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81.
Dwivedi P Puzon G Tam M Langlais D Jackson S Kaplan K Siems WF Schultz AJ Xun L Woods A Hill HH 《Journal of mass spectrometry : JMS》2010,45(12):1383-1393
Comprehensive metabolome analysis using mass spectrometry (MS) often results in a complex mass spectrum and difficult data analysis resulting from the signals of numerous small molecules in the metabolome. In addition, MS alone has difficulty measuring isobars and chiral, conformational and structural isomers. When a matrix-assisted laser desorption ionization (MALDI) source is added, the difficulty and complexity are further increased. Signal interference between analyte signals and matrix ion signals produced by MALDI in the low mass region (<1500 Da) cause detection and/or identification of metabolites difficult by MS alone. However, ion mobility spectrometry (IMS) coupled with MS (IM-MS) provides a rapid analytical tool for measuring subtle structural differences in chemicals. IMS separates gas-phase ions based on their size-to-charge ratio. This study, for the first time, reports the application of MALDI to the measurement of small molecules in a biological matrix by ion mobility-time of flight mass spectrometry (IM-TOFMS) and demonstrates the advantage of ion-signal dispersion in the second dimension. Qualitative comparisons between metabolic profiling of the Escherichia coli metabolome by MALDI-TOFMS, MALDI-IM-TOFMS and electrospray ionization (ESI)-IM-TOFMS are reported. Results demonstrate that mobility separation prior to mass analysis increases peak-capacity through added dimensionality in measurement. Mobility separation also allows detection of metabolites in the matrix-ion dominated low-mass range (m/z < 1500 Da) by separating matrix signals from non-matrix signals in mobility space. 相似文献
82.
Amina Mohamed El‐Brashy Mohamed El‐Sayed Metwally Fawzi Abdallah El‐Sepai 《中国化学会会志》2005,52(2):253-262
New simple spectrophotometric and atomic absorption spectrometric (AAS) methods have been developed for the determination of levofloxacin (I), norfloxacin (II), and ciprofloxacin (III) in pure form, tablet formulations, and spiked human urine. The methods are based on the formation of ion‐pair associates between the drugs and the inorganic complex, bismuth (III) tetraiodide. The reaction occurs in acidic medium to form orange‐red ion‐pair associates which are instantaneously precipitated. The formed precipitates are then filtered off and the residual unreacted metal complex in the filtrate is determined either spectrophotometrically at 453 nm or by AAS at 223.1 nm. Also, the precipitates may be dissolved in acetone and quantified spectrophotometrically at 469 nm or decomposed by hydrochloric acid, and the bismuth content is determined by AAS at 223.1 nm. The methods permit the determination of the three studied drugs in the range of 5–80 μg mL?1. The proposed methods were successfully applied to determine these drugs in their tablet formulations and spiked urine samples without any evidence for interference from pharmaceutical additives or biological matrix. The results were in good agreement with those obtained by the reference methods. The proposed methods, especially if automated, can be confidently applied for quality control and routine analysis of the studied drugs. 相似文献
83.
A series of novel menthone oxime ethers were synthesized in three steps starting from (–)-menthol. Analysis of the 13C NMR chemical shift differences between α carbons of oxime derivatives (O-alkyl oximes) provides a convenient and reliable means of assigning oxime stereochemistry. It has been found that carbons syn to the oxime are shifted more upfield than carbons anti to the oxime moiety. Significant E products were obtained. 相似文献
84.
Yanling Li Amina Benchohra Buqin Xu Benoît Baptiste Keevin Béneut Paraskevas Parisiades Ludovic Delbes Alain Soyer Kamel Boukheddaden Rodrigue Lescouëzec 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17425-17429
A key challenge in the design of magnetic molecular switches is to obtain bistability at room temperature. Here, we show that application of moderate pressure makes it possible to convert a paramagnetic FeIII2CoII2 square complex into a molecular switch exhibiting a full dia- to paramagnetic transition: FeIICoIII ⇔ FeIIICoII. Moreover, the complex follows a rare behavior: the higher the pressure, the broader the magnetic hysteresis. Thus, the application of an adequate pressure allows inducing a magnetic bistability at room temperature with predictable hysteresis width. The structural studies at different pressures suggest that the pressure-enhanced bistability is due to the strengthening of intermolecular interactions upon pressure increase. An original microscopic Ising-like model including pressure effects is developed to simulate this unprecedented behavior. Overall, this study shows that FeCo complexes could be very sensitive piezo switches with potential use as sensors. 相似文献
85.
