L-精氨酸改性淀粉的制备及其抗菌薄膜的性能
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摘要
以玉米淀粉(St)、丙烯酸甲酯(MA)与L-精氨酸(L-Arg)为原料,采用酯化-氨解两步法,制备了具有抑菌性能的精氨酸改性淀粉(St MA-Arg)。阐述了反应机理,用拉曼光谱、~(13)CNMR、XRD与GPC表征了产物的结构,通过单因素实验优化了反应条件。以St MA-Arg为原料制备了抗菌膜,考察了L-Arg固载率(IR)对薄膜的亲疏水性能、力学性能及抑菌性能的影响。结果表明,St MA-Arg薄膜的力学性能较天然淀粉膜显著改善,同时疏水性增强。固载率(IR)为7.48%的St MA-Arg及其薄膜对大肠杆菌(E.coli)显示出明显的抑菌活性,且膜的抑菌较小,属接触式抑菌。土壤失重实验结果显示,St MA-Arg(IR=7.48%)薄膜40d后的失重率为27.90%,远小于天然淀粉膜(40 d失重率为72.15%)。有望成为一种潜在的环境修复材料的基体。
A series of L-arginine( L-Arg) modified starch( St MA-Arg) with antibacterial activity were prepared by esterification and ammonolysis with corn starch( St),methyl acrylate( MA) and L-Arg as raw materials. The reaction mechanism was discussed. The products were characterized by Raman spectroscopy( RAM),~(13)C nuclear magnetic resonance(~(13)CNMR) spectroscopy,X-ray diffraction( XRD) and gel permeation chromatography( GPC),and the reaction conditions were optimized by single factor experiments. Subsequently,antibacterial films were prepared using St MA-Arg as raw material. The effects of L-Arg immobilization ratio( IR) on the hydrophobic properties,mechanical properties and antibacterial activity of films were investigated. The results showed that the mechanical properties of St MA-Arg film were significantly improved compared with native starch film. Meanwhile,the hydrophobicity of film was enhanced. When IR was 7. 48%,St MA-Arg and its film showed obvious antibacterial activity against Escherichia coli,and the bacteriostatic circle of film was small,which belonged to contact bacteriostasis. The results of weight loss experiments indicated that the weight loss rate of St MA-Arg( IR = 7.48%) film was 27. 90% after 40 days,which was much lower than that of native starch film( 72. 15%). The prepared St MA-Arg will be a potential substrate for environmental restoration material.
A series of L-arginine( L-Arg) modified starch( St MA-Arg) with antibacterial activity were prepared by esterification and ammonolysis with corn starch( St),methyl acrylate( MA) and L-Arg as raw materials. The reaction mechanism was discussed. The products were characterized by Raman spectroscopy( RAM),~(13)C nuclear magnetic resonance(~(13)CNMR) spectroscopy,X-ray diffraction( XRD) and gel permeation chromatography( GPC),and the reaction conditions were optimized by single factor experiments. Subsequently,antibacterial films were prepared using St MA-Arg as raw material. The effects of L-Arg immobilization ratio( IR) on the hydrophobic properties,mechanical properties and antibacterial activity of films were investigated. The results showed that the mechanical properties of St MA-Arg film were significantly improved compared with native starch film. Meanwhile,the hydrophobicity of film was enhanced. When IR was 7. 48%,St MA-Arg and its film showed obvious antibacterial activity against Escherichia coli,and the bacteriostatic circle of film was small,which belonged to contact bacteriostasis. The results of weight loss experiments indicated that the weight loss rate of St MA-Arg( IR = 7.48%) film was 27. 90% after 40 days,which was much lower than that of native starch film( 72. 15%). The prepared St MA-Arg will be a potential substrate for environmental restoration material.
引文
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[35]Zhang Hao,Wang Rui,Wang Jiankun,et al.Microwave-assisted synthesis and characterization of acetylated corn starch[J].Starch-Strke,2014,66(5/6):515-523.
[36]Bengtsson M,Koch K,Gatenholm P.Surface octanoylation of high-amylose potato starch films[J].Carbohyd Polym,2003,54(1):1-11.
[37]Shen Shiqi(沈仕奇),Zhu Zhifeng祝志峰).Effect of amphoteric grafting modification on the property of starch film[J].New Chemical Materials(化工新型材料),2015,(9):172-174.
[38]Li M,Zhu Z,Pan X.Effects of starch acryloylation on the grafting efficiency,adhesion,and film properties of acryloylated starch-gpoly(acrylic acid)for warp sizing[J].Starch-Strke,2011,63(11):683-691.
