壳寡糖-水解麦醇溶肽共聚物的制备和表征

引用本文: 江文, 周桢, 石业新, 陶仁友, 张桂罗, 周小华, 王丹. 壳寡糖-水解麦醇溶肽共聚物的制备和表征[J]. 应用化学, 2016, 33(3): 284-292. doi: 10.11944/j.issn.1000-0518.2016.03.150226 shu

Citation: JIANG Wen, ZHOU Zhen, SHI Yexin, TAO Renyou, ZHANG Guiluo, ZHOU Xiaohua, WANG Dan. Preparation and Characterization of Chitosan Oligo-Saccharide-Hydrolyzed Gliadin Copolymer[J]. Chinese Journal of Applied Chemistry, 2016, 33(3): 284-292. doi: 10.11944/j.issn.1000-0518.2016.03.150226 shu

壳寡糖-水解麦醇溶肽共聚物的制备和表征

江文 ^a, ,
周桢 ^{a,
,} ,
石业新 ^a, ,
陶仁友 ^a, ,
张桂罗 ^b, ,
周小华 ^{a,
,} ,
王丹 ^a,

a.
a. 重庆大学重庆 400044;
b.
b. 重庆利特环保工程有限公司重庆 401121

通讯作者: 周小华,教授;Tel/Fax:023-65111179;E-mail:zhou65306590@cqu.edu.cn;研究方向:生物化工及药物化学;周桢,讲师;Tel/Fax:023-65111179;E-mail:dominizhou@126.com;研究方向:药物分析; 周小华,教授;Tel/Fax:023-65111179;E-mail:zhou65306590@cqu.edu.cn;研究方向:生物化工及药物化学;周桢,讲师;Tel/Fax:023-65111179;E-mail:dominizhou@126.com;研究方向:药物分析

基金项目:
国家自然科学基金（21106191，21206175)

材料化学工程国家重点实验室（KL14-11)

中央高校基本业务费（CQDXWL-2013-019）基金资助项目

摘要: 以初步纯化的微生物转谷氨酰胺酶（MTGase）催化合成壳寡糖-水解麦醇溶肽共聚物，研究最佳合成条件并对共聚物进行了表征。结果表明，合成共聚物的最佳条件是：壳寡糖/水解麦醇溶肽质量比为1∶40，在pH值6.00～6.50、50℃下搅拌反应50 min，共聚物的生成率达到60%～70%。红外光谱分析显示，与壳寡糖相比，由于引入的吸电子基团产生诱导效应，共聚物酰胺CO基的伸展振动峰向高波数位移动且吸收强度加强。由DTA分析可知，共聚物在60.91℃处失水，387.55℃处熔融，665.25℃处开始彻底分解，与壳寡糖和麦醇溶肽的差异明显。XRD分析可知，共聚物的结晶度显著降低，晶胞数据不同于壳寡糖，表明其不易结晶。HPLC分析表明，共聚物主要由两个组分构成，占共聚物总量的80.6%，其相对分子质量分别为66069和27285。共聚物不溶于水及多种有机溶剂，微溶于1%NaOH，溶解度为0.184 mg/100 g。熔程为162～163℃。

关键词:

English

Preparation and Characterization of Chitosan Oligo-Saccharide-Hydrolyzed Gliadin Copolymer

JIANG Wen ^a, ,
ZHOU Zhen ^{a,
,} ,
SHI Yexin ^a, ,
TAO Renyou ^a, ,
ZHANG Guiluo ^b, ,
ZHOU Xiaohua ^{a,
,} ,
WANG Dan ^a,

a.
a. Chongqing University, Chongqing 400044, China;
b.
b. Chongqing Neat Environment Engineering Co., LTD, Chongqing 401121, China

