Identification of the position of mono-O-glucuronide of flavones and flavonols by analyzing shift in online UV spectrum (lambdamax) generated from an online diode array detector.
Identification of the position of mono-O-glucuronide of flavones and flavonols by analyzing shift in online UV spectrum (lambdamax) generated from an online diode array detector.
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DOI：
10.1021/jf904561e
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发表时间：
2010-09-08
影响因子：
6.1
通讯作者：
Hu M
中科院分区：
文献类型：
--
作者：
Singh R;Wu B;Tang L;Liu Z;Hu M
黄酮类化合物的有益药理学作用，如对癌症、衰老和心脏病的化学预防，由于它们在体内被UGT广泛地葡萄糖醛酸化而受到严重限制。基于底物的化学结构，UGT在类黄酮的葡萄糖醛酸化中显示出区域特异性（即位置偏好）。本文采用体外葡萄糖醛酸化反应，合成了36种黄酮和黄酮醇的葡萄糖醛酸苷。UPLC/MS/MS用于确认具有多达四个羟基的类黄酮中的葡萄糖醛酸化程度（单或二）。使用UPLC和在线二极管阵列检测器生成黄酮类化合物及其各自的单-O-葡萄糖醛酸苷的UV光谱。通过分析λmax值变化反映的谱带I和谱带II区域中葡萄糖醛酸苷光谱的偏移程度，确定葡萄糖醛酸化的位置。结果表明，3-羟基和4 '-羟基的葡萄糖醛酸化分别导致带I λmax蓝移（或蓝移）13-30 nm和5-10 nm。5-羟基的葡萄糖醛酸化使带Ⅱ λmax红移5-10 nm。相比之下，7-羟基的葡萄糖醛酸化未引起条带I或II λmax的任何λmax变化，而6-羟基的葡萄糖醛酸化未引起λmax值的可预测变化。该论文首次证明，利用在线紫外光谱中λmax变化的快速和稳健的分析方法可用于精确定位在4 '、3，5和/或7位具有羟基的黄酮和黄酮醇的区域特异性葡萄糖醛酸化。
The beneficial pharmacological effects of flavonoids such as chemo-prevention against cancer, aging and heart diseases are severely limited due to their extensive in vivo glucuronidation by UGTs. UGTs showed regiospecificity (i.e. position preference) in the glucuronidation of the flavonoids based on substrate’s chemical structure. In this paper, glucuronide(s) of 36 flavones and flavonols were generated using an in vitro glucuronidation reaction. UPLC/MS/MS was used to confirm the degree (mono- or di-) of glucuronidation in flavonoids with up to four hydroxyl group. UV spectra of flavonoids and their respective mono-O-glucuronides were generated using UPLC with an online diode-arrayed detector. Analysis of the extent of shift in spectra of glucuronides in Band I and Band II regions as reflected by changes in λmax value was used to identify the position of glucuronidation. The data showed that glucuronidation of 3- and 4’-hydroxyl resulted in Band I λmax hypsochromic shift (or blue shift) of 13–30 nm and 5–10 nm, respectively. And glucuronidation of 5-hydroxyl group caused Band II λmax hypsochromic shift of 5–10 nm. In contrast, glucuronidation of 7-hydroxyl group did not cause any λmax change in Band I or II λmax whereas glucuronidation of 6-hydroxyl group did not cause predictable changes in λmax values. The paper demonstrated for the first time that a rapid and robust analysis method using λmax changes in online UV spectra can be used to pinpoint region-specific glucuronidation of flavones and flavonols with hydroxyl groups at 4’, 3, 5, and/or 7 position(s).
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影响因子：
7.5
作者：
Hollman, PCH;Katan, MB
通讯作者：
Katan, MB
影响因子：
4.9
作者：
Liu, Xing;Tam, Vincent H.;Hu, Ming
通讯作者：
Hu, Ming
DOI：
10.1124/jpet.103.053496
发表时间：
2003-10-01
影响因子：
3.5
作者：
Hu, M;Chen, J;Lin, HM
通讯作者：
Lin, HM
影响因子：
3.9
作者：
Liu, Y;Hu, M
通讯作者：
Hu, M
DOI：
10.1124/jpet.103.063925
发表时间：
2004-07-01
影响因子：
3.5
作者：
Jeong, EJ;Lin, HM;Hu, M
通讯作者：
Hu, M