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排序方式: 共有630条查询结果,搜索用时 15 毫秒
21.
Maíra Fasciotti Gustavo B. Sanvido Vanessa G. Santos Priscila M. Lalli Michael McCullagh Gilberto F. de Sá Romeu J. Daroda Martin G. Peter Marcos N. Eberlin 《Journal of mass spectrometry : JMS》2012,47(12):1643-1647
The use of CO2 as a massive and polarizable drift gas is shown to greatly improve peak‐to‐peak resolution (Rp‐p), as compared with N2, for the separation of disaccharides in a Synapt G2 traveling wave ion mobility cell. Near or baseline Rp‐p was achieved for three pairs of sodiated molecules of disaccharide isomers, that is, cellobiose and sucrose (Rp‐p = 0.76), maltose and sucrose (Rp‐p = 1.04), and maltose and lactose (Rp‐p = 0.74). Ion mobility mass spectrometry using CO2 as the drift gas offers therefore an attractive alternative for fast and efficient separation of isomeric disaccharides. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
22.
The paper deals with the effect of different stress states on damage and failure behavior of ductile materials. To be able to model these effects a continuum damage model has been proposed taking into account the dependence of the stress intensity, the stress triaxiality and the Lode parameter on the constitutive equations. The model is based on the introduction of damaged and fictitious undamaged configurations. Only experiments are not adequate enough to determine all constitutive parameters. Therefore, additional three-dimensional micro-mechanical simulations of representative volume elements have been performed to get more insight in the complex damage mechanisms. These simulations cover a wide range of different void sizes, void shapes and void distributions. After all, the results from the micro-mechanical simulations are used to propose the damage equations and to identify corresponding parameters. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
23.
Berta Esteban-Fernández de Ávila Vanessa Escamilla-Gómez Susana Campuzano María Pedrero José M. Pingarrón 《Analytica chimica acta》2013
A novel amperometric magnetoimmunosensor using an indirect competitive format is developed for the sensitive detection of the amino-terminal pro-B-type natriuretic peptide (NT-proBNP). The immunosensor design involves the covalent immobilization of the antigen onto carboxylic-modified magnetic beads (HOOC-MBs) activated with N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (EDC) and N-hydroxysulfosuccinimide (sulfo-NHS), and further incubation in a mixture solution containing variable concentrations of the antigen and a fixed concentration of an HRP-labeled detection antibody. Accordingly, the target NT-proBNP in the sample and that immobilized on the MBs compete for binding to a fixed amount of the specific HRP-labeled secondary antibody. The immunoconjugate-bearing MBs are captured by a magnet placed under the surface of a disposable gold screen-printed electrode (Au/SPE). The amperometric responses measured at –0.10 V (vs. a Ag pseudo-reference electrode), upon addition of 3,3′,5,5′-tetramethylbenzidine (TMB) as electron transfer mediator and H2O2 as the enzyme substrate, are used to monitor the affinity reaction. The developed magnetoimmunosensor provides attractive analytical characteristics in 10-times diluted human serum samples, exhibiting a linear range of clinical usefulness (0.12–42.9 ng mL−1) and a detection limit of 0.02 ng mL−1, which can be used in clinical diagnosis of chronic heart failure in the elderly and for classifying patients at risk of death after heart transplantation. The magnetoimmunosensor was successfully applied to the analysis of spiked human serum samples. 相似文献
24.
Ultrasonic irradiation substantially improves the reaction of cyclohexene with I2 in aqueous dioxane in the presence of Cu(OAc)2 · H2O to generate the expected iodohydrin in high yield. The product undergoes cyclization to the epoxide by biphasic treatment with either Na2CO3 or KOH in a sonication‐sensitive step. 相似文献
25.
Prof. Javier A. Cabeza Dr. Pablo García‐Álvarez Dr. Enrique Pérez‐Carreño Dr. Vanessa Pruneda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3426-3436
The methylation of the uncoordinated nitrogen atom of the cyclometalated triruthenium cluster complexes [Ru3(μ‐H)(μ‐κ2N1,C6‐2‐Mepyr)(CO)10] ( 1 ; 2‐MepyrH=2‐methylpyrimidine) and [Ru3(μ‐H)(μ‐κ2N1,C6‐4‐Mepyr)(CO)10] ( 9 ; 4‐MepyrH=4‐methylpyrimidine) gives two similar cationic complexes, [Ru3(μ‐H)(μ‐κ2N1,C6‐2,3‐Me2pyr)(CO)10]+( 2 +) and [Ru3(μ‐H)(μ‐κ2N1,C6‐3,4‐Me2pyr)(CO)10]+ ( 9 +), respectively, whose heterocyclic ligands belong to a novel type of N‐heterocyclic carbenes (NHCs) that have the Ccarbene atom in 6‐position of a pyrimidine framework. The position of the C‐methyl group in the ligands of complexes 2 + (on C2) and 9 + (on C4) is of key importance for the outcome of their reactions with K[N(SiMe3)2], K‐selectride, and cobaltocene. Although these reagents react with 2 + to give [Ru3(μ‐H)(μ‐κ2N1,C6‐2‐CH2‐3‐Mepyr)(CO)10] ( 3 ; deprotonation of the C2‐Me group), [Ru3(μ‐H)(μ3‐κ3N1,C5,C6‐4‐H‐2,3‐Me2pyr)(CO)9] ( 4 ; hydride addition at C4), and [Ru6(μ‐H)2{μ6‐κ6N1,N1′,C5,C5′,C6,C6′‐4,4′‐bis(2,3‐Me2pyr)}(CO)18] ( 5 ; reductive dimerization at C4), respectively, similar reactions with 9 + have only allowed the isolation of [Ru3(μ‐H)(μ3‐κ2N1,C6‐2‐H‐3,4‐Me2pyr)(CO)9] ( 11 ; hydride addition at C2). Compounds 3 and 11 also contain novel six‐membered ring NHC ligands. Theoretical studies have established that the deprotonation of 2 + and 9 + (that have ligand‐based LUMOs) are charge‐controlled processes and that both the composition of the LUMOs of these cationic complexes and the steric protection of their ligand ring atoms govern the regioselectivity of their nucleophilic addition and reduction reactions. 相似文献
26.
