改性蒙脱土对霉菌毒素的吸附研究进展

doi:10.16085/j.issn.1000-6613.2017.02.030

摘要/Abstract

摘要： 霉菌毒素广泛地存在于腐败变质的饲料和食物中，关系到人类的食品安全问题，如何降低霉菌毒素对饲料和食品等的威胁是目前正在研究的热点，其方法之一就是采用改性蒙脱土进行脱毒处理。本文以此为目的，首先介绍了常见霉菌毒素的种类和基本脱毒方法，然后针对蒙脱土脱毒问题，介绍了蒙脱土的结构、性能与脱毒原理，重点综述了用于脱毒的蒙脱土改性方法，主要包括季铵盐改性、金属离子改性、有机酸改性及其他改性方法等。改性过程不但可以改变蒙脱土的层间距，而且可改善其表面性能，同时交换后的阳离子，如金属离子可能通过与毒素分子之间形成强相互作用而提高改性蒙脱土的脱毒素能力；与此同时，改善的杀菌能力也有助于提高脱毒素效果。在未来的应用中，新的改性方法包括研发新的可降解改性剂及其对不同霉菌毒素的综合吸附会有更为深入的研究。

关键词: 霉菌毒素, 蒙脱土, 改性, 吸附作用, 吸附剂, 复合材料

Abstract: Mycotoxins secreted by mould are widely existed in musty feedstuff and food, and they have been a global threat to the health of human beings. How to detoxify the contaminated feedstuff and food has been a hot issue to date, and one of the most effective treating methods is adsorption with montmorillonite. This paper introduces conventional mycotoxins and common detoxification methods first, followed by the structure of montmorillonite and its mechanism to detoxify feedstuff, with the focus on the advances of modification techniques using quarternary ammonium salts, metal ions, organic acids and so on. Treatment can not only modify the interlayer distance of montmorillonite, but also improve its surface property, and the exchanged cations can form strong interaction with mycotoxins, which enhances the disinfecting effects accordingly. Finally, the perspective of modified montmorillonite is discussed. It maybe expected that new modification methods including new degradable modifier reagents and combined adsorption of different mycotoxins would be focused on in the future study.

Key words: mycotoxin, montmorillonite, modification, adsorption, adsorbent, composites

中图分类号:

S816

武玉珍, 张乾, 杨顺, 周迁, 许启富. 改性蒙脱土对霉菌毒素的吸附研究进展[J]. 化工进展, 2017, 36(02): 618-625.

WU Yuzhen, ZHANG Qian, YANG Shun, ZHOU Qian, XU Qifu. Advances in study of the adsorption of mycotoxins by modified montmorillonite[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 618-625.

