摘要
儿茶素具有较强的抗氧化活性和较低的毒副作用。儿茶素分子中含有多个羟基,使得在亲水溶液中溶解性较好,但在油脂类体系中的溶解性、稳定性较差,无法发挥其优良抗氧化活性,限制了其在医药、食品等领域的应用。当前研究较多的儿茶素全酯化改性在显著提高儿茶素衍生物油溶性的同时会显著降低其固有的抗氧化活性。本研究以丁酸酐为酯化剂对儿茶素分子中的B环和C环进行定位酯化改性,合成了儿茶素-3-丁酯和儿茶素-3′,4′-二丁酯等2种部分羟基酯化的产物,采用液相色谱-质谱联用(LC-MS)和核磁共振(NMR)等技术确定改性产物的分子结构,并研究其相关性能。结果显示,制备的儿茶素-3-丁酯的纯度高达99%、产率为95%,儿茶素-3′,4′-二丁酯的纯度为97%、产率为42.7%。水分配系数的计算及大豆油中的溶解性分析结果表明,酯化改性有效提升了儿茶素的油溶性。通过β-胡萝卜素漂白实验以及ABTS、DPPH自由基清除实验对比分析发现,2种改性产物均保持较高的抗氧化活性,且在β-胡萝卜素漂白实验中展现出相当的抗氧化性能。其中儿茶素-3′,4′-二丁酯在油脂中的抗氧化活性与丁基羟基茴香醚(BHA)、二叔丁基羟基甲酚(BHT)、叔丁基对苯二酚(TBHQ)和生育酚(VE)等4种常用的油脂抗氧化剂性能相当,而儿茶素-3-丁酯的抗氧化活性仅次于叔丁基对苯二酚(TBHQ)。制备的2种儿茶素定位酯化改性产物达到了在提高油溶性的同时保留大部分抗氧化活性的目的。
Catechins have strong antioxidant activity and low toxic side effects.Several phenolic hydroxyl groups are present in catechin molecules,so they are highly soluble in aqueous solutions.However,their poor solubility and stability in lipid systems hinder their antioxidant performance,thus limiting their application in medicine,food,and other fields.To address this limitation,the B and C rings in catechin molecules were modified through targeted esterification,with butyric anhydride used as the esterifying agent.Two partially esterified products,namely catechin-3-butyl ester and catechin-3′,4′-dibutyl ester,were synthesized through this process.The molecular structure of these products were determined by liquid chromatography-mass spectrometry(LC-MS)and nuclear magnetic resonance(NMR)and their related properties were analyzed.The results showed that the purity of catechin-3-butyl ester reached 99%with a yield of 95%,while a purity of 97%and a yield of 42.7%were achieved for catechin-3′,4′-dibutyl ester.The calculation of the partition coefficient and the solubility analysis in soybean oil indicated that esterification modification effectively enhanced the oil solubility of catechins.Comparative analysis were conducted throughβ-carotene bleaching experiments and ABTS,DPPH radical scavenging assays,which revealed that both modified products maintained high antioxidant activity,and demonstrated considerable antioxidant performance in theβ-carotene bleaching experiment.The antioxidant ability of catechin-3′,4′-dibutyl ester in lipid systems was found to be comparable to that of butylhydroxyanisole(BHA),butylated hydroxytoluene(BHT),and tocopherol(VE),while catechin-3-butyl ester exhibited antioxidant activity second only to tert-butylhydroquinone(TBHQ).The findings highlighted that the directional esterification approach successfully enhanced the oil solubility of catechins while retaining most of their antioxidant activity.
作者
张亚丹
何方圆
刘业贵
曾毅
郑德勇
Zhang Yadan;He Fangyuan;Liu Yegui;Zeng Yi;Zheng Deyong(College of Materials Engineering,Fujian Agriculture and Forestry University,Fuzhou 350002;National Forestry and Grassland Administration Key Laboratory of Plant Fiber Functional Materials,Fuzhou 350002)
出处
《中国粮油学报》
北大核心
2025年第9期152-160,共9页
Journal of the Chinese Cereals and Oils Association
基金
中央财政林业科技推广示范项目(闽[2019]TG17号)
福建省“2011协同创新中心”中国乌龙茶产业协同创新中心专项(闽教科[2015]75号)。
关键词
儿茶素
丁酸酐
定位酯化
油溶性
抗氧化剂
catechin
butyric anhydride
directed esterification
oil solubility
antioxidants
作者简介
第一作者:张亚丹,女,1997年出生,硕士,轻化工程,z15093609809@163.com;通信作者:郑德勇,男,1966年出生,副教授,林产化工和树木提取物,ffczdy@163.com。
