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62.
Metabolic profiles of dioscin in rats revealed by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry 下载免费PDF全文
He Zhu Jin‐Di Xu Qian Mao Hong Shen Ming Kong Jian‐Ping Chen Song‐Lin Li 《Biomedical chromatography : BMC》2015,29(9):1415-1421
Dioscin (DIS), one of the most abundant bioactive steroidal saponins in Dioscorea sp., is used as a complementary medicine to treat coronary disease and angina pectoris in China. Although the pharmacological activities and pharmacokinetics of DIS have been well demonstrated, information regarding the final metabolic fates is very limited. This study investigated the in vivo metabolic profiles of DIS after oral administration by ultra‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry method. The structures of the metabolites were identified and tentatively characterized by means of comparing the molecular mass, retention time and fragmentation pattern of the analytes with those of the parent compound. A total of eight metabolites, including seven phase I and one phase II metabolites, were detected and tentatively identified for the first time. Oxidation, deglycosylation and glucuronidation were found to be the major metabolic processes of the compound in rats. In addition, a possible metabolic pathway on the biotransformation of DIS in vivo was proposed. This study provides valuable and new information on the metabolism of DIS, which will be helpful for further understanding its mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
63.
本文采用相场格子Boltzmann方法研究了竖直微通道内中等Atwoods数流体的单模Rayleigh-Taylor不稳定性问题,系统分析了雷诺数对相界面动力学行为以及扰动在各发展阶段演化规律的影响.数值结果表明高雷诺数条件下,不稳定性界面扰动的增长经历了四个不同的发展阶段,包括线性增长阶段、饱和速度阶段、重加速阶段及混沌混合阶段.在线性增长阶段,我们计算获得的气泡与尖钉振幅符合线性稳定性理论,并且线性增长率随着雷诺数的增加而增大.在第二个阶段,我们观察到气泡与尖钉将以恒定的速度增长,获得的尖钉饱和速度略高于Goncharov经典势能模型的解析解[Phys.Rev.Lett.200288134502],这归因于系统中产生了多个尺度的旋涡,而涡之间的相互作用促进了尖钉的增长.随着横向速度和纵向速度的差异扩大,气泡和尖钉界面演化诱导产生的Kelvin–Helmholtz不稳定性逐渐增强,从而流体混合区域出现许多不同层次的涡结构,加速了气泡与尖钉振幅的演化速度,并在演化后期阶段,导致界面发生多层次卷起、剧烈变形、混沌破裂等行为,最终形成了非常复杂的拓扑结构.此外,我们还统计了演化后期气泡与尖钉的无量纲加速度,发现气泡和尖钉的振幅在后期呈现二次增长规律,其增长率系数分别为0.045与0.233.而在低雷诺条件下,重流体在不稳定性后期以尖钉的形式向下运动而轻流体以气泡的形式向上升起.在整个演化过程中,界面变得足够光滑,气泡与尖钉在后期的演化速度接近于常数,未观察到后期的重加速与混沌混合阶段. 相似文献
64.
基于单相流体的概念,超临界流体的异常传热行为已经被研究很多年了,但是关于其流动传热机理仍没有统一的认识.本文通过理论分析和实验研究了超临界二氧化碳在竖直管内向上流动过程中,浮升力和流动加速效应对其流动结构和传热过程的影响.结果表明,没有确凿的实验证据表明超临界流体的异常传热行为是浮升力和流动加速直接导致的,存在的估计浮升力和流动加速效应准则均是在常物性流体的基础上,做了大量假设得出的,不同的研究者采用浮升力和流动加速准则分析超临界流体的传热恶化得出的结论不一致.最后,基于拟沸腾理论分析超临界流体的传热恶化过程,提出超临界沸腾数区分了超临界流体正常传热与恶化传热的转换边界,为超临界流体流动传热研究提供新思路,超临界沸腾数对建立用于不同技术的超临界流体动力循环的最佳运行条件具有重要意义. 相似文献
65.
Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway 下载免费PDF全文
Dr. Anissa Amar Dr. Paul Savel Dr. Huriye Akdas‐Kilig Dr. Claudine Katan Prof. Hacène Meghezzi Prof. Abdou Boucekkine Dr. Jean‐Pierre Malval Dr. Jean‐Luc Fillaut 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8262-8270
Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes. 相似文献
66.
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
67.
In this paper,we investigate the non-autonomous Hamilton-Jacobi equation ■ where H is 1-periodic with respect to t and M is a compact Riemannian manifold without boundary.We obtain the viscosity solution denoted by T_(t_0)~tφ(x) and show T_(t_0)~tφ(x) converges uniformly to a time-periodic viscosity solution u~*(x,t) of ?_tu+H(t,x,?_xu,u)=0. 相似文献
68.
69.
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
70.
Nonlinear Dynamics - This paper seeks to address the problem of finite-time stabilization for a class of uncertain Hamiltonian systems via sliding mode control approach. A novel sliding function in... 相似文献