密闭式微波降解法促进常见人参皂苷向稀有人参皂苷转化的规律

doi:10.7503/cjcu20140641

摘要/Abstract

摘要：

采用密闭微波技术对7种常见人参皂苷单体(Rb₁, Rb₂, Rb₃, Rc, Rd, Re和Rg₁)进行降解, 通过高效液相色谱(HPLC)分析并与相同条件下非微波降解物对比, 研究了密闭微波降解人参皂苷的产物在化学结构及组成上的变化规律, 以期快速、高效地制备生物活性高的稀有人参皂苷. 结果表明, 密闭式微波降解法能够使常见人参皂苷基本降解完全, 而相同条件下非微波降解法则基本不发生降解. 原人参二醇型人参皂苷易水解掉C20位糖, 并发生C20位构型变化, 生成20(R)-Rg₃和20(S)-Rg₃, 其中20-(R)为优势构型, C20位羟基进一步脱水产生稀有人参皂苷Rk₁和Rg₅. 同时, 20(S/R)-Rg₃失去C3位的1分子葡萄糖转化为20(S/R)-Rh₂, C20位羟基再进一步脱水生成了 Rk₂和Rh₃. 此外, 人参皂苷C20位所连的糖种类与构型影响了降解产物中各稀有皂苷的组成与比例, 但7种原人参二醇型人参皂苷密闭式微波降解产物中Rg₅含量均为最高. 密闭式微波降解对原三醇型人参皂苷的转化作用与原二醇型人参皂苷具有相似的规律, 人参皂苷Re和Rg₁的密闭式微波降解产物中Rh₄含量均为最高. 本文结果进一步说明在相同的降解条件下, 密闭式微波降解法的降解效率远高于高温高压非微波降解法, 密闭式微波降解可明显促进常见人参皂苷向稀有人参皂苷转化, 因此采用密闭微波技术对常见人参皂苷进行降解可以大量获得稀有人参皂苷.

关键词: 微波降解, 高效液相色谱, 稀有人参皂苷, 转化

Abstract:

In order to prepare the rare ginsenosides which were considered to have higher bioactivities, confined microwave method to promote the degradation of 7 kinds of major ginsenosides(Rb₁, Rb₂, Rb₃, Rc, Rd, Re, Rg₁) to rare ginsenosides were adopted. Comparing with the degradation products of non-microwave method at the same condition, the rules of conversion about the structures and ingredients of degradation products were concluded by HPLC analysis. The results indicated that confined microwave method can completely degrade all the major ginsenosides, while nearly no major ginsenosides can be degraded under the same condition of non-microwave method. Protopanaxadiol-type ginsenosides were easily deglycosylated at C20, where the conformational changes would take place. It would generate 20(S)-Rg₃ and 20(R)-Rg₃ among which the R-type was the superior configuration. Dehydration effect of the hydroxyl at C20 made 20(S/R)-Rg₃ convert to Rk₁ and Rg₅, meanwhile the losing of glucose of 20(S/R)-Rg₃ at C3 position made the generation of 20(S/R)-Rh₂. After further dehydration at C20 position, 20(S/R)-Rh₂ converted to Rk₂ and Rh₃. Moreover, the configurations of glycosyls at C20 of ginsenosides would affect the proportion and composition of rare ginse-nosides in degradation products, but Rg₅ reached highest content in all confined microwave degradation products of 7 kinds of protopanaxadiol-type ginsenosides. Protopanaxatriol-type ginsenosides had similar rules with protopanaxadiol-type ginsenosides by the confined microwave degradation method, and the products of Re and Rg₁ were determined in the highest content of Rh₄.

Key words: Microwave degradation, High performance liquid chromatography(HPLC), Rare ginsenoside, Conversion

中图分类号:

O657
O629

TrendMD:

姚华, 金永日, 杨洁, 李兰杰, 孙婷, 时晓磊, 李绪文. 密闭式微波降解法促进常见人参皂苷向稀有人参皂苷转化的规律. 高等学校化学学报, 2014, 35(11): 2317.

YAO Hua, JIN Yongri, YANG Jie, LI Lanjie, SUN Ting, SHI Xiaolei, LI Xuwen. Conversion Rule of Rare Ginsenosides Produced from Major Ginsenosides by Confined Microiwave Promoted Degradation Method^†. Chem. J. Chinese Universities, 2014, 35(11): 2317.

图/表 5

Fig.1 HPLC chromatogram of major ginsenosides Peak: 1. Rg1; 2. Re; 3. Rb1; 4. Rc;5. Rb2; 6. Rb3; 7. Rd.

Fig.2 HPLC chromatogram of rare ginsenosides Peak: 1. 20(S)-Rh1; 2. 20(R)-Rh1; 3. Rg6; 4. F4; 5. Rk3; 6. Rh4; 7. 20(S)-Rg3; 8. 20(R)-Rg3; 9. Rk1; 10. Rg5; 11. 20(S)-Rh2; 12. Rk2; 13. Rh3.

Fig.3 HPLC chromatograms of major ginsenosides treated by high temperature and pressure method a. Rg1; b. Rb1; c. Re; d. Rd; e. Rb2; f. Rb3; g. Rc. Peak: 1. Rg1; 2. Re; 3. Rb1; 4. Rc; 5. Rb2; 6. Rb3; 7. Rd; 8. 20(S)-Rg3; 9. 20(R)-Rg3; 10. Rk1; 11. Rg5.

Fig.4 HPLC chromatograms of major ginsenosides treated by confined microwave method a. Rb1; b. Rb2; c. Re; d. Rg1; e. Rb3; f. Rc; g. Rd. Peak: 1. 20(S)-Rh1; 2. 20(R)-Rh1; 3. Rg6; 4. F4; 5. Rk3; 6. Rh4; 7. 20(S)-Rg3; 8. 20(R)-Rg3; 9. Rk1; 10. Rg5; 11. 20(S)-Rh2; 12. Rk2; 13. Rh3.

Fig.5 Peak areas of major ginsenosides degradation products of confined microwave() and high temperature and pressure() method (A) Rb1. a. Rb1, b. 20(S)-Rg3, c. 20(R)-Rg3, d. Rk1, e. Rg5, f. Rh2, g. Rk2, h. Rh3; (B) Rb2. a. Rb2, b. 20(S)-Rg3, c. 20(R)-Rg3, d. Rk1, e. Rg5, f. Rh2, g. Rk2, h. Rh3; (C) Rb3. a. Rb3, b. 20(S)-Rg3, c. 20(R)-Rg3, d. Rk1, e. Rg5, f. Rh2, g. Rk2, h. Rh3; (D) Rc. a. Rc, b. 20(S)-Rg3, c. 20(R)-Rg3, d. Rk1, e. Rg5, f. Rh2, g. Rk2, h. Rh3; (E) Rd. a. Rd, b. 20(S)-Rg3, c. 20(R)-Rg3, d. Rk1, e. Rg5, f. Rh2, g. Rk2, h. Rh3; (F) Re. a. Re, b. 20(S)-Rh1, c. 20(R)-Rh1, d. Rg6, e. F4, f. Rk3, g. Rh4, h. Rg2; (G) Rg1. a. Rg1, b. 20(S)-Rh1, c. 20(R)-Rh1, d. Rg6, e. F4, f. Rk3, g. Rh4.

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