Dissociation of proteins and peptides by 193 nm ultraviolet photodissociation (UVPD) has gained momentum in proteomic studies because of the diversity of backbone fragments that are produced and subsequent unrivaled sequence coverage obtained by the approach. The pathways that form the basis for the production of particular ion types are not completely understood. In this study, a statistical approach is used to probe hydrogen atom elimination from a + 1 radical ions, and different extents of elimination are found to vary as a function of the identity of the C-terminal residue of the a product ions and the presence or absence of hydrogen bonds to the cleaved residue.
A series of highly porous University of Michigan Crystalline Material (UMCM-1) type Zn-based metal-organic frameworks (MOFs) were synthesized from mono- and bi-functionalized benzenedicarboxylate (BDC) ligands. In total, 16 new functionalized UMCM-1 derivatives were obtained by a combination of pre- and postsynthetic functionalization. Through postsynthetic modification (PSM), amino-halo bifunctional MOFs were converted into amide-halo materials via solid-state acylation reactions. A series of bifunctional MOFs containing Cl, Br, and I groups revealed that PSM conversion is not affected by the size of the halide, only by the steric bulk of the reagent used in these solid-state organic transformations. 相似文献
The paper introduces a number of risk-rating models for UK small businesses applying an accounting-based approach, which uses financial ratios to predict corporate bankruptcy. An enhancement to these models is considered through features typical to retail credit risk modelling. A common problem of default prediction consists in the relatively small number of bankruptcies or real defaults available for model-building. In order to expand the ‘default’ group beyond bankrupt companies, the paper considers adopting four different definitions of ‘a failing business’ by investigating combinations of financial distress levels. The impact of each default definition on the choice of predictor variables and on the model's predictive accuracy is explored. In addition, the paper examines the value of categorizing financial ratios used as predictor variables. 相似文献
The effective conjugation of ortho and ortho-alt-para-arylene ethynylenes, with appropriately positioned pyridine and pyrazine heterocycles, increases upon binding to Ag(I) and Pd(II) cations. Significant bathochromic shifts in the electronic spectra, witnessed upon introduction of these metal bridges, are consistent with enhanced electron delocalization in the unsaturated backbone. Control studies suggest that this electronic behavior is attributable exclusively (in the case of Ag(I)) or partially (in the case of Pd(II)) to conformational restrictions of the conjugated backbones. 相似文献
2,3-Dihydro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one ( (Stegobinone), the sex pheromone of the drugstore beetle, was successfully prepared from 4,6-dimethyl-3,5,7-nonatrione () by a biogenetically plausible scheme. 相似文献
As the dysprosocenium complex [Dy(Cpttt)2][B(C6F5)4] (Cpttt=C5H2tBu3-1,2,4, 1-Dy ) exhibits magnetic hysteresis at 60 K, similar lanthanide (Ln) complexes have been targeted to provide insights into this remarkable property. We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] ( 1-Ln ) for all the heavier Ln from Gd–Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F5-κ1-F)B(C6F5)3}] ( 1-Ln ; La–Nd) are isolated from reactions of parent [Ln(Cpttt)2(Cl)] ( 2-Ln ) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] ( 1-Sm ) is isolated, which like heavier 1-Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1-Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals. 相似文献
Antimicrobial resistance (AMR), the ability of a bacterial species to resist the action of an antimicrobial drug, has been on the rise due to the widespread use of antimicrobial agents. Per the World Health Organization, AMR has an estimated annual cost of USD 34 billion in the US and is predicted to be the number one cause of death worldwide by 2050. One way AMR bacteria can spread, and by which individuals can contract AMR infections, is through contaminated water. Monitoring AMR bacteria in the environment currently requires that samples be transported to a central laboratory for slow and labor intensive tests. We have developed an inexpensive assay using paper-based analytical devices (PADs) that can test for the presence of β-lactamase-mediated resistance. To demonstrate viability, the PAD was used to detect β-lactam resistance in wastewater and sewage and identified resistance in individual bacterial species isolated from environmental water sources. 相似文献
Actin is a key protein in the dynamic processes within the eukaryotic cell. To date, methods exploring the molecular state of actin are limited to insights gained from structural approaches, providing a snapshot of protein folding, or methods that require chemical modifications compromising actin monomer thermostability. Nanopore sensing permits label-free investigation of native proteins and is ideally suited to study proteins such as actin that require specialised buffers and cofactors. Using nanopores, we determined the state of actin at the macromolecular level (filamentous or globular) and in its monomeric form bound to inhibitors. We revealed urea-dependent and voltage-dependent transitional states and observed the unfolding process within which sub-populations of transient actin oligomers are visible. We detected, in real-time, filament-growth, and drug-binding at the single-molecule level demonstrating the promise of nanopore sensing for in-depth understanding of protein folding landscapes and for drug discovery.Nanopipettes were used for real-time investigation into actin dynamics and drug binding at single-molecule resolution, showing promise for a better understanding of the mechanism of protein–protein interactions and drug discovery.相似文献
Resistometric and Mössbauer measurements of the isothermal crystallization of nearly eutectic Fe-V-B amorphous alloys containing up to 8 at.%V were performed. The concentration dependence of the hyperfine fields of the crystallization products was found. The α-Fe-V and tetragonal mixed boride were detected and their contents in the course of crystallization estimated. The crystallization kinetics corresponds to the growth of α-phase nuclei proved by CEMS at the contact surface. 相似文献