参考文献

[1] 谢晓鹏,易卫,庄智明,等. 饲料中的霉菌毒素及其防制措施[J]. 中国畜牧兽医,2013,40(5):101-106. XIE X P,YI W,ZHUANG Z M,et al. Mycotoxins in feed and its prevention measures[J]. China Animal Husbandry & Veterinary Medicine,2013,40(5):101-106.
[2] 戎晓平,赵丽红,计成,等. 我国部分地区饲料原料及配合饲料玉米赤霉烯酮污染情况调研[J]. 中国畜牧杂志,2015,51(22):20-24. RONG X P,ZHAO L H,JI C,et al. Research of zearalenone contamination of feedstuffs and feeds[J]. Chinese Journal of Animal Science,2015,51(22):20-24.
[3] 周庆雨,朱道荣,单玉平. 霉菌毒素对畜禽的危害及其控制[J]. 中国家禽,2005,27(2):24-26. ZHOU Q Y,ZHU D R,SHAN Y P. The detrimental effects to livestock and their controls from mycotoxin[J]. China Pouhry,2005,27(2):24-26.
[4] CHAUHAN R,SINGH J,SACHDEV T,et al. Recent advances in mycotoxins detection[J]. Biosens Bioelectron,2016,81:532-45.
[5] WANG X,NIESSNER R,TANG D P,et al. Nanoparticle-based immunosensors and immunoassays for aflatoxins[J]. Anal Chim Acta,2016,912:10-23.
[6] DANICKE S,WINKLER J. Invited review:diagnosis of zearalenone (ZEN) exposure of farm animals and transfer of its residues into edible tissues (carry over)[J]. Food Chem Toxicol,2015,84:225-249.
[7] SUN C,JI J,WU S L,et al. Saturated aqueous ozone degradation of deoxynivalenol and its application in contaminated grains[J]. Food Control,2016,69:185-190.
[8] 迟俊,于安琳. 颗粒饲料霉变的原因和对策[J]. 安徽农业,1998(1):43. CHI J,YU A L. The causes of feedstuff moulding and its countermeasures[J]. Anhui Agriculture,1998(1):43.
[9] 戈娜,袁慧. 霉菌毒素免疫抑制作用的研究进展[J]. 中国畜牧兽医,2008,35(3):126-128. GE N,YUAN H. The development of research on immunosuppression of mycotoxin[J]. China Animal Husbandry & Veterinary Medicine,2008,35(3):126-128.
[10] 刘艳丽,杨斌,常志顺,等. 霉菌毒素脱毒的研究进展[J]. 中国畜牧兽医,2012,39(1):85-88. LIU Y L,YANG B,CHANG Z S,et al. Recent advanced research on the mycotoxin removing[J]. China Animal Husbandry & Veterinary Medicine,2012,39(1):85-88.
[11] ABBES S,OUANES Z,SALAH-ABBES J B,et al. Preventive role of aluminosilicate clay against induction of micronuclei and chromosome aberrations in bone-marrow cells of Balb/c mice treated with Zearalenone[J]. Mutation Research/Genetic Toxicology and Environmental Mutagenesis,2007,631(2):85-92.
[12] ZHOU H T. Mixture of palygorskite and montmorillonite (Paly-Mont) and its adsorptive application for mycotoxins[J]. Applied Clay Science,2016,131:140-143.
[13] 彭凯,吴薇,龙蕾,等. 饲料中霉菌毒素的危害及脱毒方法[J]. 饲料工业,2015,36(6):58-61. PENG K,WU W,LONG L,et al. Harm and detoxification methods of mycotoxins in feed[J]. Feed Industry,2015,36(6):58-61.
[14] ALLAMEH A,SAFAMEHR A,MIRHADI S A,et al. Evaluation of biochemical and production parameters of broiler chicks fed ammonia treated aflatoxin contaminated maize grains[J]. Animal Feed Science and Technology,2005,122(3/4):289-301.
[15] 房祥军,邹晓庭. 饲料霉菌毒素污染的危害及其防治[J]. 中国饲料,2006(11):34-37. FANG X J,ZOU X T. Harms of mycotoxin contamination and its prevention and elimination in feed[J]. China Feed,2006(11):34-37.
[16] ZHANG X,YI H,ZHAO Y L,et al. Study on the differences of Na- and Ca-montmorillonites in crystalline swelling regime through molecular dynamics simulation[J]. Advanced Powder Technology,2016,27(2):779-785.
[17] 李娜,马建中,鲍艳. 蒙脱土改性研究进展[J]. 化学研究,2009(1):98-103. LI N,MA J Z,BAO Y. Development on modification of montmorillonite[J]. Chemical Research,2009(1):98-103.
[18] ZHU J X,WANG T,ZHU R L,et al. Novel polymer/surfactant modified montmorillonite hybrids and the implications for the treatment of hydrophobic organic compounds in wastewaters[J]. Applied Clay Science,2011,51(3):317-322.