Isam M. Salih Amina S. Aljaber Mohamed A-Z Eltayeb Yousif Sulfab 《Transition Metal Chemistry》2013,38(2):213-218
The kinetics of oxidation of N,N′-ethylenebis(isonitrosoacetyleacetoneimine)copper(II) complex, CuIIL, by N-bromosuccinimide (SBr) in weakly aqueous acidic solutions was studied under pseudo-first-order conditions. Plots of ln(A ∞ ? A t ) versus time where A t and A ∞ are absorbance values of the Cu(III) product at time t and infinity, respectively, showed marked deviations from linearity. The curves showed an acceleration of reaction rate consistent with an autocatalytic behavior. In the presence of Hg(II) ions, plots of ln(A ∞ ? A t ) versus time are linear up to >85 % of reaction. The value of the observed rate constant, k obs, increases with decreasing pH. At constant reaction conditions, the dependence of the observed rate constants, k obs, is described by Eq. (1). 1 $$ k_{\text{obs}} = k_{\text{o}} + k_{1} \left[ {{\text{H}}^{ + } } \right] $$ The dependence of both k o and k 1 on [SBr] is not linear. The mechanism of the title reaction is consistent with an inner sphere mechanism in which a pre-equilibrium step precedes the electron transfer step. The overall rate law is represented by Eq. (2) where [CuIIL]t and K 1 represent the total copper(II) complex concentration and the pre-equilibrium formation constant, respectively. 2 $$ d\left[ {{\text{Cu}}^{\text{III}} {\text{L}}^{ + } } \right]/dt = \left\{ {\left( {k_{\text{o}} + k_{1} \left[ {{\text{H}}^{ + } } \right]} \right)\left[ {\text{SBr}} \right]\left[ {{\text{Cu}}^{\text{II}} {\text{L}}} \right]_{t} } \right\}/\left( {1 + K_{1} \left[ {\text{SBr}} \right]} \right) $$ . 相似文献
86.
Bechir Mrabet Aymen Mejbri Samia Mahouche Sarra Gam‐Derouich Mireille Turmine Mourad Mechouet Philippe Lang Hilaire Bakala Moncef Ladjimi Amina Bakhrouf Sven Tougaard Mohamed M. Chehimi 《Surface and interface analysis : SIA》2011,43(11):1436-1443
Poly(oligoethylene glycol methacrylate), POEGMA, brushes were prepared by surface‐initiated atom transfer radical polymerization (SI‐ATRP) on gold‐coated silicon wafers. Prior to ATRP, the substrates were grafted by brominated aryl initiators via the electrochemical reduction of a noncommercial parent diazonium salt of the formula BF4?, +N2‐C6H4‐CH(CH3)Br. The diazonium‐modified gold plates (Au‐Br) served as macroinitiators for ATRP of OEGMA which resulted in hydrophilic surfaces (Au‐POEGMA) that could be used for two distinct objectives: (i) resistance to fouling by Salmonella Typhimurium; (ii) specific recognition of the same bacteria provided that the POEGMA grafts are activated by anti‐Salmonella. The Au‐POEGMA plates were characterized by XPS, polarization modulation‐infrared reflection‐absorption spectroscopy (PM‐IRRAS) and contact angle measurements. Both Beer‐Lambert equation and Tougaard's QUASES software indicated a POEGMA thickness that exceeds the critical ~10 nm value necessary for obtaining a hydrophilic polymer with effective resistance to cell adhesion. The Au‐POEGMA slides were further activated by trichlorotriazine (TCT) in order to covalently bind anti‐Salmonella antibodies (AS). The antibody‐modified Au‐POEGMA specimens were found to specifically attach Salmonella Typhimurium bacteria. This work is another example of the diazonium salt/ATRP process to provide biomedical polymer surfaces. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
87.
