Identification of chemical markers in Cordyceps sinensis by HPLC-MS/MS.

Identification of chemical markers in Cordyceps sinensis by HPLC-MS/MS.
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DOI:
10.1007/s00216-015-8978-6
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发表时间:
2015-10
影响因子:
4.3
通讯作者:
Liu YM
Liu YM
中科院分区:
化学2区
文献类型:
--
作者:
Hu H;Xiao L;Zheng B;Wei X;Ellis A;Liu YM

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冬虫夏草是一种珍贵而昂贵的天然产品,具有多种健康益处,其认证和质量评估具有重要意义。为了确定有效的化学标记物,正宗的C。采用HPLC-MS/MS技术对冬虫夏草中的糖甙成分进行了全面的分离和鉴定,并首次从冬虫夏草中分离出环丙氨酸亮氨酸鼠李糖和苯丙氨酸邻葡萄糖两种糖甙成分。选择虫草素、D-甘露醇、苯丙氨酸、苯丙氨酸邻葡萄糖、环甘氨酸脯氨酸和环丙氨酸亮氨酸鼠李糖等6种成分作为化学标记物。HPLC-MS/MS方法的开发,同时定量与灵敏度和特异性。该方法的检测限范围为0.008 μg mL−1(虫草素)至0.75 μg mL−1(环-Gly-Pro)。在所有试验中,回收率在96%-103%之间。为了评价所提出的标记库的有效性,对5个真实的C。分析了5个冬虫夏草及其替代品样品。虫草素,D-甘露醇,苯丙氨酸被发现存在于所有的样品。虫草素含量范围为0.0076 - 0.029%(w/w),甘露醇含量范围为0.33 - 18.9%,苯丙氨酸含量范围为0.0013 - 0.642%。有趣的是,两种糖苷,Phe-o-葡萄糖和环-Ala-Leu-鼠李糖仅在真实的C.中国样品。这些结果表明,所提出的基于HPLC-MS/MS定量标记物的方案可能具有很大的潜力,在认证和质量评价的C。中国产。
Authentication and quality assessment of Cordyceps sinensis, a precious and pricey natural product that offers a variety of health benefits is highly significant. To identify effective chemical markers, authentic C. sinensis was thoroughly screened by using HPLC-MS/MS. In addition to many previously reported ingredients, two glycosides, i.e. cyclo-Ala-Leu-rhamnose and Phe-o-glucose were detected for the first time in this material. Six ingredients detected, including cordycepin, D-mannitol, Phe, Phe-o-glucose, cyclo-Gly-Pro, and cyclo-Ala-Leu-rhamnose, were selected as a collection of chemical markers. An HPLC-MS/MS method was developed to simultaneously quantify them with sensitivity and specificity. The method had limits of detection ranging from 0.008 μg mL−1 for cordycepin to 0.75 μg mL−1 for cyclo-Gly-Pro. Recovery was found between 96% and 103% in all tests. To evaluate the effectiveness of the marker collection proposed, 5 authentic C. sinensis samples and 5 samples of its substitutes were analyzed. Cordycepin, D-mannitol, and Phe were found present in all samples. The contents ranged from 0.0076 to 0.029% (w/w) for cordycepin, 0.33 to 18.9 % for mannitol, and 0.0013 to 0.642% for Phe. Interestingly, the two glycosides, Phe-o-glucose and cyclo-Ala-Leu-rhamnose were detected only in authentic C. sinensis samples. These results indicated that the proposed protocol based on HPLC-MS/MS quantification of the markers might have a great potential in authentication and quality assessment of C. sinensis.