Corresponding author: 周小华,教授;Tel/Fax:023-65111179;E-mail:zhou65306590@cqu.edu.cn;研究方向:生物化工及药物化学;周桢,讲师;Tel/Fax:023-65111179;E-mail:dominizhou@126.com;研究方向:药物分析; 周小华,教授;Tel/Fax:023-65111179;E-mail:zhou65306590@cqu.edu.cn;研究方向:生物化工及药物化学;周桢,讲师;Tel/Fax:023-65111179;E-mail:dominizhou@126.com;研究方向:药物分析

Received Date: 03 July 2015
Fund Project:
国家自然科学基金（21106191，21206175)

材料化学工程国家重点实验室（KL14-11)

中央高校基本业务费（CQDXWL-2013-019）基金资助项目

Abstract: The optimal conditions for the synthesis of chitosan oligosaccharide-hydrolyzed gliadin copolymer by roughly-purified microbial transglutaminase(MTGase) catalysis were investigated, and the structures of obtained copolymer were characterized. These optimal conditions are estimated as the substrates mass ratio of chitosan chitosan oligosaccharide and hydrolyzed gliadin is 1:40 under pH 6.00~6.50, and 50 min stirring at 50℃. The grafting rate at these conditions can reach up to 60%~70%. Infrared spectrum analysis of the copolymer shows that, compared with chitosan oligosaccharide, the introduction of electron withdrawing group to chitosan oligosaccharide-hydrolyzed gliadin copolymer has inductive effects on the amide C=O, and causes the vibration peak shift to higher wave number with enhanced absorption intensity. DTA curve indicates that the chitosan oligosaccharide-hydrolyzed gliadin copolymer begins to lose the associated water at 60.91℃, melt at 387.55℃, and completely degrade at 665.25℃. This is significantly different to that of chitosan oligosaccharide and gliadin. XRD analysis shows that the crystallinity of grafted copolymers is greatly reduced, the cell data is different from those of chitosan oligosaccharide. HPLC analysis shows that the copolymer has two main components, accounting together for 80.6% of the total mass. The relative molecular masses of the two main components are 66069 and 27285, respectively. The copolymer does not dissolve in water and many organic solvents, but is slightly soluble in 1% NaOH, with a solubility at 0.184 mg/100 g. The melting range of the copolymer is 162~163℃.

Key words:

