本文旨在总结葡萄与蛇葡萄两种植物中存在的多酚,并分析其结构相关性。通过总结2010年至今的文献,发现存在于葡萄或蛇葡萄植物中的多酚共有39种,如白藜芦醇、反-ε-葡萄素、蛇葡萄素、杨梅素-3-O-β-D-葡萄糖苷、山奈酚-3-O-α-L-鼠李糖苷、(+)-花旗松素、3,5,7-三羟基色原酮、儿茶素、表儿茶素-3-O-没食子酸酯、原花青素、咖啡酸、对–香豆酸、没食子酸甲酯。结构相关性分析表明:这些多酚可归为茋及低聚茋、色原酮与黄酮、儿茶素与花青素、酚酸及其酯四大类;而且,低聚茋可由茋类聚合而成的,黄酮则可由色原酮转化而得,花青素则可由儿茶素聚合而得。这些结构相关性进一步提示:每一大类的多酚之间,可能存在生物转化关系;且葡萄与蛇葡萄存在一定的亲缘关系。 This study aims to summarize the phenolics in grape and Ampelopsis grossedentata, and then to analyze the structural correlation between two plants and between these phenolics. Through a literature search from 2010, it is found that there are 39 phenolics in grape or Ampelopsis plants, mainly including resveratrol, trans-ε-viniferin, ampelopsin A, myricetin-3-O-β-D-glucoside, kaempferol-3-O-α-L-rhamnoside, (+) taxifolin, 3,5,7-trihydroxychromone, catechin, epicatechin-3-O-gallate, proanthocyanidin, caffeic acid, p-coumaric acid, and methyl gallate. The structural correlation analysis showed that these phenolics could be classified into four types: stilbene and oligostilbene type, chromogen and flavonoid type, catechin and anthocyanin type, and phenolic acid and its ester type. Further analysis indicated that, the oligostilbenes can be polymerized from stilbenes; and flavonoids can be transformed from chromogen; while catechins can be polymerized into anthocyanins. These structural correlations further suggest that: 1) there may be a bio-conversion relationship between two subtypes in the same phenolic type; 2) And there is a certain genetic relationship between grape plant and Ampelopsis plant.
本文旨在总结葡萄与蛇葡萄两种植物中存在的多酚,并分析其结构相关性。通过总结2010年至今的文献,发现存在于葡萄或蛇葡萄植物中的多酚共有39种,如白藜芦醇、反-ε-葡萄素、蛇葡萄素、杨梅素-3-O-β-D-葡萄糖苷、山奈酚-3-O-α-L-鼠李糖苷、(+)-花旗松素、3,5,7-三羟基色原酮、儿茶素、表儿茶素-3-O-没食子酸酯、原花青素、咖啡酸、对–香豆酸、没食子酸甲酯。结构相关性分析表明:这些多酚可归为茋及低聚茋、色原酮与黄酮、儿茶素与花青素、酚酸及其酯四大类;而且,低聚茋可由茋类聚合而成的,黄酮则可由色原酮转化而得,花青素则可由儿茶素聚合而得。这些结构相关性进一步提示:每一大类的多酚之间,可能存在生物转化关系;且葡萄与蛇葡萄存在一定的亲缘关系。
葡萄属,多酚,茋,黄酮,结构相关性
Jianwu Li1, Xiaojun Zhao2, Xican Li2*
1School of Pharmacy and Food Science, Zhuhai College, Jilin University, Zhuhai Guangdong
2School of Pharmaceutical Sciences, Guangzhou University of Chinese Medicine, Guangzhou Guangdong
Received: Feb. 1st, 2022; accepted: Feb. 25th, 2022; published: Mar. 4th, 2022
This study aims to summarize the phenolics in grape and Ampelopsis grossedentata, and then to analyze the structural correlation between two plants and between these phenolics. Through a literature search from 2010, it is found that there are 39 phenolics in grape or Ampelopsis plants, mainly including resveratrol, trans-ε-viniferin, ampelopsin A, myricetin-3-O-β-D-glucoside, kaempferol-3-O-α-L-rhamnoside, (+) taxifolin, 3,5,7-trihydroxychromone, catechin, epicatechin-3-O-gallate, proanthocyanidin, caffeic acid, p-coumaric acid, and methyl gallate. The structural correlation analysis showed that these phenolics could be classified into four types: stilbene and oligostilbene type, chromogen and flavonoid type, catechin and anthocyanin type, and phenolic acid and its ester type. Further analysis indicated that, the oligostilbenes can be polymerized from stilbenes; and flavonoids can be transformed from chromogen; while catechins can be polymerized into anthocyanins. These structural correlations further suggest that: 1) there may be a bio-conversion relationship between two subtypes in the same phenolic type; 2) And there is a certain genetic relationship between grape plant and Ampelopsis plant.
