基于活性自由基聚合的槲皮素分子印迹聚合物的合成及在维药祖卡木颗粒活性成分分析中的应用

doi:10.7503/cjcu20150357

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (12): 2402.doi: 10.7503/cjcu20150357

基于活性自由基聚合的槲皮素分子印迹聚合物的合成及在维药祖卡木颗粒活性成分分析中的应用

买买提·吐尔逊, 古丽巴哈尔·达吾提, 热萨莱提·伊敏, 楚刚辉, 买合木提江·杰力, 木合塔尔·吐尔洪()

喀什大学化学与环境科学学院, 新疆特色药食用植物资源化学重点实验室, 喀什 844000

收稿日期:2015-05-04 出版日期:2015-12-10 发布日期:2015-11-17
作者简介:联系人简介: 木合塔尔·吐尔洪, 男, 教授, 主要从事环境及药物分析方面的研究. E-mail:maimat@163.com
基金资助:
新疆维吾尔自治区自然科学基金项目(批准号: 201318101-15)资助

Preparation of Quercetin Imprinted Polymer by Living Radical Polymerization and Its Application in the Composition Analysis of Zukamu Granules for Uighur Medicine^†

TURSON Mamat, DAWUT Gulbahar, EMIN Risalat, CHU Ganghui, JELIL Mahmutjan, TURHON Muhetar^*()

College of Chemistry and Environmental Science,Key Laboratory of Xinjiang Native Medicinal and Edible Plant Resources Chemistry,Kashgar University, Kashgar 844000, China

Received:2015-05-04 Online:2015-12-10 Published:2015-11-17
Contact: TURHON Muhetar E-mail:maimat@163.com
Supported by:
† Supported by the Natural Science Foundation of Xinjiang Uygur Autonomous Region of China(No.201318101-15)

摘要/Abstract

摘要：

以二苄基三硫代碳酸酯(DBTTC)为可逆加成-断裂链转移剂(RAFT试剂), 槲皮素(Quercetin)为印迹化合物, 分别以甲基丙烯酸(MAA)、丙烯酰胺(AM)、丙烯酸(AA)、 4-乙烯基吡啶(4-VP)和2-乙烯基吡啶(2-VP)作为功能单体, 利用可逆加成-断裂链转移自由基聚合法制备了槲皮素分子印迹聚合物. 实验考察了不同的制备条件, 利用氮吸附测试及扫描电子显微镜对聚合物的结构进行了测定, 采用色谱法对印迹聚合物的识别能力及分离效率进行了评价. 研究了聚合条件-聚合物结构-分离效率的关系, 探讨了利用活性自由基合成分子印迹聚合物的方法及特点; 并将合成的分子印迹聚合物用作固定相, 对维药祖卡木颗粒中的槲皮素进行了分离富集. 研究结果表明, 通过活性自由基聚合法合成的分子印迹聚合物具有更好的形态结构, 对目标分子具有很好的吸附效率.

关键词: 活性自由基聚合, 分子印迹聚合物, 槲皮素, 维药祖卡木颗粒, 高效液相色谱法

Abstract:

Quercetin imprinted polymer was synthesized by a reversible addition-fragmentation chain transfer(RAFT) polymerization method, combining molecular imprinting with living radical polymerization techniques, usingthe dibenzyltrithiocarbonate(DBTTC) as reversible RAFT reagent, quercetin as the imprinted compound, and the methacrylic acid(MAA), acrylamide(AM), acrylic acid(AA), 4-vinylpyridine(4-VP) and 2-vinylpyridine(2-VP) as functional monomers, ethyleneglycoldim ethacrylate(EDMA) as cross-linker and 2,2-azob isisobuty ronitrile(AIBN) as initiator.The preparation of molecular imprinted polymers(MIPs) were conducted under different experimental conditions, and the structures of the MIPs were characterized by nitrogen adsorption and scanning electron microscopy, respectively. The identify ability and separation efficiency of MIPs for quercetin were evaluated by high performance liquid chromatography(HPLC). The relationship among the polymerization conditions, structure of polymer and separation efficiency was studied, and the synthetic method and characteristics of MIPs prepared by living radical polymerization were also explored. The quercetin was separated and enriched in Zukamu Granules for Uighur medicine, using synthesized MIPs as stationary phase. The results showed that the MIPs synthesized by living radical polymerization method exhibited a better morphology, and a good adsorption efficiency for the target molecule.