27.
Sergey V. Prikhodko Diana C. Rambaldi Andrew King Elizabeth Burr Vanessa Muros Ioanna Kakoulli 《Journal of Raman spectroscopy : JRS》2015,46(7):632-635
In the past decade Surface Enhanced Raman Scattering (SERS) has emerged as a powerful technique for the analysis of artistic, historical and archaeological material culture. However, the identification of organic compounds in complex samples using SERS can be challenging owing to the complexity in optimizing the adsorption of target analytes onto the plasmonic substrate and the difficulty to identify proper areas on the sample for robust SERS analysis using optical systems. Scanning electron microscopy (SEM) interfaced with Raman spectromicroscopy (μRS) provides an ideal hyphenated system to overcome the last challenge by: (1) evaluating the nanoparticles coverage/distribution on the sample and (2) locating suitable areas for successful and reproducible SERS analysis. In this paper we demonstrate the potential of a system interfacing SEM and μRS for single fiber, extractionless analysis in the characterization of dyes from reference collections and archaeological textiles. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
28.
Spatiotemporal pattern formation in a product-activated enzymic reaction at high enzyme concentrations is investigated. Stochastic simulations show that catalytic turnover cycles of individual enzymes can become coherent and that complex wave patterns of molecular synchronization can develop. The analysis based on the mean-field approximation indicates that the observed patterns result from the presence of Hopf and wave bifurcations in the considered system. 相似文献
29.
Multiplexed Determination of Amino‐Terminal Pro‐B‐Type Natriuretic Peptide and C‐Reactive Protein Cardiac Biomarkers in Human Serum at a Disposable Electrochemical Magnetoimmunosensor
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Berta Esteban‐Fernández de Ávila Vanessa Escamilla‐Gómez Valentina Lanzone Susana Campuzano María Pedrero Dario Compagnone José M. Pingarrón 《Electroanalysis》2014,26(2):254-261
A rapid magnetoimmunosensor for the simultaneous determination of two cardiac biomarkers, amino‐terminal pro‐B‐type natriuretic peptide (NT‐proBNP) and C‐reactive protein (CRP), in human serum is described. Specific capture antibodies were covalently immobilized onto carboxylic acid‐modified magnetic beads. The quantification of NT‐proBNP and CRP was performed by using indirect competitive and sandwich configurations, respectively, and horseradish peroxidase‐labeled tracers. The use of dual screen‐printed carbon electrodes allowed the achievement of simultaneous independent amperometric readout for each cardiac biomarker. The developed methodology showed very low limits of detection (0.47 ng mL?1). An international standard for CRP serum spiked with NT‐proBNP was analyzed to evaluate the usefulness of the magnetoimmunosensor. 相似文献
30.
Elevated Catalytic Activity of Ruthenium(II)–Porphyrin‐Catalyzed Carbene/Nitrene Transfer and Insertion Reactions with N‐Heterocyclic Carbene Ligands
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Ka‐Ho Chan Dr. Xiangguo Guan Dr. Vanessa Kar‐Yan Lo Prof. Dr. Chi‐Ming Che 《Angewandte Chemie (International ed. in English)》2014,53(11):2982-2987
Bis(NHC)ruthenium(II)–porphyrin complexes were designed, synthesized, and characterized. Owing to the strong donor strength of axial NHC ligands in stabilizing the trans M?CRR′/M?NR moiety, these complexes showed unprecedently high catalytic activity towards alkene cyclopropanation, carbene C? H, N? H, S? H, and O? H insertion, alkene aziridination, and nitrene C? H insertion with turnover frequencies up to 1950 min?1. The use of chiral [Ru(D4‐Por)(BIMe)2] ( 1 g ) as a catalyst led to highly enantioselective carbene/nitrene transfer and insertion reactions with up to 98 % ee. Carbene modification of the N terminus of peptides at 37 °C was possible. DFT calculations revealed that the trans axial NHC ligand facilitates the decomposition of diazo compounds by stabilizing the metal–carbene reaction intermediate. 相似文献