[19] 于志纲,贾朝霞. 蒙脱土改性的研究进展[J]. 精细石油化工进展,2005,6(8):5-8. YU Z G,JIA Z X. Research progress on montmorillonites modification[J]. Advances in Fine Petrochemicals,2005,6(8):5-8.
[20] 梁云,贾德民. 蒙脱土的改性研究进展[J]. 化工矿物与加工,2004,33(2):1-5. LIANG Y,JIA D M. Advance in montmorillonites modification[J]. Industrial Minerals & Processing,2004,33(2):1-5.
[21] SRINIVASAN K R,FOGLER H S. Use of inorgano-organo-clays in the removal of priority pollutants from industrial wastewaters:adsorption of benzo (a) pyrene and chlorophenols from aqueous solutions[J]. Clays and Clay Minerals,1990,38(3):287-293.
[22] 臧运波. 蒙脱土对重金属离子吸附的研究进展[J]. 安徽农业科学,2008,36(29):12884-12886. ZANG Y B. Research advance of the adsorption of heavy metal on montmorillonite[J]. Journal of Anhui Agricultural Sciences,2008,36(29):12884-12886.
[23] 程华丽,李瑾,王涵,等. 壳聚糖/蒙脱土插层复合物对活性红染料的吸附动力学及解吸性能[J]. 环境化学,2014,33(1):115-122. CHENG H L,LI J,WANG H,et al. Adsorption kinetics of chitosan/montmorillonite intercalation composites for Reactive Red dye and desorption properties[J]. Environmental Chemistry,2014,33(1):115-122.
[24] ELMORE S E,MITCHELL N,MAYS T,et al. Common African cooking processes do not affect the aflatoxin binding efficacy of refined calcium montmorillonite clay[J]. Food Control,2014,37:27-32.
[25] MAKI C R,MONTEIRO A P A,ELMORE S E,et al. Calcium montmorillonite clay in dairy feed reduces aflatoxin concentrations in milk without interfering with milk quality, composition or yield[J]. Animal Feed Science and Technology,2016,214:130-135.
[26] 周轩榕,卢滇楠,邵曼君,等. 表面接枝季铵盐型高分子材料抗菌过程的特性研究[J]. 高等学校化学学报,2003,24(6):1131-1135. ZHOU X R,LU D N,SHAO M J,et al. Characterization of the disinfection process using quaternary ammonium salts grafted cellulose fiber[J]. Chemical Journal of Chinese Universities,2003,24(6):1131-1135.
[27] LEMKE S L,GRANT P G,PHILLIPS T D. Adsorption of zearalenone by organophilic montmorillonite clay[J]. Journal of Agricultural and Food Chemistry,1998,46(9):3789-3796.
[28] 齐德生,刘凡,于炎湖,等. 蒙脱石及改性蒙脱石对黄曲霉毒素B1的吸附研究[J]. 畜牧兽医学报,2003,34(6):620-622. QI D S,LIU F,YU Y H,et al. Adsorption law of montmorillonite and organic montmorillonite for aflatoxin B1[J]. Acta Veterinaria Et Zootechnica Sinica,2003,34(6):620-622.
[29] FENG J L,SHAN M,DU H H,et al. In vitro adsorption of zearalenone by cetyltrimethyl ammonium bromide-modified montmorillonite nanocomposites[J]. Microporous and Mesoporous Materials,2008,113(1/2/3):99-105.
[30] 骆翼,陈峰. 季铵盐处理蒙脱石的结构及其对玉米赤霉烯酮的吸附[J]. 饲料工业,2014(s1):114-117. LUO J,CHEN F. The microstructure and zearalenone adsorption of montmorillonite modified by quaternary ammonium salts[J]. Feed Industry,2014(s1):114-117.
[31] LI Y J,ZENG L,ZHOU Y,et al. Preparation and characterization of montmorillonite intercalation compounds with quaternary ammonium surfactant:adsorption effect of zearalenone[J]. Journal of Nanomaterials,2014. http://dx.doi.org/10.1155/2014/167402.
[32] 秦嘉旭,张亚涛,陈义丰,等. 无机纳米抗菌剂及其载体[J]. 材料导报,2011,25(18):67-72. QIN J X,ZHANG Y T,CHEN Y F,et al. Inorganic nano-antibacterial agent and its carriers[J]. Materials Review,2011,25(18):67-72.
[33] 汤戈,王振家. 无机抗菌材料的发展和应用[J]. 材料科学与工程,2002,20(2):298-301. TANG G,WANG Z J. Development and application of inorganic antibacterial materials[J]. Materials Science &Engineering,2002,20(2):298-301.
[34] MALACHOVA K,PRAUS P,RYBKOVA Z,et al. Antibacterial and antifungal activities of silver, copper and zinc montmorillonites[J]. Applied Clay Science,2011,53(4):642-645.