Keywords:Vitis, Phenolics, Stilbene, Flavonoid, Structural Correlation
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葡萄与蛇葡萄是葡萄科的两大常见植物,它们都属于葡萄科(学名:Vitaceae Juss);但又属于不同的属。葡萄属于葡萄属(学名:Vitis L.),其植物名为Vitis vinifera L;而蛇葡萄则属于蛇葡萄属(Ampelopsis Michx.),含广东蛇葡萄(Ampelopsis cantoniensis) [
在葡萄科中,葡萄与蛇葡萄也是研究得最多的两种植物。近年来的植物化学研究表明,二者都含有大量的多酚成分。从2010至今,共有3篇综述文章总结了这些多酚的名称 [
有鉴于此,本文拟重新检索相关的文献,并详细地绘制所有多酚的化学结构式。通过对这些化学结构式的总结、对比、分析,我们期望从中找到这些多酚的异同点。这将为阐明它们之间的生物合成关系,以及葡萄与蛇葡萄两大常见植物的亲缘关系,提供重要信息。
茋是一类以1,2-二苯乙烯为骨架的天然多酚物质。低聚茋指少量的茋类分子聚合而成的化合物。葡萄与蛇葡萄中茋及低聚茋主要有:白藜芦醇 [
图1. 葡萄与蛇葡萄中的茋及低聚茋的结构式(内图中的白藜芦醇为低聚茋的单体;结构式中明确地标注了每个手性碳的立体构型)
色原酮简称为色酮,是指含有苯并-γ-吡喃酮的骨架结构。色原酮往往与黄酮共存。研究表明:葡萄与蛇葡萄中色原酮与黄酮主要有19种,它们是:蛇葡萄素(二氢杨梅素) [
有趣的是,这19种化合物,实际上都是以色原酮为基础构建而成的。在3,5,7-三羟基色原酮的基础上,连接一个羟基-OH,就变成了黄酮。最简单是芹菜素;芹菜素增加一个羟基(3-OH),转变为山柰酚;芹菜素增加一个羟基(4'-OH),就变成了槲皮素;槲皮素再增加一个羟基-OH,转变为杨梅素。芹菜素如果苷化,则生成紫云英苷;山柰酚如果苷化、氢化则生成山奈酚-3-O-α-L-鼠李糖苷和二氢山柰酚;槲皮素如果苷化、氢化则生成槲皮素-3-O-α-L-鼠李糖苷、芦丁、(+)花旗松素;杨梅素苷化得到杨梅素-3-O-β-D-吡喃木糖苷、杨梅素-3-O-β-D-半乳糖苷、杨梅素-3-O-α-L-鼠李糖苷;杨梅素氢化得到二氢杨梅素。这种结构相关性提示,这些多酚可能是在植物中通过生成合成(如苷化、氢化等生化反应),实现结构转化。
图2. 葡萄与蛇葡萄中的色原酮与黄酮的结构式(结构式中明确地标注了每个手性碳的立体构型;花旗松素,也称二氢槲皮素,文献中多标为“(+)花旗松素”)
儿茶素的结构与黄酮相似,但不含羰基(C=O)。如果儿茶素聚合就可以形成花青素。花青素,又称花色素,是存在于植物中的水溶性天然色素。葡萄与蛇葡萄植物中的儿茶素与花青素主要有:儿茶素 [
图3. 葡萄与蛇葡萄中儿茶素与花青素的结构式(结构式中明确地标注了每个手性碳的立体构型)
酚酸是一类含有酚羟基的有机酸。它如果与醇发生酯化反应就得到酚酸酯,所以酚酸和酚酸酯往往共存于同一种或同一属的植物当中。葡萄与蛇葡萄中酚酸及其酯主要有没食子酸 [
图4. 葡萄与蛇葡萄中酚酸及其酯的结构式
目前已发现的葡萄与蛇葡萄植物中存在至少39种多酚成分。它们是:白藜芦醇 [
这39种多酚大致可归为茋及低聚茋、色原酮与黄酮、儿茶素与花青素、酚酸及其酯四大类。对其化学结构进行对比分析发现,两植物中的低聚茋可又由茋类聚合而成的;两植物中的黄酮则可在色原酮的基础上转化而成的;两植物中的儿茶素酯与花青素可以由儿茶素通过酯化与聚合得到。这种结构相关性,提供了一个重要信息,即:两植物的同类多酚之间,可能存在生物转化关系。另外,12个多酚(白藜芦醇、反式-ε-葡萄素、蛇葡萄素A、R-葡萄素、槲皮素、杨梅素、蛇葡萄素、山柰酚、芦丁、杨梅素-3-O-β-D-葡萄糖苷、儿茶素、表儿茶素)为葡萄与蛇葡萄所共有,这也提示葡萄与蛇葡萄存在一定的亲缘关系。
本文得到广东省中医药管理局科研项目资助(20201087)。
李鉴无,赵小军,李熙灿. 葡萄与蛇葡萄多酚的研究进展与结构相关性Research Advance and Structural Correlation of Phenolics from Grape and Ampelopsis[J]. 植物学研究, 2022, 11(02): 108-114. https://doi.org/10.12677/BR.2022.112015