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61.
Coon JJ Shabanowitz J Hunt DF Syka JE 《Journal of the American Society for Mass Spectrometry》2005,16(6):880-882
Ion/ion reactions of multiply deprotonated peptide anions with xenon radical cations result in electron abstraction to generate
charge-reduced peptide anions containing a free-radical site. Peptide backbone cleavage then occurs by hydrogen radical abstraction
from a backbone amide N to facilitate cleavage of the adjacent C-C bond, thereby producing a- and x-type product ions. Introduction
of free-radical sites to multiply charged peptides allows access to new fragmentation pathways that are otherwise too costly
(e. g., lowers activation energies). Further, ion/ion chemistry, namely electron transfer reactions, presents a rapid and
efficient means of generating odd-electron multiply charged peptides; these reactions can be used for studying gas-phase chemistries
and for peptide sequence analysis. 相似文献
62.
Two-dimensional semiconductors (2DSCs) are promising materials for a wide range of optoelectronic applications. While the fabrication of 2DSCs with thicknesses down to the monolayer limit has been demonstrated through a variety of routes, a robust understanding of carrier transport within these materials is needed to guide the rational design of improved practical devices. In particular, the influence of different types of structural defects on transport is critical, but difficult to interrogate experimentally. Here, a new approach to visualizing carrier transport within 2DSCs, Carrier Generation-Tip Collection Scanning Electrochemical Cell Microscopy (CG-TC SECCM), is described which is capable of providing information at the single-defect level. In this approach, carriers are locally generated within a material using a focused light source and detected as they drive photoelectrochemical reactions at a spatially-offset electrolyte interface created through contact with a pipet-based probe, allowing carrier transport across well-defined, µm-scale paths within a material to be directly interrogated. The efficacy of this approach is demonstrated through studies of minority carrier transport within mechanically-exfoliated n-type WSe2 nanosheets. CG-TC SECCM imaging experiments carried out within pristine basal planes revealed highly anisotropic hole transport, with in-plane and out-of-plane hole diffusion lengths of 2.8 µm and 5.8 nm, respectively. Experiments were also carried out to probe recombination across individual step edge defects within n-WSe2 which suggest a significant surface charge (∼5 mC m−2) exists at these defects, significantly influencing carrier transport. Together, these studies demonstrate a powerful new approach to visualizing carrier transport and recombination within 2DSCs, down to the single-defect level.Probe-based electrochemical techniques can be used to map carrier transport and recombination within two-dimensional semiconductors. 相似文献
63.
We have designed and constructed an atmospheric pressure laser desorption/chemical ionization (AP-LD/CI) source that utilizes a laser pulse to desorb intact neutral molecules, followed by chemical ionization via reagent ions produced by a corona discharge. This source employs a heated capillary atmospheric pressure inlet coupled to a quadrupole ion trap mass spectrometer and allows sampling under normal ambient air conditions. Preliminary results demonstrate that this technique provides approximately 150-fold increase in analyte ions compared to the ion population generated by atmospheric pressure infrared matrix-assisted laser desorption/ionization (AP-IR-MALDI). 相似文献
64.
The interfacial tension of hybrids composed of a tin-based phosphate glass (Pglass) and thermoplastic polymers, low-density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) was investigated using pendant drop and droplet deformation methods. High surface tension values were determined for the pure Pglass and subsequently used to obtain interfacial tension values that were found to be greater than that of most polymer blends reported in the literature. Small amplitude oscillatory shear data were fitted to the Choi-Schowalter and Palierne emulsion models in order to estimate the interfacial tension and to validate the accuracy (or lack thereof) of using a polymer emulsion model on the special Pglass-polymer systems. Although some of the hybrids showed satisfactory agreement with the emulsion models, wide ranges of interfacial tensions were obtained, suggesting that a more complicated theory that explicitly takes the Pglass-polymer interactions, shape factor, and size distributions of the dispersed Pglass phase into account may be necessary for more accurate modeling of these special hybrid systems with enhanced benefits. 相似文献
65.