[35] MAGDALENA TOMASEVIC-CANOVIC A D,MARKOVIC V,STOJSIC D. The effect of exchangeable cations in clinoptilolite and montmorillonite on the adsorption of aflatoxin B1[J]. Serb. Chem. Soc,2001,66(8):555-561.
[36] XU Z R,YE Y,XIA M S,et al. Nano-feed additive, its preparation and feedstuffs including this kind of additive:PCT/CN02/00538[P]. 2003-09-25.
[37] DAKOVIC A,MATIJASEVIC S,ROTTINGHAUS G E,et al. Aflatoxin B(1) adsorption by natural and copper modified montmorillonite[J]. Colloids Surf B Biointerfaces,2008,66(1):20-25.
[38] DAKOVIĆ A,KRAGOVIC M,ROTTINGHAUS G E,et al. Preparation and characterization of zinc-exchanged montmorillonite and its effectiveness as aflatoxin B1 adsorbent[J]. Materials Chemistry and Physics,2012,137(1):213-220.
[39] ZENG L,WANG S,PENG X Q,et al. Al-Fe PILC preparation, characterization and its potential adsorption capacity for aflatoxin B1[J]. Applied Clay Science,2013,83/84:231-237.
[40] XU M,CHOI Y S,KIM Y K,et al. Synthesis and characterization of exfoliated poly(styrene-co-methyl methacrylate)/clay nanocomposites via emulsion polymerization with AMPS[J]. Polymer,2003,44(20):6387-6395.
[41] AFLAKI J M,DADVAND K A,SHEYKHAN M. Experimental study of the removal of copper ions using hydrogels of xanthan, 2-acrylamido-2-methyl-1-propane sulfonic acid, montmorillonite:kinetic and equilibrium study[J]. Carbohydr. Polym.,2016,142:124-32.
[42] 姚佳佳,康福星,高彦征. 低分子量腐殖酸改性蒙脱土对黄曲霉素的吸附作用[J]. 环境科学,2012,33(3):958-964. YAO J J,KANG F X,GAO Y Z. Adsorption of aflatoxin on montmorillonite modified by low-molecular-weight humic acids[J]. Environmental Science,2012,33(3):958-964.
[43] WANNGAH W S,TEONG L C,HANAFIAH M. Adsorption of dyes and heavy metal ions by chitosan composites:a review[J]. Carbohydrate Polymers,2011,83(4):1446-1456.
[44] ANNADURAI G,LING L Y,LEE J F. Adsorption of reactive dye from an aqueous solution by chitosan:isotherm, kinetic and thermodynamic analysis[J]. J. Hazard Mater.,2008,152(1):337-346.
[45] CELIS R,ADELINO M A,HERMOSIN M C,et al. Montmorillonite-chitosan bionanocomposites as adsorbents of the herbicide clopyralid in aqueous solution and soil/water suspensions[J]. J. Hazard Mater.,2012,209/210:67-76.
[46] 刘佳洪. 改性蒙脱土脱除黄曲霉毒素B2的研究[D]. 天津:天津大学,2009. LIU J H. Study on removal of aflatoxins B2 by modified montmorillonite[D]. Tianjin:Tianjin University,2009.
[47] 孟娜,周宁琳,刘颖,等. 羧甲基壳聚糖-银/蒙脱土纳米抗菌中间体的制备及性能研究[J]. 功能材料,2007,38(6):958-960. MENG N,ZHOU N L,LIU Y,et al. Synthesis and properties of CMC-Ag/MMT antimicrobial nanocomposites[J]. Journal of Functional Materials,2007,38(6):958-960.
[48] KITTINAOVARAT S,KANSOMWAN P,JIRATUMNUKUL N. Chitosan/modified montmorillonite beads and adsorption Reactive Red 120[J]. Applied Clay Science,2010,48(1):87-91.
[49] JAYNES W F,ZARTMAN R E. Aflatoxin toxicity reduction in feed by enhanced binding to surface-modified clay additives[J]. Toxins,2011,3(6):551-565.
[50] 任荣,王爱娟,李克勋,等. 好氧污泥对季铵盐吸附性能的研究[J]. 水处理技术,2011,37(1):39-43. RENG R,WANG A J,LI K X,et al. Adsorption of quaternary ammonium compounds to aerobic activated sludge[J]. Technology of Water Treatment,2011,37(1):39-43.
[51] 吴乐,陶乃旺,江水旺. 季铵盐检测技术研究进展[J]. 涂料工业,2015,45(9):83-87. WU L,TAO N W,JAING S W. Progress in quaternary ammonium analysis technology[J]. Paint & Coatings Industry,2015,45(9):83-87.
[52] 刘少伟,阮赞林. 黑木耳"增肥"术——硫酸铜、硫酸镁的危害[J]. 质量与标准化,2015(9):37. LIU S W,RUAN Z L. The fattening method of black fungus-The dangers from copper sulfate and magnesium sulfate[J]. Quality and Starldardization,2015(9):37.