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121.
Fuyu Guan Cornelius E. Uboh Lawrence R. Soma Mary Robinson George A. Maylin Xiaoqing Li 《Analytical and bioanalytical chemistry》2013,405(14):4707-4717
Dermorphin is a unique opioid peptide that is 30–40 times more potent than morphine. It was misused and went undetected in horse racing until 2011 when intelligence obtained from a few North American race tracks suggested its use. To prevent such misuse, a reliable analytical method became necessary for detection and identification of dermorphin in post-race horse samples. This paper describes the first liquid chromatography–tandem mass spectrometry (LC–MS/MS) method for such a purpose. Equine plasma and urine samples were pre-treated with ethylenediamine tetra-acetic acid and urea prior to solid-phase extraction (SPE) on Oasis MCX cartridges. Resulting eluates were dried under vacuum and analyzed by LC–MS/MS for dermorphin. The matrix effect, SPE efficiency, intra-day and inter-day accuracy and precision, and stability of the analyte were assessed. The limit of detection was 10 pg/mL in plasma and 20 pg/mL in urine, and the limit of confirmation was 20 pg/mL in plasma and 50 pg/mL in urine. Dermorphin in plasma is stable at ambient temperature, but its diastereomer is unstable. With isotopically labeled dermorphin as an internal standard, the quantification range was 20–10,000 pg/mL in plasma and 50–20,000 pg/mL in urine. The intra-day and inter-day accuracy was from 91 % to 100 % for the low, intermediate, and high concentrations. The intra-day and inter-day coefficients of variation were less than 12 %. The method differentiates dermorphin from its diastereomer. This method is very specific for identification of dermorphin in equine plasma and urine, as assessed by BLAST search and targeted SEQUEST search, and by MS/MS spectrum library search. The method has been successfully applied to analysis of samples collected following dermorphin administration to research horses and of official post-race samples. Figure
? 相似文献
122.
Following Solid‐Acid‐Catalyzed Reactions by MAS NMR Spectroscopy in Liquid Phase—Zeolite‐Catalyzed Conversion of Cyclohexanol in Water 下载免费PDF全文
Aleksei Vjunov Mary Y. Hu Dr. Ju Feng Dr. Donald M. Camaioni Dr. Donghai Mei Dr. Jian Z. Hu Dr. Chen Zhao Prof. Dr. Johannes A. Lercher 《Angewandte Chemie (International ed. in English)》2014,53(2):479-482
A microautoclave magic angle spinning NMR rotor is developed enabling in situ monitoring of solid–liquid–gas reactions at high temperatures and pressures. It is used in a kinetic and mechanistic study of the reactions of cyclohexanol on zeolite HBEA in 130 °C water. The 13C spectra show that dehydration of 1‐13C‐cyclohexanol occurs with significant migration of the hydroxy group in cyclohexanol and the double bond in cyclohexene with respect to the 13C label. A simplified kinetic model shows the E1‐type elimination fully accounts for the initial rates of 1‐13C‐cyclohexanol disappearance and the appearance of the differently labeled products, thus suggesting that the cyclohexyl cation undergoes a 1,2‐hydride shift competitive with rehydration and deprotonation. Concurrent with the dehydration, trace amounts of dicyclohexyl ether are observed, and in approaching equilibrium, a secondary product, cyclohexyl‐1‐cyclohexene is formed. Compared to phosphoric acid, HBEA is shown to be a more active catalyst exhibiting a dehydration rate that is 100‐fold faster per proton. 相似文献
123.
The reaction of epibromohydrin with hydroxyquinazolin-2-(1H)one derivatives. Novel oxazine formation
Mary Lou Cotter Victor Bandurco Elizabeth Wong Zoltan G. Hajos 《Journal of heterocyclic chemistry》1979,16(3):623-624
Epibromohydrin was found to react with 7-hydroxy-2-methylpyrrolo[1,2-c]quinazolin-5(6H)-one ( 4 ) in the presence of sodium hydroxide to form the novel oxazine 5 . The structure of compound 5 was proven by cmr and pmr analysis. 相似文献
124.
Kim Henrick Mary McPartlin Glen B. Deacon Roderic J. Phillips 《Journal of organometallic chemistry》1980,204(3):287-294
An X-ray crystallographic study has shown that the complex (C6H5)2TlO2CC6F5(OPPh3) has a dimeric structure with unsymmetrical pentafluorobenzoate bridging (TlO 2.531 and 2.789 Å) but an exact crystallographic centre of symmetry. The pentafluorobenzoate groups are also unsymmetrically chelated to thallium (TlO 2.389 and 2.531 Å.), which overall has irregular six coordination. 相似文献
125.
Mary E. Gimon-Kinsel Gary R. Kinsel Ricky D. Edmondson David H. Russell 《Journal of the American Society for Mass Spectrometry》1995,6(7):578-587
A two-stage linear time-of-flight mass spectrometer is used to investigate the requirements for performance of laser photodissociation of peptide and protein ions. Results are presented that demonstrate that desorption and dissociation laser pulses can be synchronized to irradiate ions that travel at high velocities down the drift tube of a time-of-flight mass spectrometer. For example, 193-nm photodissociation of bovine insulin and doubly charged lysozyme is demonstrated, and laser power studies suggest that dissociation is initiated by the absorption of a single 193-nm photon. These results are encouraging because they suggest that laser photodissociation of high molecular weight proteins can lead to fragmentation on time scales compatible with time-of-flight mass spectrometry. 相似文献
126.
