β-环糊精及其衍生物对黄曲霉毒素B1荧光增强机理研究

食品科学 ›› 2012, Vol. 33 ›› Issue (15): 28-33.

β-环糊精及其衍生物对黄曲霉毒素B1荧光增强机理研究

张敏1,2，郭婷1，刘馨1，肖洁1，张宇昊1,3，马良1,3,*

1.西南大学食品科学学院 2.四川省资阳产品质量监督检验所 3.重庆市特色食品工程技术研究中心

收稿日期:2011-07-04 修回日期:2012-06-20 出版日期:2012-08-15 发布日期:2012-09-07
通讯作者: 张敏 E-mail:zhang.min.min.min@163.com
基金资助:
国家“863”计划;中央高校基本科研业务费专项资金;西南大学研究生科技创新基金项目

Mechanisms Underlying Fluorescence Enhancement of Aflatoxin B1 by β-Cyclodextrin and Its Derivatives

Received:2011-07-04 Revised:2012-06-20 Online:2012-08-15 Published:2012-09-07

摘要/Abstract

摘要： 利用光谱法、Benesi-Hildebrand法、热力学方法研究β-环糊精(β-CD)及其衍生物对黄曲霉毒素B1(AFB1)荧光增强机理，探讨溶剂中甲醇体积比、M-β-CD浓度、时间、干扰离子等因素对荧光增强作用的影响。根据Benesi-Hildebrand法确定7种β-环糊精及其衍生物在低浓度时与AFB1包络比为1:1，高浓度时包络比为2:1。采用热力学方法计算了包合常数最大的M-β-CD与AFB1包合过程的熵变(ΔS)、焓变(ΔH)及自由能变化(ΔG)均为负值，说明包合反应是放热反应且能自发进行，焓变是形成超分子包络物的主要驱动力。紫外吸收光谱及KI淬灭实验表明AFB1进入M-β-CD空腔从而使荧光得到保护。得出结论：7种β-环糊精及其衍生物与AFB1通过形成超分子包络物可大幅增强AFB1荧光发射强度，提高AFB1荧光分析法的检测灵敏度。

关键词: β-环糊精, AFB1, 荧光增强, 超分子包络物

Abstract: The mechanisms underlying fluorescence enhancement of aflatoxin B1 (AFB1) by β-cyclodextrin (β-CD) and its derivatives were explored using spectroscopy, Benesi-Hidebrand analysis and thermodynamics. Moreover the effects of methanol volume percentage, M-β-CD concentration, reaction time and interfering ions on fluorescence enhancement were analyzed. β-CD and its six derivatives showed an inclusion ratio to AFB1 of 1:1 at low concentrations and 2:1 at high concentrations. The thermodynamic parameters entropy change (ΔS), enthalpy change (ΔH) and free energy change (ΔG) for maximum inclusion constant between M-β-CD and AFB1 were negative, suggesting that the inclusion reaction is exothermic and can occur spontaneously. Enthalpy change was the dominant force during the formation of inclusion complexes. UV absorption spectra and KI quenching experiments showed that AFB1 could enter M-β-CD cavity to protect fluorescence. Therefore, β-cyclodextrin and its derivatives can allow considerable enhancement in the fluorescence emission intensity of AFB1 by the formation of supramolecular inclusion complexes, resulting in increased sensitivity of AFB1 fluorescence analysis.

Key words: β-cyclodextrin, aflatoxin B1, fluorescence enhancement, supramolecular inclusion

中图分类号:

TS207.3

张敏1,2，郭婷1，刘馨1，肖洁1，张宇昊1,3，马良1,3,*. β-环糊精及其衍生物对黄曲霉毒素B1荧光增强机理研究[J]. 食品科学, 2012, 33(15): 28-33.

