A型原花青素衍生物的制备、抗氧化和α-葡萄糖苷酶抑制活性研究

doi:10.5246/jcps.2021.04.023

中国药学(英文版) ›› 2021, Vol. 30 ›› Issue (4): 280-288.DOI: 10.5246/jcps.2021.04.023

A型原花青素衍生物的制备、抗氧化和α-葡萄糖苷酶抑制活性研究

张慧文¹^,², 许海燕¹, 张玉¹, 马超美¹^,^*()

1. 内蒙古大学生命科学学院牧草与特色作物生物技术教育部重点实验室, 内蒙古呼和浩特 010070
2. 内蒙古医科大学, 内蒙古呼和浩特 010110

收稿日期:2020-12-06 修回日期:2021-01-03 接受日期:2021-01-15 出版日期:2021-04-30 发布日期:2021-04-30
通讯作者: 马超美
作者简介:
+ Tel./Fax: +86-471-4992435, E-mail: cmma@imu.edu.cn
基金资助:
National Natural Science Foundation of China (Grant No. 81860688), College Students Innovation and Entrepreneurship Project of Inner Mongolia (Grant No. 202010132013) and the Scientific Research Project of introductory high-level talents in Inner Mongolia.

A-type procyanidin derivatives with antioxidant and much enhanced α-glucosidase inhibitor activities

Huiwen Zhang¹^,², Haiyan Xu¹, Yu Zhang¹, Chaomei Ma¹^,^*()

1 Key Laboratory of Forage and Endemic Crop Biotechnology of Ministry of Education, School of Life Sciences, Inner Mongolia University, Hohhot 010070, China
2 Inner Mongolia Medical University, Hohhot 010110, China

Received:2020-12-06 Revised:2021-01-03 Accepted:2021-01-15 Online:2021-04-30 Published:2021-04-30
Contact: Chaomei Ma

摘要/Abstract

摘要：

原花青素是一类具有良好生物活性的天然化合物, 但由于其结构中含有大量的酚羟基, 造成其极性大、生物利用度较低的特点。制备A型原花青素衍生物是改变其极性和生物活性的有效手段。本文采用两种安全可靠的制备方法, 合成了一系列A型原花青素衍生物, 并通过¹H NMR、¹³C NMR、H MBC、¹H-¹H COSY和MS对其结构进行鉴定, 其中有两种新的原花青素A型二聚体衍生物: 原花青素A1-丙酮缩合物(6)和原花青素A2-半胱氨酸衍生物(9)。活性测试结果表明所有化合物均具有较强的DPPH自由基清除活性。化合物6对α-葡萄糖苷酶有较强的抑制活性, IC₅₀值为8.7 μg/mL, 其前体化合物原花青素A1对α-葡萄糖苷酶无抑制作用。采用L-cystein 对花生红衣中原花青素多聚体进行降解研究, 实验结果表明花生红衣中原花青素多聚体的主要结构单元为A型原花青素二聚体。

关键词: 花生红衣, A型原花青素-丙酮缩合物, A型原花青素-半胱氨酸衍生物, α-葡萄糖苷酶抑制活性

Abstract:

Procyanidins are natural compounds with good biological activity. However, due to a large number of phenolic hydroxyl groups in the structure, they have high polarity and low bioavailability. The preparation of A-type proanthocyanidin derivatives is an effective way to change their polarity and biological activity. In this paper, a series of A-type procyanidin derivatives were designed and synthesized by two practical and safe methods, and two new dimeric A-type procyanidin derivatives, procyanidin A1-acetone conjugate (6) and procyanidin A2-cystein conjugate (9) were obtained and reported for the first time. Their structures were characterized and confirmed by ¹H NMR, ¹³C NMR, HMBC, ¹H-¹H COSY and MS. All the compounds showed strong DPPH scavenging activities. Compound 6 showed inhibitory effects on α-glucosidase with an IC₅₀ value of 8.7 μg/mL, while its parental compound, procyanidin A1, had no inhibitory effects. Degradation of procyanidins from peanut skin by L-cystein was studied. The results showed that the main structural unit of procyanidins in peanut skin was A-type proanthocyanidins dimer.

Key words: Peanut skin, A-type procyanidin-acetone conjugate, A-type procyanidin-cystein conjugate, Inhibition on α-glucosidase

Supporting:

张慧文, 许海燕, 张玉, 马超美. A型原花青素衍生物的制备、抗氧化和α-葡萄糖苷酶抑制活性研究[J]. 中国药学(英文版), 2021, 30(4): 280-288.

Huiwen Zhang, Haiyan Xu, Yu Zhang, Chaomei Ma. A-type procyanidin derivatives with antioxidant and much enhanced α-glucosidase inhibitor activities[J]. Journal of Chinese Pharmaceutical Sciences, 2021, 30(4): 280-288.

图/表 7

Scheme 1. Preparation of catechin-acetone conjugate (Compound 5).

Scheme 2. Preparation of the procyanidin A1-acetone conjugate (Compound 6).

Scheme 3. Chemical structures and degradation products of polymers (connection orders of the extender units may be exchangeable, 4→6 connections may also exist).

Table 1. The contents of the degradation products of procyanidin polymers*.

Figure 1. The key correlations of 9 in HMBC and 1H-1H COSY spectra.

Table 2. Comparison of 1H and 13C NMR data of compounds 3, 4, 6 and 9 (methanol-d4).

Table 3. The bioactivities of peanut skin procyanidin monomers, oligomers and their derivatives.

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A型原花青素衍生物的制备、抗氧化和α-葡萄糖苷酶抑制活性研究

A-type procyanidin derivatives with antioxidant and much enhanced α-glucosidase inhibitor activities

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