分子印迹固相萃取和电喷雾质谱法联用测定茶叶中四种儿茶素

doi:10.13305/j.cnki.jts.2009.3.009

茶叶科学 ›› 2009, Vol. 29 ›› Issue (3): 231-235.doi: 10.13305/j.cnki.jts.2009.3.009

分子印迹固相萃取和电喷雾质谱法联用测定茶叶中四种儿茶素

干宁¹, 李榕生¹, 陈亚东^1,2, 徐伟明¹, 曹玉廷¹

1. 宁波大学材料科学与化学工程学院,新型功能材料及其制备科学国家重点实验室,浙江宁波 315211;
2. 宁波职业技术学院华丰学院,浙江宁波 315200

收稿日期:2008-10-07 修回日期:2009-03-31 出版日期:2009-06-15 发布日期:2019-09-06
作者简介:干宁(1974— ),男,浙江平湖人,博士,副教授,研究方向为分析化学。E-mail: ganning@nbu.edu.cn
基金资助:
浙江省自然科学基金(Y24080023, Y4080017 & 2008F70043),宁波市自然科学基金(No 2008A610043, 2008C50012 & 2008C50014)

Determination of Four Tea Catechins Content with Molecular Imprinting -SPE Extraction and Electrospray Mass Spectrometry

GAN Ning¹, LI Rong-sheng¹, CHEN Ya-dong^1,2, XU Wei-Ming¹, CAO Yu-ting¹

1. The State Key Laboratory base of Novel Functional Materials and Preparation science, The Faculty of Materials science & Chemical Engineering, Ninbo University, Ningbo 315211, China;;
2. Huafeng Institute of Ningbo Career College, Ningbo 315200, China

Received:2008-10-07 Revised:2009-03-31 Online:2009-06-15 Published:2019-09-06

摘要/Abstract

摘要： 为了对茶叶样品中微量儿茶素进行快速准确分析,利用分子印迹固相萃取（MIPs-SPE）与电喷雾质谱（EIMS）联用技术进行了茶叶中四种儿茶素—表儿茶素（EC）、表没食子儿茶素（EGC）、表儿茶素没食子酸酯（ECG）、表没食子儿茶素没食子酸酯（EGCG）的分离测定。首先以表儿茶素（EC）为模板分子,采用紫外聚合方法合成分子印迹聚合物（EC-MIPs）,功能单体为甲基丙烯酸(MAA),交联剂为乙烯二醇二甲基丙烯酸酯(EDMA),引发剂为偶氮二异丁腈(AIBN)。利用EC-MIPs作为固定相制备EC-MIPs-SPE柱,对茶叶样品进行分离萃取后采用EIMS对洗脱液中儿茶素单体进行检测,分别与常规C₁₈和非分子印迹聚合物（NIP）固相萃取方法进行比较。结果表明EC-MIPs-SPE法对儿茶素类单体有特异性识别能力,对茶中主要干扰物质咖啡因、茶碱的结合能力远小于儿茶素分子。最佳萃取条件为：水相上样,用50%（v/v）甲醇/水溶液淋洗除去非特异性结合干扰物,1%（v/v）醋酸的甲醇洗脱特异性结合的四种儿茶素单体。对真实茶叶样品测试发现：经过EC-MIPs-SPE法预富集,可以去除94.2%的咖啡因和全部茶碱干扰,同时可得四个主要儿茶素信号,相对强度分别为：EC（12.1%）,EGC（8.2%）,ECG（35.4%）,EGCG（45.7%）。本法可特异性地识别和分离儿茶素单体,有效消除咖啡因和茶碱干扰,可用于茶叶中微量儿茶素分离鉴定。