Exposure to artificial UV wavelengths and the UV component of sunlight delays positive phototaxis in the green alga Volvox aureus. Broad band wavelength filters were used to modify the output from UV-B sources (280-320 nm) and natural sunlight. The delay in phototaxis by artificial UV is increased with exposure to shorter UV-B wavelengths. Natural sunlight experiments were performed with exposure to full sunlight and to its UV component only. The UV component present in summer sunlight produced long periods of inhibition in phototaxis and even lethality, while exposure to the total spectrum of sunlight had no significant effects on movement or survival. The data indicate that although this species of alga is well equipped to deal with present levels of UV exposure, increases in the short UV-B wavelengths in sunlight may force an alteration in patterns of photomovement. 相似文献
127.
Two approaches for performing competitive binding immunoassays by HPLC and other flow-based systems are the simultaneous and sequential injection methods. Both these techniques make use of a column with a limited amount of antibody, onto which is injected a sample and a fixed amount of a labeled analyte analog. An indirect measure of the unlabeled analyte in the sample is then obtained by looking at the amount of analog in either the nonretained or retained peaks. In the simultaneous injection mode, the sample and labeled analog are applied at the same time to the column, while in the sequential mode the sample is injected first, followed by the analog. This results in a difference in the analytical characteristics of these two approaches. This study used chromatographic theory and previous data obtained for injections of human serum albumin (HSA) onto an anti-HSA antibody column to compare the response, detection limits, range, and sensitivity of these methods. Under equivalent conditions, it was found that the sequential method always provided the best lower limit of detection and sensitivity. However, the simultaneous mode had a broader dynamic range and higher upper limit of detection. From these observations, several guidelines were developed regarding the use and selection of such assays for new applications. 相似文献
128.
Boris U. Stambuk Mary Ann Franden Arjun Singh Min Zhang 《Applied biochemistry and biotechnology》2003,106(1-3):255-263
The kinetics and regulation of d-xylose uptake were investigated in the efficient pentose fermentor Candida succiphila, and in Kluyveromyces marxianus, which assimilate but do not ferment pentose sugars. Active high-affinity (K
m
∼ 3.8 mM; V
max ∼ 15 nmol/[mg·min]) and putative facilitated diffusion low-affinity (K
m
∼ 140 mM; V
max ∼ 130 nmol/[mg·min]) transport activities were found in C. succiphila grown, respectively, on xylose or glucose. K. marxianus showed facilitated diffusion low-affinity (K
m
∼ 103 mM; V
max ∼ 190 nmol/[mg·min]) transport activity when grown on xylose under microaerobic conditions, and both a low-affinity and an
active high-affinity (K
m
∼ 0.2 mM; V
max ∼ 10 nmol/[mg·min]) transport activity when grown on xylose under fully aerobic conditions. 相似文献
129.
E. Pollert J. Hejtmnek K. Kní
ek M. Mary
ko J. P. Doumerc J. C. Grenier J. Etourneau 《Journal of solid state chemistry》2003,170(2):368-373
The electric and magnetic properties of the perovskites Nd0.8Na0.2Mn(1−x)CoxO3 (0x0.2) prepared by the usual ceramic procedure were investigated. The insulator-to-metal-like (IM) transition, closely related to a ferromagnetic arrangement, was revealed for the composition of x=0.04 and a similar tendency was detected for x=0. The insulating behavior persists down to low temperatures for higher contents of cobalt ions in spite of the transition to the bulk ferromagnetism. The properties are interpreted in terms of the steric distortion, tilting of the Mn(Co)O6 octahedra and the double-exchange interactions of the type Mn3+–O2−–Mn4+and Mn3.5+δ–O2−–Co2+, respectively. Presence of antiferromagnetic domains in the ferromagnetic matrix for the most of cobalt-substituted samples is supposed. 相似文献
130.
Mary E. Carter James L. Nash Joseph W. Drueke James W. Schwietert George B. Butler 《Journal of polymer science. Part A, Polymer chemistry》1978,16(5):937-959
β-Nitrostyrene and many of its derivatives have been shown to yield high polymers via anionic initiation with alkoxide ions in protic solvents, e.g., alcohols. A study was conducted to determine the effect of certain substituents on the polymerization characteristics of representative monomers of this series and the properties of their polymers. A kinetic study was conducted and the relative rates of propagation were unexpectedly found to correlate well with brown's σ+ values. The rates of initiation of two representative monomers, β-nitrostyrene and p-methoxy-β-nitrostyrene, with sodium ethoxide were found to be 3.51 and 2.86 liter/mole sec, respectively. The rate of chain transfer in ethanol was studied qualitatively by using gel-permeation chromatography (GPC) to obtain molecular weight distribution (MWD) curves. The low values of the M w/M n ratios indicated little chain transfer in the protic solvent. 相似文献