherms or a small increase of Ts→n (B‐N and RD1000), or increased significantly Ts→n (COTBP). Moreover, when heat treatment was carried out approximately 40°C below the respective Ts→n, the mechanical Young's modulus, E, along the extrusion axis, increased for all LCPs. Strikingly, for COTBP, E increased over 100% relative to the as‐extruded film. The results also showed that the optimum treatment time for improving the Young modulus, under dry air atmosphere, was between 3 and 4 h. Wide‐angle X‐ray scattering showed a significant sharpening of crystalline reflections and concentration of the 002 meridional reflection as a result of thermal treatment, suggesting the elimination of defects and a better alignment of the molecular chains along the extrusion axis. This would explain the increase in tensile modulus. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
894.
Lisa M. Jones Hao Zhang Weidong Cui Sandeep Kumar Justin B. Sperry James A. Carroll Michael L. Gross 《Journal of the American Society for Mass Spectrometry》2013,24(6):835-845
As therapeutic monoclonal antibodies (mAbs) become a major focus in biotechnology and a source of the next-generation drugs, new analytical methods or combination methods are needed for monitoring changes in higher order structure and effects of post-translational modifications. The complexity of these molecules and their vulnerability to structural change provide a serious challenge. We describe here the use of complementary mass spectrometry methods that not only characterize mutant mAbs but also may provide a general framework for characterizing higher order structure of other protein therapeutics and biosimilars. To frame the challenge, we selected members of the IgG2 subclass that have distinct disulfide isomeric structures as a model to evaluate an overall approach that uses ion mobility, top-down MS sequencing, and protein footprinting in the form of fast photochemical oxidation of proteins (FPOP). These three methods are rapid, sensitive, respond to subtle changes in conformation of Cys?→?Ser mutants of an IgG2, each representing a single disulfide isoform, and may be used in series to probe higher order structure. The outcome suggests that this approach of using various methods in combination can assist the development and quality control of protein therapeutics. 相似文献
895.
Devrishi Goswami Srikripa Devarakonda Michael J. Chalmers Bruce D. Pascal Bruce M. Spiegelman Patrick R. Griffin 《Journal of the American Society for Mass Spectrometry》2013,24(10):1584-1592
Application of typical HDX methods to examine intrinsically disordered proteins (IDP), proteins that are natively unstructured and highly dynamic at physiological pH, is limited because of the rapid exchange of unprotected amide hydrogens with solvent. The exchange rates of these fast exchanging amides are usually faster than the shortest time scale (10 s) employed in typical automated HDX-MS experiments. Considering the functional importance of IDPs and their association with many diseases, it is valuable to develop methods that allow the study of solution dynamics of these proteins as well as the ability to probe the interaction of IDPs with their wide range of binding partners. Here, we report the application of time window expansion to the millisecond range by altering the on-exchange pH of the HDX experiment to study a well-characterized IDP; the activation domain of the nuclear receptor coactivator, peroxisome proliferator-activated receptor gamma coactivator-1 alpha (PGC-1α). This method enabled mapping the regions of PGC-1α that are stabilized upon binding the ligand binding domain (LBD) of the nuclear receptor peroxisome proliferator-activated receptor gamma (PPARγ). We further demonstrate the method’s applicability to other binding partners of the IDP PGC-1α and pave the way for characterizing many other biologically important ID proteins. Figure
? 相似文献
896.
Tamer Shoeib Junfang Zhao Houssain EI Aribi Alan C. Hopkinson K. W. Michael Siu 《Journal of the American Society for Mass Spectrometry》2013,24(1):38-48
The fragmentations of [AA + M]+ complexes, where AA = Phe, Tyr, Trp, or His, and M is a monovalent metal (Li, Na, or Ag), have been exhaustively studied through collision-induced dissociation (CID) and through deuterium labeling. Dissociations of the Li- and Ag-containing complexes gave a large number of fragment ions; by contrast, the sodium/amino acid complexes have lower binding energies, and dissociation resulted in much simpler spectra, with loss of the entire ligand dominating. Unambiguous assignments of these fragment ions were made and formation mechanisms are proposed. Of particular interest are fragmentations in which the charge was retained on the organic fragment and the metal was lost, either as a metal hydride (AgH) or hydroxide (LiOH) or as the silver atom (Ag?). Caption for Graphical Abstract
CID products of Li+, Na+, and Ag+ complexes of Phe, Tyr, Trp, and His are reported and mechanisms by which they are formed are proposed. 相似文献
897.
Aliphatic Polyester Blends Based upon Poly(Lactic Acid) and Oligomeric Poly(Hexamethylene Succinate)
Abstract In an attempt to gain a degree of control over the mechanical and degradation properties of poly(lactic acid) [PLA], large-scale efforts are underway to alter the phase morphology of PLA through chemical and physical modification. Consistent with this theme, our work aims to adjust the molecular architecture of highly amorphous PLA with an increasing concentration of hydroxy-terminated oligomeric poly(hexamethylene succinate) [PHS]. Gel-permeation chromatography (GPC) verifies the enhanced presence of PHS in the blends with a concomitant reduction in number-average molecular weight as the weight fraction of PHS is raised from 0.10 to 0.40. Differential scanning calorimetry (DSC) indicates amorphous phase compatibility between PHS and PLA at weight compositions of 10/90 and 20/80. However, as the amount of PHS approaches 30 and 40 wt%, the PHS exhibits the ability to crystallize independently from the induced PLA crystalline phase. Dynamic mechanical thermal analysis (DMTA) illustrates variable behavior of the materials under tension as a consequence of structural alterations generated by the oligoester. Finally, preliminary results suggest that these alterations may suppress the hydrolytic degradation of PLA. 相似文献
898.
C. Michael Elliott S. J. Schmittle J. G. Redepenning E. M. Balk 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10-11):1215-1225
Complexes of ruthenium with 2,2′-bipyridines having electron-withdrawing ester functions in the 5,5′ positions have been prepared, and they are polymerizable. Films can be cast on electrodes from solutions of the monomer and then polymerized thermally. Once formed, the films are electroactive and quite stable in the absence of O2. The ruthenium complexes in this polymer have a rich electrochemistry and can exist in seven stable oxidation states. The spectral properties of the polymer are such that, as the oxidation state of the complex is changed successively from 2+ to 4-, the polymer undergoes vivid changes in color. The material is thus of interest as an electrochromic material. Additionally, when the polymer is reduced to the formal zero-valent form it becomes an ohmic conductor with semiconductorlike properties. 相似文献
899.
Heterocycles derived from Tröger's base were shown to complex with metal salts in 2:1 ligand:salt ratios as monodentate or bidentate ligands depending on structure. 相似文献
900.