1. [1] WANG Yupeng,WANG Chunhua,QU Rongjun,et al. Progress in the Study of Antibacterial Fiber[J]. Ludong Univ J(Nat Sci Edn),2009,25(3):256-262(in Chinese).王玉鹏,王春华,曲荣君,等. 抗菌纤维的研究进展[J]. 鲁东大学学报(自然科学版),2009,25(3):256-262.[1] WANG Yupeng,WANG Chunhua,QU Rongjun,et al. Progress in the Study of Antibacterial Fiber[J]. Ludong Univ J(Nat Sci Edn),2009,25(3):256-262(in Chinese).王玉鹏,王春华,曲荣君,等. 抗菌纤维的研究进展[J]. 鲁东大学学报(自然科学版),2009,25(3):256-262.
2. [2] Yeo S Y,Lee H J,Jeong S H. Preparation of Nanocomposite Fibers for Permanent Antibacterial Effect[J]. J Mater Sci,2003,38(10):2143-2147.[2] Yeo S Y,Lee H J,Jeong S H. Preparation of Nanocomposite Fibers for Permanent Antibacterial Effect[J]. J Mater Sci,2003,38(10):2143-2147.
3. [3] Ye W J,Man F L,John X,et al. Novel Core-Shell Particles with Poly(n-butyl acrylate) Cores and Chitosan Shells as an Antibacterial Coating for Textiles[J]. Polymer,2005,46(23):10538-10543.[3] Ye W J,Man F L,John X,et al. Novel Core-Shell Particles with Poly(n-butyl acrylate) Cores and Chitosan Shells as an Antibacterial Coating for Textiles[J]. Polymer,2005,46(23):10538-10543.
4. [4] FENG Decai,LIU Xiaolin,YANG Qi,et al. Progress in Antibacterial Agents and Antibacterial Fibers[J]. China Synth Fiber Ind,2005,28(4):40-42(in Chinese).冯德才,刘小林,杨其,等. 抗菌剂与抗菌纤维的研究进展[J]. 合成纤维工业,2005,28(4):40-42.[4] FENG Decai,LIU Xiaolin,YANG Qi,et al. Progress in Antibacterial Agents and Antibacterial Fibers[J]. China Synth Fiber Ind,2005,28(4):40-42(in Chinese).冯德才,刘小林,杨其,等. 抗菌剂与抗菌纤维的研究进展[J]. 合成纤维工业,2005,28(4):40-42.
5. [5] Yao F,Fu G D,Zhao J P,et al. Antibacterial Effect of Surface-functionalized Polypropylene Hollow Ber Membrane from Surface-initiated Atom Transfer Radical Polymerization[J]. J Membr Sci,2008,319(2):149-157.[5] Yao F,Fu G D,Zhao J P,et al. Antibacterial Effect of Surface-functionalized Polypropylene Hollow Ber Membrane from Surface-initiated Atom Transfer Radical Polymerization[J]. J Membr Sci,2008,319(2):149-157.
6. [6] Fillat A,Gallardo O,Vidal T,et al. Enzymatic Grafting of Natural Phenols to Fax Fbres:Development of Antimicrobial Properties[J]. Carbohydr Polym,2012,87(1):146-152.[6] Fillat A,Gallardo O,Vidal T,et al. Enzymatic Grafting of Natural Phenols to Fax Fbres:Development of Antimicrobial Properties[J]. Carbohydr Polym,2012,87(1):146-152.
7. [7] ZHOU Xiaohua,LUO Hui,ZHOU Zhen. Synthesis of Chitosan-Gelatin Copolymer by MTGase and Main Properities[J]. Chinese J Appl Chem,2008,25(3):334-339 (in Chinese).周小华,骆辉,周桢. 壳聚糖-明胶共聚物的酶促合成及主要性质[J]. 应用化学,2008,25(3):334-339.[7] ZHOU Xiaohua,LUO Hui,ZHOU Zhen. Synthesis of Chitosan-Gelatin Copolymer by MTGase and Main Properities[J]. Chinese J Appl Chem,2008,25(3):334-339 (in Chinese).周小华,骆辉,周桢. 壳聚糖-明胶共聚物的酶促合成及主要性质[J]. 应用化学,2008,25(3):334-339.
8. [8] Hirano S H,Noishiki Y H,Kinugawa J K. Chitin and Chitosan for Use as a Novel Biomedical Material[J]. Polym Mater Sci Eng,1985,53(2):649-653.[8] Hirano S H,Noishiki Y H,Kinugawa J K. Chitin and Chitosan for Use as a Novel Biomedical Material[J]. Polym Mater Sci Eng,1985,53(2):649-653.
9. [9] Jun H O,Baowu W,Perris D. Field,et al. Characteristics of Edible Films Made from Dairy Proteins and Zein Hydrolysate Cross-linked with Transglutaminase[J]. Int J Food Sci Technol,2004,39(3):287-294.[9] Jun H O,Baowu W,Perris D. Field,et al. Characteristics of Edible Films Made from Dairy Proteins and Zein Hydrolysate Cross-linked with Transglutaminase[J]. Int J Food Sci Technol,2004,39(3):287-294.
