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91.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
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高能重带电粒子能直接穿透靶原子核外电子层,与原子核发生直接碰撞,发生散裂反应,产生一系列具有放射性的剩余产物核.重带电粒子诱发靶材放射性剩余核与辐射防护和人员安全有着密切联系,当前,大部分剩余核产额主要依靠蒙特卡罗粒子输运程序进行模拟计算,其准确程度亟需通过实验测量进行准确评估.本文利用能量为80.5 MeV/u的(12)^C6+粒子对薄铜靶开展了辐照实验与伽玛射线测量,结合伽玛谱学分析方法,得出了辐照产生的18种放射性剩余产物的初始活度和产生截面值,并与PHITS模拟结果进行对比.结果表明,PHITS模拟程序对放射性剩余核种类的估计具有较高可靠性,在其绝对产额方面,与实验测量仍具有较大偏差. 相似文献
97.
Yablokov M. Yu. Shchegolikhin A. N. Lebedev O. V. Goncharuk G. P. Ozerin A. N. 《Russian Chemical Bulletin》2021,70(9):1816-1821
Russian Chemical Bulletin - Gradient polymer composites were prepared by melt-mixing of carbon black and polypropylene in a compounder and subsequent hot pressing of pellets. The thermally treated... 相似文献
98.
Yimei Wang Yi Qiao Xiaomin Xu Xiaohong Ding Weiwei Li Bo Yuan Haiyan Xu 《Biomedical chromatography : BMC》2019,33(8)
A sensitive and reliable LC–MS/MS method was developed and validated for simultaneous quantification of the major components of Huangqi–Honghua extact in rat plasma, including hydroxysafflor yellow A (HSYA), astragaloside IV (ASIV), calycosin‐7‐O‐β‐d ‐glucoside (CAG), calycosin, calycosin‐3′‐O‐glucuronide (C‐3′‐G) and calycosin‐3′‐O‐sulfate (C‐3′‐S). After extraction by protein precipitation with acetonitrile and methanol from plasma, the analytes were separated on a Hypersil BDS C18 column by gradient elution with acetonitrile and 5 mM ammonium acetate. The detection was carried out on a triple quadrupole tandem mass spectrometer equipped with electrospray ionization source switched between negative and positive modes. HSYA was monitored in negative ionization mode from 0 to 4.9 min, and ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S were determined in positive ionization mode from 4.9 to 10 min. The lower limits of quantification of the analytes were 6.25 ng/mL for HSYA, 0.781 ng/mL for CAG and 1.56 ng/mL for ASIV and calycosin. The intra‐ and inter‐assay precision (RSD) values were within 13.43%, and accuracy (RE) ranged from ?8.75 to 9.92%. The validated method was then applied to the pharmacokinetic study of HSYA, ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S in rat after an oral administration of Huangqi–Honghua extract. 相似文献
99.
Gelikonov G. V. Ksenofontov S. Yu. Shilyagin P. A. Gelikonov V. M. 《Radiophysics and Quantum Electronics》2019,62(3):228-236
Radiophysics and Quantum Electronics - We propose and experimentally test a numerical method for correction of the influence of fluctuations in the distance to objects during noncontact probing in... 相似文献
100.
Kai He Tsegaye TadesseTsega Xi Liu Jiantao Zai Xin‐Hao Li Xuejiao Liu Wenhao Li Nazakat Ali Xuefeng Qian 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(34):12029-12035
The modulation of electron density is an effective option for efficient alternative electrocatalysts. Here, p‐n junctions are constructed in 3D free‐standing FeNi‐LDH/CoP/carbon cloth (CC) electrode (LDH=layered double hydroxide). The positively charged FeNi‐LDH in the space‐charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs. RHE) of FeNi‐LDH/CoP/CC achieves ca. 10‐fold and ca. 100‐fold increases compared to those of FeNi‐LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH? has a stronger trend to adsorb on the surface of FeNi‐LDH side in the p‐n junction compared to individual FeNi‐LDH further verifying the synergistic effect in the p‐n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities. 相似文献