D.Allan Butterfield Joshua ColvinJiangling Liu Jianquan WangLeonidas Bachas Dibakar Bhattacharrya 《Analytica chimica acta》2002,470(1):29-36
The immobilization of biological molecules onto polymeric membranes to produce biofunctional membranes is used for selective catalysis, separation, analysis, and artificial organs. Normally, random immobilization of enzymes onto polymeric membranes leads to dramatic reduction in activity due to chemical reactions involved in enzyme immobilization, multiple-point binding, etc., and the extent of activity reduction is a function of membrane hydrophilicity (e.g. activity in cellulosic membrane?polysulfone membrane). We have used molecular biology to effect site-specific immobilization of enzymes in a manner that orients the active site away from the polymeric membrane surface, thus resulting in higher enzyme activity that approaches that in solution and in increased stability of the enzyme relative to the enzyme in solution. A prediction of this site-specific method of enzyme immobilization, which in this study with subtilisin and organophosphorus hydrolase consists of a fusion tag genetically added to these enzymes and subsequent immobilization via the anti-tag antibody and membrane-bound protein A, is that the active site conformation will more closely resemble that of the enzyme in solution than is the case for random immobilization. This hypothesis was confirmed using a new electron paramagnetic resonance (EPR) spin label active site titration method that determines the amount of spin label bound to the active site of the immobilized enzyme. This value nearly perfectly matched the enzyme activity, and the results suggested: (a) a spectroscopic method for measuring activity and thus the extent of active enzyme immobilization in membrane, which may have advantages in cases where optical methods can not be used due to light scattering interference; (b) higher spin label incorporation (and hence activity) in enzymes that had been site-specifically immobilized versus random immobilization; (c) higher spin label incorporation in enzymes immobilized onto hydrophilic bacterial cellulose membranes versus hydrophobic modified poly(ether)sulfone membranes. These results are discussed with reference to analysis and utilization of biofunctional membranes. 相似文献
66.
67.
Couch and Torrence suggest that the vacuum Einstein equations admit a larger class of asymptotically flat solutions than those exhibiting the peeling property. Starting with the assumption that
, (d/dr)
and (/x
A
)
, wherex
A
(A = 2, 3) are angular coordinates, they show that
, where 1 2 and 1<0;
, where 2 1 and 1< 1; and 4 and 3 peel as they would under the stronger peeling conditions. The Winicour-Tamburino energy-momentun and angular momentum integrals for these solutions, in general, diverge. In fact, since Couch and Torrence determine only the radial dependence of the solution, it is not clear that the solutions are well defined. We find that the stronger assumption
, (d/dr)
, and (/x
A
)
does result in well-defined solutions for which both the energy-momentum and angular momentum intergrals are not only finite but result in the same expressions as are obtained for peeling space-times. This assumption appears to be the minimal assumption that is necessary for investigating outgoing radiation at null infinity.In part based on a dissertation by Stephanie Novak and submitted to Syracuse University in partial fulfillment of the requirement for the Ph.D. degree. 相似文献
68.
Michael F. Rectenwald Joshua R. Gaffen Prof. Arnold L. Rheingold Dr. Alexander B. Morgan Prof. John D. Protasiewicz 《Angewandte Chemie (International ed. in English)》2014,53(16):4173-4176
The functionalized catecholate, tetraethyl (2,3‐dihydroxy‐1,4‐phenylene)bis(phosphonate) (H2‐DPC), has been used to prepare a series of lithium salts Li[B(DPC)(oxalato)], Li[B(DPC)2], Li[B(DPC)F2], and Li[P(DPC)3]. The phosphoryl‐rich character of these anions was designed to impart flame‐retardant properties for their use as potential flame‐retardant ions (FRIONs), additives, or replacements for other lithium salts for safer lithium‐ion batteries. The new materials were fully characterized, and the single‐crystal structures of Li[B(DPC)(oxalato)] and Li[P(DPC)3] have been determined. Thermogravimetric analysis of the four lithium salts show that they are thermally stable up to around 200 °C. Pyrolysis combustion flow calorimetry reveals that these salts produce high char yields upon combustion. 相似文献
69.
Madeleine A. Dallaston Christian J. Bettencourt Dr. Sharon Chow Joshua Gebhardt Jordan Spangler Dr. Martin R. Johnston Craig Wall Dr. Jason S. Brusnahan Prof. Craig M. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9614-9618
Common oxidants used in chemical synthesis, including newly developed perruthenates, were evaluated in the context of understanding (and better appreciating) the sensitiveness and associated potential hazards of these reagents. Analysis using sealed cell differential scanning calorimetry (scDSC) facilitated Yoshida correlations, which were compared to impact sensitiveness and electrostatic discharge experiments (ESD), that enabled sensitiveness ranking. Methyltriphenylphoshonium perruthenate (MTP3, 8 ), isoamyltriphenylphosphonium perruthenate (ATP3, 7 ) and tetraphenylphosphonium perruthenate (TP3, 9 ) were found to be the most sensitive followed by 2-iodoxybenzoic acid (IBX, 2 ) and benzoyl peroxide (BPO, 10 ), whereas the most benign were observed to be Oxone ( 12 ), manganese dioxide (MnO2, 13 ), and N-bromosuccinimide (NBS, 17 ). 相似文献