10. [10] RAN Lan,ZHANG Rong,WEN Xia,et al. Study On Determination of Glucosamine Hydrochloride Tablets by Colorimetry[J]. West China J Pharm Sci,200l,16(3):217-218(in Chinese).冉兰,张榕,文霞,等. 比色法测定盐酸氨基葡萄糖片的含量[J]. 华西药学杂志,2001,16(3):217-218.[10] RAN Lan,ZHANG Rong,WEN Xia,et al. Study On Determination of Glucosamine Hydrochloride Tablets by Colorimetry[J]. West China J Pharm Sci,200l,16(3):217-218(in Chinese).冉兰,张榕,文霞,等. 比色法测定盐酸氨基葡萄糖片的含量[J]. 华西药学杂志,2001,16(3):217-218.
11. [11] LU Jian. Protein Purification Technology and Its Application[M]. Beijing:Chemical Industry Press,2005:29-52(in Chinese).陆健. 蛋白质纯化技术及应用[M]. 北京:化学工业出版社,2005:29-52.[11] LU Jian. Protein Purification Technology and Its Application[M]. Beijing:Chemical Industry Press,2005:29-52(in Chinese).陆健. 蛋白质纯化技术及应用[M]. 北京:化学工业出版社,2005:29-52.
12. [12] ZHOU Feng. Molecular Dynamics Simulation of Polymer Melts Flow in Nanochannel[D] Dalian:Dalian University of Technology,2014( in Chinese).周峰. 纳米通道中高聚物熔体流动分子动力学模拟[D]. 大连:大连理工大学,2014.[12] ZHOU Feng. Molecular Dynamics Simulation of Polymer Melts Flow in Nanochannel[D] Dalian:Dalian University of Technology,2014( in Chinese).周峰. 纳米通道中高聚物熔体流动分子动力学模拟[D]. 大连:大连理工大学,2014.
13. [13] Ana L C G,Silvana P D G F. Action of Microbial Transglutaminase(MTGase) in the Modification of Food Proteins:A Review[J]. Food Chem,2015,171(2):315-322.[13] Ana L C G,Silvana P D G F. Action of Microbial Transglutaminase(MTGase) in the Modification of Food Proteins:A Review[J]. Food Chem,2015,171(2):315-322.
14. [14] FANG Yun,XIA Yongmei.Aliphatic Amino Acid Surfactants[J]. Daily Chem Ind,1988,(6):16-22(in Chinese).方云,夏永梅. 脂肪族氨基酸型表面活性剂[J]. 日用化学工业,1988,(6):16-22.[14] FANG Yun,XIA Yongmei.Aliphatic Amino Acid Surfactants[J]. Daily Chem Ind,1988,(6):16-22(in Chinese).方云,夏永梅. 脂肪族氨基酸型表面活性剂[J]. 日用化学工业,1988,(6):16-22.
15. [15] MA Yongqiang,YUE Wenjing,ZHANG Na,et al. Determination of Transglutaminase Activity Group[J]. Food Mach,2011,27(4):7-9(in Chinese).马永强,岳文静,张娜,等. 转谷氨酰胺酶活性基团研究[J]. 食品与机械,2011,27(4):7-9.[15] MA Yongqiang,YUE Wenjing,ZHANG Na,et al. Determination of Transglutaminase Activity Group[J]. Food Mach,2011,27(4):7-9(in Chinese).马永强,岳文静,张娜,等. 转谷氨酰胺酶活性基团研究[J]. 食品与机械,2011,27(4):7-9.
16. [16] LI Yuhong. Determination of Formula Weight and Molecular Weight Distribution of High Polymer PVA by GFC[J]. Nat Gas Chem Ind,2003,28:57-59(in Chinese).李宇虹. 凝胶过滤色谱测定高分子量聚乙烯醇分子量和分子量分布[J]. 天然气化工,2003,28:57-59.[16] LI Yuhong. Determination of Formula Weight and Molecular Weight Distribution of High Polymer PVA by GFC[J]. Nat Gas Chem Ind,2003,28:57-59(in Chinese).李宇虹. 凝胶过滤色谱测定高分子量聚乙烯醇分子量和分子量分布[J]. 天然气化工,2003,28:57-59.

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壳寡糖-水解麦醇溶肽共聚物的制备和表征

English

Preparation and Characterization of Chitosan Oligo-Saccharide-Hydrolyzed Gliadin Copolymer

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

壳寡糖-水解麦醇溶肽共聚物的制备和表征

English

Preparation and Characterization of Chitosan Oligo-Saccharide-Hydrolyzed Gliadin Copolymer

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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