Key words: Living radical polymerization, Molecular imprinted polymer, Quercetin, Zukamu granules for Uighur medicine, High performance liquid chromatography

中图分类号:

O657

TrendMD:

买买提·吐尔逊, 古丽巴哈尔·达吾提, 热萨莱提·伊敏, 楚刚辉, 买合木提江·杰力, 木合塔尔·吐尔洪. 基于活性自由基聚合的槲皮素分子印迹聚合物的合成及在维药祖卡木颗粒活性成分分析中的应用. 高等学校化学学报, 2015, 36(12): 2402.

TURSON Mamat, DAWUT Gulbahar, EMIN Risalat, CHU Ganghui, JELIL Mahmutjan, TURHON Muhetar. Preparation of Quercetin Imprinted Polymer by Living Radical Polymerization and Its Application in the Composition Analysis of Zukamu Granules for Uighur Medicine^†. Chem. J. Chinese Universities, 2015, 36(12): 2402.

图/表 11

Scheme 1 Synthesis of DBTTC

Table 1 Lengths of strong hydrogen bonds in the complex of quercetin and MAA polymer

Bond	Bond length/nm	Bond type	Bond	Bond length/nm	Bond type
O12—H28	0.112855	Covalent bond	O51—H27	0.141021	Hydrogen bond
O13—H28	0.133938	Hydrogen bond	O21—H33	0.111729	Covalent bond
O13—H46	0.137195	Hydrogen bond	O63—H33	0.137623	Hydrogen bond
O39—H25	0.155918	Hydrogen bond	O64—H70	0.110604	Covalent bond
O11—H27	0.109424	Covalent bond	O22—H70	0.137756	Hydrogen bond

Fig.1 Optimized geometries for the most stable complexes between quercetin and MAA at molar ratio of 1:3

Fig.2 Polymerization of quercetin molecularly imprinted polymer

Fig.3 Adsorption kinetics curves of MIPs synthesized by different functional monomers for quercetin a. MMA; b. AM; c. AA; d. 4-VP.

Fig.4 SEM images of MIPs P1(A), P2(B), P3(C) and P4(D)

Fig.5 Pore size distribution of MIPs P1—P6

Table 2 Synthetic conditions and structure characterizations of the MIPs

MIP	n(monomer)/n(AIBN)/n(DBTTC)	Specific surface area/(m²·g^-1)	Characteristic dimension of the globules/μm
P1	200:1:0	17.2	2—4
P2	200:1:1	20.6	2—4
P3	200:1:2	39.4	2—3
P4	200:1:3	35.1	2—3.5
P5	200:2:2	20.9	1.5—3.5
P6	200:2:0	14.9	1.5—4
P7	300:1:2	16.3	1—4
P8	150:1:2	9.23	0.2—0.5

Fig.6 Adsorption kinetics curves of MIPs and NIPs for quercetin and kaempferol a. MIP-quercetin; b. MIP-kaempferol;c. NMIP-quercetin; d. NIP-kaempferol.

Fig.7 Effects of adsorption for different synthetic conditions of MIPs for kaempferol and quercetin

Fig.8 Chromatograms of selectivity of molecularly imprinted solid extraction (A) Zukamu solution; (B) solution after extraction; (C) eluate. Peak a: quercetin; peak b: kaempferol.

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基于活性自由基聚合的槲皮素分子印迹聚合物的合成及在维药祖卡木颗粒活性成分分析中的应用

Preparation of Quercetin Imprinted Polymer by Living Radical Polymerization and Its Application in the Composition Analysis of Zukamu Granules for Uighur Medicine^†

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