Degradation Kinetics and Mechanism of Lithospermic Acid under Low Oxygen Condition Using Quantitative 1H NMR with HPLC-MS.

Degradation Kinetics and Mechanism of Lithospermic Acid under Low Oxygen Condition Using Quantitative 1H NMR with HPLC-MS.
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使用定量 1H NMR 和 HPLC-MS 分析低氧条件下紫精酸的降解动力学和机制

DOI:
10.1371/journal.pone.0164421
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发表时间:
2016
期刊:
影响因子:
3.7
通讯作者:
Qu H
Qu H
中科院分区:
综合性期刊3区
文献类型:
--
作者:
Pan J;Gong X;Qu H

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提出了一种新的定量1H NMR(Q-NMR)结合HPLC-MS的方法来研究中药成分的降解过程。该方法实现了中药多酚酸类化合物紫草酸在低氧条件下降解动态过程的原位监测。该方法简便、快速、专属性强。降解动力学运行已经进行了系统的研究两个关键的环境因素,初始pH值和温度的影响。本研究共检测到8种LA的主要降解产物,其中7种经NMR和LC-MS初步鉴定,丹参素A(SalA)是LA的主要降解产物。提出了LA可能的降解途径。结果表明,LA的降解符合准一级动力学。表观降解动力学常数随磷酸盐缓冲液初始pH值的增大而增大。在给定的条件下,总降解速率常数与温度的函数关系服从Arrhenius方程。结果表明,Q-NMR结合HPLC-MS技术是研究中药有效成分降解过程的最有前途的技术之一。
A novel quantitative 1H NMR (Q-NMR) combined with HPLC-MS method has been proposed for investigating the degradation process of traditional Chinese medicine (TCM) components. Through this method, in-situ monitoring of dynamics degradation process of lithospermic acid (LA), one of the popular polyphenolic acids in TCM, was realized under low oxygen condition. Additionally, this methodology was proved to be simple, rapid and specific. Degradation kinetic runs have been carried out to systematically investigate the effects of two key environmental factors, initial pH values and temperatures. Eight main degradation products of LA were detected, seven of which were tentatively structural elucidated with the help of both NMR and LC-MS in this work and salvianolic acid A (Sal A) was the primary degradation product of LA. A possible degradation pathway of LA was proposed, subsequently. The results showed that the degradation of LA followed pseudo-first-order kinetics. The apparent degradation kinetic constants increased as the initial pH value of the phosphate buffer increased. Under the given conditions, the rate constants of overall degradation as a function of temperature obeyed the Arrhenius equation. Our results proved that the Q-NMR combined with HPLC-MS method can be one of the most promising techniques for investigating degradation process of active components in TCM.
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