[39]Rabea E I,Badawy M E,Steurbaut W,et al.Fungicidal activity of new N-alkyl and N-aryl chitosan derivatives[J].Commun Agric.Appl Biol Sci,2004,69(4):789-792.
[40]Hong K N,Na Y P,Lee S H,et al.Antibacterial activity of chitosans and chitosan oligomers with different molecular weights[J].Int J Food Microbiol,2002,74(1/2):65-72.
[2]Hekmatzadeh A A,Karimi-Jashni A,Talebbeydokhti N,et al.Adsorption kinetics of nitrate ions on ion exchange resin[J].Desalination,2013,326(5):125-134.
[3]Zhang Lei(张雷),Li Danjun(李丹君),Li Jing(李晶),Ou Yang Xinping(欧阳新平).Fabrication of starch-based carbon and adsorption capacity for heavy metal ions[J].Fine Chemicals(精细化工),2010,27(5):476-479.
[4]Zhao P,Jiang J,Zhang F W,et al.Adsorption separation of Ni(Ⅱ)ions by dialdehyde O-phenylenediamine starch from aqueous solution[J].Carbohyd Polym,2010,81(4):751-757.
[5]Yi Xianjun(易先君),Ju Benzhi(具本植),Zhang Shufen(张淑芬).Synthesis and adsorption performance of aminothiazole schiffbase of water soluble oxidized starch with high carbonyl content[J].Fine Chemicals(精细化工),2013,30(7):766-770,780.
[6]Taheri S,Baier G,Majewski P,et al.Synthesis and antibacterial properties of a hybrid of silver-potato starch nanocapsules by miniemulsion/polyaddition polymerization[J].J Mater Chem,2014,2(13):1838-1845.
[7]Liu F,Qin B,He L,et al.Novel starch/chitosan blending membrane:antibacterial,permeable and mechanical properties[J].Carbohyd Polym,2009,78(1):146-150.
[8]Nouri L,Mohammadi N A.Antibacterial,mechanical,and barrier properties of sago starch film incorporated with betel leaves extract[J].Int.J.Biol.Macromol,2014,66(5):254-259.
[9]Priya B,Gupta V K,Pathania D,et al.Synthesis,characterization and antibacterial activity of biodegradable starch/PVA composite films reinforced with cellulosic fibre[J].Carbohyd Polym,2014,109(6):171-179.
[10]Mehdizadeh T,Tajik H,Rohani S M R,et al.Antibacterial,antioxidant and optical properties of edible starch-chitosan composite film containing thymus kotschyanus essential oil[C].RES VET,2012:167-173.
[11]Mariab V,Silviak F,Carmena C,et al.Antimicrobial ativity and physical properties of chitosan-tapioca starch based edible films and coatings[J].Food Res Int,2009,42(7):762-769.
[12]Dai Xiaomin(戴小敏),Zuo Xiujin(左秀锦),Liu Xiudong(刘袖洞),et al.Preparation and degradability of starch based membrane[J].Polymer Materials Science and Engineering(高分子材料科学与工程),2013,29(3):158-160,164.
[13]Wang Liqiang(王利强),Jia Chao(贾超),Lu Lixin(卢立新),et al.Study on preparation and properties of potato starch-based antimicrobial films containing thymolor clove oil[J].Food and Fermentation Industries(食品与发酵工业),2013,39(1):86-91.
[14]Maizura M,Fazilah A,Norziah M H.Short communication antibacterial activity of modified sago starch-alginate based edible film incorporated with lemongrass(cymbopogon citratus)oil.[J].Food Res Int,2008,15(2):233-236.
[15]Zhang Yi(张毅),Zhang Zhuanling(张转玲),Zhang Hao(张昊),et al.Preparation and properties of amino acid-modified Chitosan-based material for metal ion adsorption[J].Chinese Journal of Materials Research(材料研究学报),2016,30(11):825-833.
[16]Tang H,Zhang P,Kieft T L,et al.Antibacterial action of a novel functionalized chitosan-arginine against gram-negative bacteria[J].Acta Biomater,2010,6(7):2562-2571.
[17]Liu W G,Zhang J R,Cao Z Q,et al.A chitosan-arginine conjugate as a novel anticoagulation biomaterial[J].J Mater SciMater Med,2004,15(11):1199-1203.
[18]Liu Zijie(刘子杰),Liang Xingtang(梁兴唐),Zhong Shuming(钟书明),et al.Synthesis and characterization of starch-graftacrylic acid hydrogels under microwave irradiation for adsorption of Pb2+[J].Fine Chemicals(精细化工),2016,33(10):1135-1140,1182.