关键词: 固相萃取, 分子印迹技术, 儿茶素, 茶叶, 电喷雾质谱

Abstract: A rapid method using molecular imprinted polymers (MIPs) as solid phase extraction (SPE) sorbent in pretreatment and electrospray mass spectrometry (EIMS) were investigated to separate and determine trace amount of four main catechins, such as epicatechin (EC), epigallocatechin (EGC), epicatechin gallate (ECG), and epigallocatechin gallate (EGEG) respectively in tea samples. MIPs for EC (EC-MIPs) were prepared using methacrylic acid (MAA) as a monomer, ethylene glycol dimethacrylate (EDMA) as a cross linker, and azo-bis-isobutyronitrile (AIBN) as an initiator by UV radical polymerization method; and EC-MIPs were used as SPE sorbents (EC-MIPs-SPE) for selectively trapping and preconcentrating four catechins from eluate, and were then analysed by EIMS. The results showed EC-MIPs-SPE could selectively recognize catechins. Its binding capability and selectivity for catechins were better than that of caffeine and theophylline. The optimal extraction protocol was to load samples in the aqueous phase (v/v), to wash with 50% methanol and to elute with methanol containing 1% acetatic acid. Under above conditions, the interference of caffeine was eliminated to 94.2%, and of theophylline, 100%. The relative intensity was 12.1%, 8.2%, 35.4%, and 45.7% for EC, EGC, ECG, and EGCG respectively.

Key words: solid phased extraction, molecular imprinted polymers, catechins, tea, electrospray mass spectrometry

中图分类号:

TS272
O657.8

干宁, 李榕生, 陈亚东, 徐伟明, 曹玉廷. 分子印迹固相萃取和电喷雾质谱法联用测定茶叶中四种儿茶素[J]. 茶叶科学, 2009, 29(3): 231-235. doi: 10.13305/j.cnki.jts.2009.3.009.

GAN Ning, LI Rong-sheng, CHEN Ya-dong, XU Wei-Ming, CAO Yu-ting. Determination of Four Tea Catechins Content with Molecular Imprinting -SPE Extraction and Electrospray Mass Spectrometry[J]. Journal of Tea Science, 2009, 29(3): 231-235. doi: 10.13305/j.cnki.jts.2009.3.009.

参考文献

[1] Fernandez P L, Martin M J, Gonzalez A G, et al. HPLC determination of catechins and caffeine in tea Differentiation of green, black and instant teas[J]. Analyst, 2000, 125: 421~425.
[2] 林金科, 陈荣冰, 陈常颂, 等. 高酯型儿茶素含量的茶树资源筛选研究[J]. 茶叶科学, 2005, 25(1): 30~36
[3] Andreas F, Susanne K, Engelhardt U H.Review Chromatography of tea constituents[J]. J of Chromatography, 1992, 624: 293~315.
[4] Dalluge J J, Nelson B C, Thomas J B, et al. Selection ofcolumn and gradient elution system for the separation of catechins ingreen tea using high performance liquid chromatography[J]. J of Chromatograph A, 1998, 793: 265~274.
[5] Mitsuaki Sano, Michiko Tabata, Masazumi Suzuki, et al. Simultaneous determinationof twelve tea catechins by high performance liquid chromatography with electrochemical detection[J]. Analyst, 2001, 126: 816~820.
[6] Schmitz H H, Keen C L.Stability of the Flavanols Epicatechin and Catechin and Related Dimeric Procyanidins Derived from Cocoa[J]. J Agric Food Chem, 2002, 50: 1700~1705.
[7] 吕海鹏, 谷记平, 林智, 等. 普洱茶的化学成分及生物活性研究进展[J]. 茶叶科学, 2007, 27(1): 8~18.
[8] Khokhar S, Magnusdottir S G M. Total Phenol, Catechin, and Caffeine Contents of Teas Commonly Consumed in the United Kingdom[J]. J Agric Food Chem, 2002, 50: 565~570.
[9] Matteo B, Piero C, Marco P, et al. Fast Determination of Catechins and Xanthines in Tea Beverages by Micellar Electrokinetic Chromatography[J]. J Agric Food Chem, 2003, 51: 1141~1147.
[10] 李礼, 胡树国, 何锡文, 等. 应用分子印迹-固相萃取法提取中药活性成分非瑟酮[J]. 高等学校化学学报, 2006, 27(4): 608~611.
[11] Ramstrom, O, Kristina S,John H, et al. Food Analyses Using Molecularly Imprinted Polymers[J]. J Agric Food Chem, 2001, 49(5): 2106~2112.
[12] Takaomi K, Yasuhiro M, Puchalapalli S.Molecular imprinting of caffeine and its recognition assay by quartz-crystal microbalance[J]. Anal Chim Acta, 2001, 435: 141~149.
[13] Mateus N, Silva A M S, Celestino S-B, et al. Identification of Anthocyanin-Flavanol Pigments in Red Wines by NMR and Mass Spectrometry[J]. J Agric Food Chem, 2002, 50: 2110~2116.