参考文献

[1]付成平, 欧阳华学, 刘瑜.柱前衍生化高效液相色谱法测定中草药提取物中的黄曲霉毒素B1[J].西南农业学报,2009,22(2):522-524
[2]FERREIRA I M P L V O, MENDES E, OLIVEIRAl M B P P.Quantification of Aflatoxins B1, B2, G1, and G2 in Pepper by HPLC/Fluorescence[J].Journal of Liquid Chromatography & Related Technologies,2004,27:325-334
[3]ABBAS H K , SHIER W T, HORN B W, et al.Cultural Methods for Aflatoxin Detection[J].Journal of Toxicology: Toxin Reviews,2004,　23(2-3):-
[4] 马良. 黄曲霉毒素B1高灵敏度检测技术研究[D]. 北京: 中国农业科学院研究生院, 2007
[5]李培武, 马良, 杨金娥, 等.粮油产品黄曲霉毒素B1检测技术研究进展[J].中国油料作物学报,2005,27(2):77-81
[6]童林荟. 环糊精化学——基础与应用[M]. 北京: 科学出版社, 2001: 145
[7]文先红, 郭明.光谱法研究环糊精与艾地苯醌的超分子作用[J].光谱实验室,2009,26(1):1-4
[8]MORGAN P, Bao H A, CHRISTOPHER H E.Cyclodextrins as phototoxicity inhibitors in drug formulations:studies on model systems involving naproxen and β-cyclodextrin[J].Journal of Photochemistry and Photobiology A: Chemistry,2001,140(1):67-74
[9]段秀芬, 张煜, 查建蓬.β-环糊精对普鲁卡因青霉素荧光增强作用的研究[J].药物研究与分析,2008,30(1):106-
[10]王秋亚.β-环糊精对葛根素的荧光增敏作用及其应用[J].西南民族大学学报﹒自然科学版,2008,34(5):985-989
[11]董峰光, 姜子涛, 李荣.环糊精及其衍生物包结赤藓红的荧光光谱研究[J].食品科技,2009,34(6):67-74
[12]JAIMEZ J, FENTE C A, VAZQUEZ BI, et al.Application of the assay of aflatoxins by liquid chromatography with fluorescence detection in food analysis[J].Journal of Chromatography,2000,882:1-10
[13]ABDEL-SHAFI A A, AL-SHIHRY S S.Fluorescence enhancement of 1-napthol-5-sulfonate by forming inclusion complex with β-cyclodextrin in aqueous solution[J].Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy,2009,72(3):533-537
[14] ZHANG Yongxia. Measurement of dissolved oxygen based on the phosphorescence of lumophore and auantumdots[D]. America: The University of Alabama, 2006
[15]Wagner Brian D, McManus Gregory J.Enhancement of the fluorescence and stability of o-phthalaldehyde-derived isoindoles of amino acids using hydroxypropyl-β-cyclodextrin[J].Analytical Biochemistry,2003,317:233-239
[16]ZHU Xiashi, SUN Jing, HU Yanyan.Determination of protein by hydroxypropyl-β-cyclodextrin sensitized fluorescence quenching method with erythrosine sodium as a fluorescence probe[J].Analytica Chimica Acta,2007,596(2):298-302
[17]FRANCO C M, FENTE F A, VAZQUEZ B I, et al.Interaction between cyclodextrins and aflatoxins Q, M, and P Fluorescence and chromatographic studies[J].Journal of Chromatography A,1998,815:21-29
[18]CAVALIERE C, FOGLIA P, PASTORINI E, et al.Liquid chromatography/ tandem mass spectrometric confirmatory method for determining aflatoxin M1 in cow milk Comparison between electrospray and atmospheric pressure photoionization sources[J].Journal of Chromatography A,2006,1101:69-78
[19]刘雪芬, 李培武, 张文.环糊精对花生黄曲霉毒素B1荧光增强作用与应用研究[J].中国油料作物学报,2010,32(4):546-550
[20]COLY A, AARON J J.Fluorimetric analysis of pesticides: Methods, recent developments and applications[J].Analytica Chimica Acta,1992,360:129-
[21]戴良香, 万书波, 张志萌, 等.不同类型花生品种主要矿质元素含量分布及相关性分析[J].营养学报,2009,31(6):606-608