[19]Tan Yiqiu(谭义秋),Huang Zuqiang(黄祖强).Adsorption behavior and mechanism of cassava carboxymethyl starch on Cu(Ⅱ)[J].Fine Chemicals(精细化工),2012,29(1):57-61,90.
[20]Lu S,Chen C Y,Li C Y.Gel-chromatography fractionation and thermal characterization of rice starch affected by hydrothermal treatment[J].Cereal Chemistry,1996,73(1):5-11.
[21]Li Dan(李丹).Study on the preparation and the charactristics of antimicrobial film of starch acetate[D].Guangzhou:South China University of Technology(华南理工大学),2010.
[22]Teng Liju(滕丽菊).Preparation and property of chitosan complex film[D].Guangzhou:Jinan University(暨南大学),2008.
[23]Cochran J C.Advanced organic chemistry:reactions,mechanisms,and structure(March,Jerry)[M].Mc Graw-Hill,1968.
[24]Wade L G.Organic chemistry:Pearson new international edition[M].New York:Pearson Education Inc.,2011.
[25]Wang Xiaojuan(王晓娟),Ju Benzhi(具本植),Zhang Shufen(张淑芬).Synthesis of dialdehyde starch-aniline schiff-base[J].Fine Chemicals(精细化工),2012,29(6):601-605,610.
[26]Katritzky A R,Drewniak M,Lue P.Chem Inform abstract:the chemistry of benzotriazole.part 9.A conceptually new approach to the synthesis of secondary amides and thioamides[J].Cheminform,1989,20(22):5854-5856.
[27]Wang Yuanhao(汪源浩),Ju Benzhi(具本植),Zhang Shufen(张淑芬).Preparation and viscosity properties of hexylated carboxymethyl starch[J].Fine Chemicals(精细化工),2012,29(6):606-610.
[28]Fechner P M,Wartewig S,Kleinebudde P,et al.Studies of the retrogradation process for various starch gels using raman spectroscopy[J].Carbohydr Res,2005,340(16):2563-2568.
[29]Kizil R,Irudayaraj J,Seetharaman K.Characterization of irradiated starches by using FT-Raman and FTIR Spectroscopy[J].J Agric Food Chem,2002,50(14):3912-3918.
[30]Wang L,Shen J,Men Y,et al.Corn starch based graft copolymers prepared via ATRP at the molecular level[J].Polymer Chemistry,2015,6(18):3480-3488.
[31]Wang S,Wang Q,Fan X,et al.Synthesis and characterization of starch-poly(methyl acrylate)graft copolymers using horseradish peroxidase[J].Carbohydrate Polymers,2016,136(1):1010-1016.
[32]Liu W G,Zhang J R,Cao Z Q,et al.A chitosan-arginine conjugate as a novel anticoagulation biomaterial[J].Journal of Materials Science:Materials in Medicine,2004,15(11):1199-1203
[33]Liang Yong(梁勇),Zhang Benshan(张本山),Yang Liansheng(杨连生),et al.Study of degradation characteristics of potato starch in noncrystalline granular state by microorganisms[J].Fine Chemicals(精细化工),2003,20(6):361-363,380.
[34]Liu Qiaoyu(刘巧瑜),Zhao Siming(赵思明),Xiong Shanbai(熊善柏),et al.Preparation of cross-linking sweet potato starch dodecenylsuccinate[J].Journal of the Chinese Cereals and Oil Association(中国粮油报),2003,(1):28-30,45.
[35]Zhang Hao,Wang Rui,Wang Jiankun,et al.Microwave-assisted synthesis and characterization of acetylated corn starch[J].Starch-Strke,2014,66(5/6):515-523.
[36]Bengtsson M,Koch K,Gatenholm P.Surface octanoylation of high-amylose potato starch films[J].Carbohyd Polym,2003,54(1):1-11.
[37]Shen Shiqi(沈仕奇),Zhu Zhifeng祝志峰).Effect of amphoteric grafting modification on the property of starch film[J].New Chemical Materials(化工新型材料),2015,(9):172-174.
[38]Li M,Zhu Z,Pan X.Effects of starch acryloylation on the grafting efficiency,adhesion,and film properties of acryloylated starch-gpoly(acrylic acid)for warp sizing[J].Starch-Strke,2011,63(11):683-691.
[39]Rabea E I,Badawy M E,Steurbaut W,et al.Fungicidal activity of new N-alkyl and N-aryl chitosan derivatives[J].Commun Agric.Appl Biol Sci,2004,69(4):789-792.
[40]Hong K N,Na Y P,Lee S H,et al.Antibacterial activity of chitosans and chitosan oligomers with different molecular weights[J].Int J Food Microbiol,2002,74(1/2):65-72.