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微波辐射制备甲壳低聚糖衍生物及抗氧化、杀菌活性研究
其他题名Study on Preparation, Antioxidant and Fungicidal Activity of Chitooligosaccharide Derivatives by Microwave Irradiation
刘松
学位类型博士
2008-06-01
学位授予单位中国科学院海洋研究所
学位授予地点海洋研究所
关键词甲壳低聚糖 微波辐射 甲壳低聚糖硫酸酯 金属配合物 氧自由基 抗氧化活性 杀菌活性
摘要微波辐射下的化学合成反应具有反应速度快、产率高、选择性好、产物易控制等优点,还可以节约能源。本文采用微波辐射方法降解壳聚糖制备了不同分子量的甲壳低聚糖,并以甲壳低聚糖为原料,在微波辐射下进行硫酸酯化、羧甲基化、希夫碱化、金属配位等反应,合成了多种新型甲壳低聚糖衍生物,并研究其抗氧化和抗菌机理,为甲壳低聚糖及其衍生物的进一步应用奠定理论基础。 研究微波可控性降解反应,制备了不同分子量的甲壳低聚糖,探讨反应介质、氧化剂与壳聚糖配比、辐射功率和辐射时间等因素对降解反应的影响。结果表明:选择不同的反应条件,微波辐射1-10min就可制备出相对分子量在0.3-10万之间不同分子量大小的甲壳低聚糖,且反应产率高、重复性好。研究了氯化钠等电解质对微波降解的影响,通过改变反应时间和微波功率,添加电解质可加速微波场中壳聚糖的降解。 在微波辐射下进行甲壳低聚糖的羧甲基化反应,制备羧甲基低聚糖。在此基础上,不同分子量的低聚糖及羧甲基低聚糖与金属盐溶液在微波场中反应制备甲壳低聚糖基金属衍生物。采用紫外、红外等分析手段对配位基团和配位方式进行了分析。 甲壳低聚糖及其铜、锌配合物首次在微波辐射下进行硫酸酯化修饰,合成新型甲壳低聚糖硫酸酯金属衍生物,产物具有良好的水溶性、硫酸基含量在30%以上。研究了微波促进希夫碱化反应,合成了5种羟丙基甲壳低聚糖希夫碱,并对其结构进行了分析确定。 对上述四类甲壳低聚糖衍生物进行了抗氧化和抗菌活性筛选,结果发现四类衍生物对超氧阴离子自由基和羟自由基均具有较好的清除作用,对几种常见农作物病原菌也具有明显的抑制活性。证明接入的活性基团、金属离子等对其衍生物的生物活性起到一定促进作用,具有加合性和增效性。为今后进一步研究和应用奠定了基础。
其他摘要Microwave irradiation can provide chemical processes with special attributes sucn as enhanced reaction rates, higher yields, greater selectivity, the ease of manipulation and energy conservation. In this dissertation, a study of preparation of different molecular chitooligosaccharide under microwave irradiation was made. Several new chitooligosaccharide-base derivatives were synthesized via Sulfonation , Carboxymethylation, Schiff Base formation, and metal Coordination with chitooligosaccharide. Studies on antioxidant activity and antimicrobial activity of these derivatives, which can provide theory base for further application of chitooligosaccharide and its derivatives. Studies on microwave controllability degradation reaction and preparation different molecular chitooligosaccharide. The effects of various factors:reaction solution,oxidant/Chitosan ratio, microwave irradiation power and time on the degradation reaction were investigated in this paper. The results showed that chitosans with 3-100 thousand molecular weight were prepared in 1-10 minutes by microwave irradiation under the different reaction conditions. At the same time the yield was higher and repetition was well. The effect of inorganic salts such as sodium chloride on the hydrolysis of chitosan in a microwave field was investigated. The addition of some inorganic salts was shown to ffectively accelerate the degradation of chitosan under microwave irradiation by changing the reaction time and/or the radiation power. The carboxymethyl chitooligosaccharide has been prepared under microwave irradiation condition. Furthermore, the complexes of chitooligosaccharide with metal and the complexes of carboxymethyl chitooligosaccharide with metal have been synthesized by metal solution reacted with chitooligosaccharide or carboxymethyl chitooligosaccharide under microwave irradiation. The configurations of these derivatives were analyzed by UV and IR spectra. For the first time, chitosan and its complexes with copper(Ⅱ) or zinc(Ⅱ) were sulfation modified by using microwave irradiation. The metal complexes with sulfation chitosan have been synthesized. All were soluble in water and the SO42- content was over 30%. Five compounds were synthesized under microwave irradiation by the reaction of chitooligosaccharide with salicylaldehyde, and the configurations of them were analyzed. Based on the results of the fungicidal activity and antioxidant activity of the above four kinds of derivatives, we found these derivatives had excellent ability for scavenging the superoxide anion radical and hydroxyl radical and had also inhibition effects on the growth of crop pathogenic fungi(Valsa mali). It was proved that the activity group and metal ion can advance biology activity of these derivatives. It was estabished the foundations for research and application of chitooligosaccharide and its derivatives for the future.
页数111
语种中文
文献类型学位论文
条目标识符http://ir.qdio.ac.cn/handle/337002/423
专题海洋环流与波动重点实验室
推荐引用方式
GB/T 7714
刘松. 微波辐射制备甲壳低聚糖衍生物及抗氧化、杀菌活性研究[D]. 海洋研究所. 中国科学院海洋研究所,2008.
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