6-羧基壳寡糖螯合钙制备工艺与络合性能研究  

Preparation Technology and Complexing Properties of 6-Carboxy Chitooligosaccharides Chelate Calcium(CCOS-Ca(Ⅱ))

作　　者：胡雪芳[1,2] 田志清 梁亮[1,2] 张志民 王士奎[1,2] HU Xuefang;TIAN Zhiqing;LIANG Liang;ZHANG Zhimin;WANG Shikui(Chinese Academy of Agricultural Engineering, Beijing 100125, China;Key Laboratory of Agro-products Postharvest Handling, Ministry of Agriculture, Beijing 100121 , China)

机构地区：[1]农业部规划设计研究院,北京100125 [2]农业部农产品产后处理重点实验室,北京100121

出　　处：《农业机械学报》2018年第4期381-388,共8页Transactions of the Chinese Society for Agricultural Machinery

基　　金："十二五"国家科技支撑计划项目(2013BAB01B00)

摘　　要：以壳寡糖(COS)为试验材料,采用TEMPO氧化法将壳寡糖C6位上的羟甲基直接氧化成为羧基,制备6-羧基壳寡糖(CCOS)。以Ca Cl2作为钙源,通过探讨体系pH值、反应温度、反应时间、CCOS与Ca Cl2质量比对CCOS-Ca(Ⅱ)得率的影响,采用三因素五水平中心旋转组合设计优化了制备工艺。并对产物进行傅里叶变换红外光谱扫描及元素分析。使用Design-Expert软件对响应面试验数据进行回归分析。所得CCOS-Ca(Ⅱ)制备最佳工艺参数为:反应pH值为8.3,反应时间60 min,反应温度50℃,CCOS与Ca Cl2质量比为34。在此优化工艺条件下,验证试验螯合率为88.86%。通过红外光谱及元素分析,证明了钙螯合物的形成,CCOS-Ca(Ⅱ)配合物的结构初步认为CCOS与Ca2+摩尔比为2∶1。CCOS分子除了含有—OH、—NH2外,还含有—COOH,能够对钙进行有效螯合,体系pH值、反应温度、配体质量比对螯合结果影响显著,所得CCOS-Ca(Ⅱ)络合物不仅能发挥壳寡糖本身独特的生物活性,而且有可能起到协同效应,增强各自的生物活性。The chelating ability of chitosan derivative 6-carboxy-chitooligosaccharide （CCOS） to calcium ions was studied, and the preparation technology of 6-carboxyl chitosan chelated calcium （CCOS- Ca （Ⅱ）） was established, to provide new ideas for the development of chitooligosaceharide-based metal complexes and high-performance calcium supplement. Chitooligosaccharides （COS） was used as experimental materials to prepare CCOS by oxidation of hydroxymethyl groups at the C6 position of chitooligosaccharides into carboxyl groups by TEMPO oxidation. Using CaC12 as the calcium source, through the discussion of pH value, reaction temperature, reaction time, CCOS and CaCl2 mass ratio on CCOS- Ca （Ⅱ） rate were studied, using three factors and five levels central composite rotatable design to optimize the preparation process. The products were analyzed by Fourier transform infrared spectrum scanning （FT - IR） and elemental analysis （EA）. Regression analysis of response surface test data was carried out by using Design-Expert software. The optimum process parameters for CCOS - Ca （ Ⅱ ） preparation were as follows： the pH value was 8.3, the reaction time was 60 min, the reaction temperature was 50℃ , and the mass ratio of CCOS to CaCl2 was 34. Under the optimized conditions, the chelating rate was 88.86%. The structure of CCOS - Ca （ ℃ ） complex was confirmed by IR and EA analysis, and the molar ratio of CCOS to Ca^2＋ was 2： 1. The CCOS molecule contained -OH, -NH2 and -COOH, which can effectively chelate calcium. The effect of pH value, reaction temperature and ligand mass ratio on the chelation results was significant. CCOS- Ca （ Ⅱ ） complex can not only play the unique biological activity of chitooligosaccharides, but also may play a synergistic effect, enhance both the ehitooligosaccharides and Ca^2＋ biological activity, and it was expected to prepare new calcium supplements.

关 键 词：壳寡糖衍生物 6-羧基壳寡糖螯合钙 螯合工艺 元素分析 红外表征 

分 类 号：TS202.1[轻工技术与工程—食品科学] S985[轻工技术与工程—食品科学与工程]