The present article reports the formation of arsenic sulfide films on GaAs by the potentiodynamic polarization in acidified thiourea (TU) electrolytes under photo-illumination. Oxidation of TU competes with the oxidation of GaAs itself and leads to the formation of surface arsenic-sulfide films. Surface chemical composition is investigated by X-ray photoelectron spectroscopy (XPS), demonstrating the formation of As-sulfide as the XPS peaks at binding energies of 42.6 and 162.5 eV for As 3d and S 2p, respectively, are observed. XPS results also show diminishing of Ga species from the surface while As-sulfide is forming. Though, As-sulfide is predominantly formed on the surface, but the inductive coupling plasma-mass spectroscopy (ICP-MS) analysis still shows a preferential dissolution of As ions into electrolytes. These results indicate that Ga ions diffuse into the bulk of the electrode material. The formation of As-sulfide, initially, enhances the photocurrent generation; presumably, due to suppressing electron-hole recombination processes. Further deposition of As-sulfide deteriorates GaAs photoactivity due to retarding light absorptivity because of depositing a thick As-sulfide film. The morphology of the As-sulfide film is characterized by scanning electron microscopy (SEM) that shows the formation of smooth and nonporous films in TU electrolytes acidified by H2SO4 of concentration ≥0.2 M. Electrochemical impedance measurements show that GaAs corrosion is limited by the growth and oxidation of the sulfide layer. 相似文献
88.
Schiff bases of the type salicylidene 2-aminobenzothiazole and o-nitrobenzylidene 2-aminobenzothiazole were prepared by condensation of 2-aminobenzothiazole with salicylaldehyde and o-nitrobenzaldehyde. The bases react with cobalt(II), nickel(II) and copper(II) chlorides to give 1:1 and 1:2 complexes. Electronic spectra, magnetic susceptibility measurements and infrared data are used to infer the structures. The thermal decomposition of the complexes and evaluation of the thermodynamic parameters are also reported. 相似文献
89.
This article presents an experimental study conducted on a six-lobed rectangular jet at a very low Reynolds number of 800. The near-exit flow dynamics is compared to the reference counterpart circular jet with same initial conditions. Flow dynamics is analyzed using time-resolved flow-visualizations, hot-wire anemometry and laser Doppler velocimetry. In the round jet, flow motion is dominated by large primary Kelvin–Helmholtz (K–H) structures. In the six-lobed rectangular jet, the K–H vortices are very thin compared to the large secondary vortices generated by the high shear at the lobed nozzle lip. The inspection of mean-velocity profiles and streamwise evolutions of the spreading rates in the major and the minor planes of the lobed jet confirm the absence of the switching-over phenomenon not observed on flow images. The streamwise structures that develop in orifice troughs render the volumetric flow rate significantly higher than that of the reference circular jet. Comparison of the obtained results to available data of the literature of similar rectangular six-lobed jets investigated at very high Reynolds numbers reinforces the notion that the three-dimensional flowfields at very low and very high Reynolds numbers are similar if the geometry of the lobed nozzle is conserved. However, important variations in flow dynamics might occur if one or several geometric parameters of the lobed nozzle are modified. 相似文献
90.
Nucleus-acoustic(NA) solitary waves(SWs) propagating in a self-gravitating degenerate quantum plasma(SDQP)system(containing non-relativistically degenerate heavy and light nuclei,and non-/ultra-relativistically degenerate electrons) have been theoretically investigated.The modified Korteweg–de Vries(m K-d V) equation has been derived for both planar and non-planar geometry by employing the reductive perturbation technique.It is shown that the NA SWs exist with positive(negative) electrostatic(self-gravitational) potential.It is also observed that the effects of non-/ultra-relativistically degenerate electron pressure,dynamics of non-relativistically light nuclei,spherical geometry,etc.significantly modify the basic features(e.g.,amplitude,width,speed,etc.) of the NA SWs.The applications of our results,which are relevant to astrophysical compact objects,like white dwarfs and neutron stars,are briefly discussed. 相似文献