[1]	晏朵, 余鹏辉, 龚雨顺. 萎凋过程中环境胁迫对茶叶品质影响研究进展[J]. 茶叶科学, 2025, 45(1): 1-14.
[2]	马雪晴, 吴华伟, 曹春霞, 郑娇莉. 茶园根际解磷菌的筛选及其对茶叶产量、品质及土壤性质的影响[J]. 茶叶科学, 2025, 45(1): 110-120.
[3]	罗璐璐, 赵悦汐, 王彦博, 幸怡, 齐洋, 马宏炜, 程林峰, 张芳琳. 表没食子儿茶素没食子酸酯抗汉滩病毒效果研究[J]. 茶叶科学, 2025, 45(1): 145-156.
[4]	杨楠, 李转, 刘玫辰, 马骏杰, 石云桃, 魏湘凝, 林阳顺, 毛宇源, 高水练. 钾营养对茶树EGCG生物合成的调控作用研究[J]. 茶叶科学, 2024, 44(6): 887-900.
[5]	赵建诚, 倪惠菁, 王波, 蔡春菊, 杨振亚. 毛竹立竹密度对林下茶树生理生长和茶叶品质的影响[J]. 茶叶科学, 2024, 44(6): 928-940.
[6]	许文琪. 微波消解-电感耦合等离子体质谱（ICP-MS）法准确测定茶叶中总硒含量[J]. 茶叶科学, 2024, 44(6): 1014-1022.
[7]	徐晴晴, 聂晴, 刘助生, 郭青, 刘仲华, 蔡淑娴. 康普茶细菌纤维素的形成途径及其在废弃茶叶资源高效利用中的应用[J]. 茶叶科学, 2024, 44(5): 707-717.
[8]	侯智炜, 吕永铭, 马宽, 张汇源, 顾哲, 张然, 李乐, 金俞谷, 苏祝成, 陈红平. 不同茶树品种的径山茶挥发性成分差异研究[J]. 茶叶科学, 2024, 44(5): 747-762.
[9]	丁树洽, 谢昕雅, 刘助生, 廖贤军, 刘仲华, 蔡淑娴. 茶叶成分EGCG与L-theanine联合应用的神经保护作用研究[J]. 茶叶科学, 2024, 44(5): 779-792.
[10]	姚蕾珺, 陈燕秋, 林浩, 汪璐瑶, 石培育, 张阳阳, 黄婷, 宋娟, 王义, 戴琴, 刘川. 一体化QuEChERS净化-超高效液相色谱-串联质谱法测定茶叶中27种吡咯里西啶类生物碱[J]. 茶叶科学, 2024, 44(5): 831-842.
[11]	李文燕, 张琳, 陈利燕, 张颖彬, 周苏娟, 洪一苇, 梁思辰, 孙洪峰, 陈红平. 我国茶叶产品质量标准中理化指标差异性分析[J]. 茶叶科学, 2024, 44(5): 843-852.
[12]	张怡, 胡林英, 伊晓云, 陈富桥, 姜爱芹. 新式茶饮消费对传统茶消费意愿的反哺效应分析[J]. 茶叶科学, 2024, 44(5): 853-868.
[13]	陈佳欣, 张锦佳, 左会灵, 焦宇航, 石安华. 表没食子儿茶素没食子酸酯预防并改善非酒精性脂肪性肝病的作用机制及研究进展[J]. 茶叶科学, 2024, 44(4): 543-553.
[14]	甘芳瑗, 刘振平, 傅丙生, 龙道崎, 庞钶靖, 姜容. 气相色谱-离子迁移谱技术在茶叶领域应用的研究进展[J]. 茶叶科学, 2024, 44(4): 565-574.
[15]	杜茜雅, 刘馨秋, 卢勇. 长江流域茶叶产地历史变迁及其影响因素[J]. 茶叶科学, 2024, 44(4): 694-706.

分子印迹固相萃取和电喷雾质谱法联用测定茶叶中四种儿茶素

Determination of Four Tea Catechins Content with Molecular Imprinting -SPE Extraction and Electrospray Mass Spectrometry

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

本文评价

推荐阅读 0