模板分子中作用基团的数目及位置对印迹聚合物印迹效应的影响

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (6): 1126.

模板分子中作用基团的数目及位置对印迹聚合物印迹效应的影响

张铁莉¹, 刘锋², 李克安²

1. 唐山师范学院化学系, 唐山 063000;
2. 北京大学化学与分子工程学院, 生物有机与分子工程教育部重点实验室, 北京 100871

收稿日期:2009-11-30 出版日期:2010-06-10 发布日期:2010-06-10
通讯作者: 张铁莉, 女, 博士, 教授, 主要从事分子印迹聚合物和分子发光研究. E-mail: 3306160@tstc.edu.cn
基金资助:
唐山市重点实验室基金(批准号: 04360701B-6)和唐山师范学院博士基金(批准号: 04D02)资助.

Influence of the Number and Relative Position of the Interacting Groups in Template Molecule on Molecular Imprinting Effect

ZHANG Tie-Li^1*, LIU Feng², LI Ke-An²

1. Department of Chemistry, Tangshan Teachers College, Tangshan 063000, China;
2. Key Laboratory of Bioorganic and Molecular Engineering, Ministry of Education, College of Chemistry & Molecular Engineering, Peking University, Beijing 100871, China

Received:2009-11-30 Online:2010-06-10 Published:2010-06-10
Contact: ZHANG Tie-Li. E-mail: 3306160@tstc.edu.cn
Supported by:
唐山市重点实验室基金(批准号: 04360701B-6)和唐山师范学院博士基金(批准号: 04D02)资助.

摘要/Abstract

摘要：

为了研究模板分子中作用基团的数目和位置对印迹聚合物印迹效应的影响, 分别以含有羟基数目和位置不同的羟基苯甲酸化合物3,4,5-三羟基苯甲酸(3,4,5-THBA), 3,4-二羟基苯甲酸(3,4-DHBA), 2,4-二羟基苯甲酸(2,4-DHBA)和3-羟基苯甲酸(3-HBA)为模板分子, 以丙烯酰胺为功能单体, 乙二醇二甲基丙烯酸酯为交联剂和乙腈(MeCN)为致孔剂, 采用非共价本体聚合方法制备了对应的印迹聚合物, 用色谱法评价了其分子识别性能. 结果表明, 制备的印迹聚合物对相应的模板分子均具有印迹效应, 在流动相H₂O/MeCN(体积比1/99)中, 各印迹聚合物对相应的模板分子3,4,5-THBA, 3,4-DHBA, 2,4-DHBA和3-HBA的印迹因子分别为5.51, 5.55, 2.60和2.03. 通过与同样条件下制备的龙胆酸(GA)、水杨酸(SA)和对-羟基苯甲酸(4-HBA)印迹聚合物对其模板分子印迹效应的比较发现, 模板分子中作用基团数目越多, 印迹效率越高; 模板分子中作用基团—COOH和—OH的相对位置对印迹效率影响很大, 当—COOH和—OH在苯环上处于对位时的印迹效率, 高于其处于间位的印迹效率; 当—COOH和—OH在苯环上处于邻位时, 由于形成分子内氢键会降低其印迹效率. 实验还发现, 3,4-DHBA的印迹聚合物可以实现其结构类似物3,4,5-THBA和2,4-DHBA的基线分离, 为生物活性组分3,4,5-THBA的分离和测定提供了依据.

关键词: 分子印迹聚合物; 分子识别; 印迹效应; 羟基苯甲酸; 高效液相色谱

Abstract:

In order to explore the influence of the interacting group′s number and relative position of the template molecule on molecular imprinting effect, in the present study four molecularly imprinted polymers(MIPs) were prepared using a series of hydroxybenzoic acids with different numbers of —OH groups and their positio-nal isomers such as 3,4,5-trihydroxybenzoic acid(3,4,5-THBA), 3,4-dihydroxybenzoic acid(3,4-DHBA), 2,4-dihydroxybenzoic acid(2,4-DHBA) and 3-hydroxybenzoic acid(3-HBA) as model templates, respectively, acrylamide as functional monomer, ethyleneglycol dimethacrylate as cross-linker and acetonitrile(MeCN) as porogen by bulk non-covalent imprinting technique. The molecular recognition performances were characte-rized by high-performance liquid chromatography. The results showed that all of the imprinted polymers exhibited molecular imprinting effects for the corresponding templates and the imprinting factors were 5.51, 5.55, 2.60 and 2.03 for 3,4,5-THBA, 3,4-DHBA, 2,4-DHBA and 3-HBA, respectively, in the mobile phase of H₂O/MeCN(volume ratio, 1:99). Furthermore, the comparison of molecular recognition ability was made among them and gentisic acid-, salicylic acid-, 4-hydroxybenzoic acid-imprinted polymers, which were previously prepared under the same conditions as the above four hydroxybenzoic acids-imprinted polymers except for the template molecules. By comparative study on all of the above mentioned hydroxybenzoic acid-imprinted polymers, the following conclusions are drawn: (1) the template with multi-functional groups facilitates the preparation of MIP with high imprinting efficiency; (2) it was found that the positions of —COOH relative to —OH on the benzene ring have marked influence on the imprinting effects of templates. Specifically, the imprinting efficiency is higher for the template with —COOH and —OH at para-position than that at meta-position, whereas the imprinting effect will decrease if —COOH and —OH are at ortho-position owing to their forming intramolecular hydrogen bond. In addition, a baseline separation of the mixture of 3,4,5-THBA and 2,4-DHBA was obtained on 3,4-DHBA-imprinted polymer, which is a close analogue of 3,4,5-THBA. This provides the potentiality for the selective separation and detection of bioactive 3,4,5-THBA.

Key words: Molecularly imprinted polymer; Molecular recognition; Imprinting effect; Hydroxybenzoic acid; High-performance liquid chromatography

TrendMD:

张铁莉, 刘锋, 李克安. 模板分子中作用基团的数目及位置对印迹聚合物印迹效应的影响. 高等学校化学学报, 2010, 31(6): 1126.

ZHANG Tie-Li*, LIU Feng, LI Ke-An. Influence of the Number and Relative Position of the Interacting Groups in Template Molecule on Molecular Imprinting Effect. Chem. J. Chinese Universities, 2010, 31(6): 1126.

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