菊糖衍生物的制备及其生物活性研究

发布时间：2018-05-15 15:39

本文选题：菊糖 + 化学修饰　；参考：《烟台大学》2017年硕士论文

【摘要】：菊糖是作为一种天然的植物性多糖,本身具有良好的理化性质和生理功能,是一种廉价易得、生物相容的可再生生物资源。目前,菊糖被广泛应用于食品、饲料、保健品、化工、生物能源以及医药等行业中,对菊糖这种可再生生物资源潜在价值的开发与利用具有重大的科学意义。我国菊糖的开发起步较晚,虽然菊糖已经在食品加工业得到广泛应用,但是,在某些领域的研究处于起步阶段,仍然具有很大的发展空间。本文以天然菊糖为原料,参考国内外的研究热点,并结合本专业的知识,通过对菊糖进行针对性的化学修饰,设计、合成了一系列的菊糖衍生物,使之具有不同的生物活性,为实现菊糖的高值化利用提供理论参考。本文以菊糖为骨架,首先将菊糖与氯乙酰氯反应生成氯乙酰菊糖(CAIL)中间体,然后通过不同含氮或磷的化合物与CAIL的乙酰基发生亲核取代反应,将活性基团引入菊糖分子。首次合成了季铵盐类菊糖衍生物、季膦盐类菊糖衍生物和卤代苯类菊糖衍生物。合成方法具有简单、高效,反应条件温和,产物单一,易于分离等优点。然后采用红外光谱法、核磁共振光谱法对新合成的化合物进行结构鉴定。继而研究了季铵盐类菊糖衍生物的抗氧化活性和季膦盐类、卤代苯类菊糖衍生物的抑菌活性。对季铵盐类菊糖衍生物进行了羟自由基、DPPH自由基和超氧阴离子自由基的清除能力测试。测试结果表明季铵盐改性菊糖衍生物可以明显提高菊糖的抗氧化活性。2-咪唑-氯乙酰菊糖(IAIL)对羟自由基和超氧阴离子自由基的清除能力最强,其在浓度为0.4 mg/mL时对羟自由基的清除率达到84.6%,在1.6 mg/mL时,对超氧阴离子自由基的清除率达到67.8%,均远高于菊糖;2-(N,N-二甲基癸胺)-氯乙酰菊糖(DMDAAIL)对DPPH自由基的清除能力最强,在浓度为1.6 mg/mL时,达到80.7%。对季膦盐类和卤代苯类菊糖衍生物采用菌丝生长速率法进行了抑真菌活性测试。选用三种农业常见致病真菌(黄瓜炭疽病菌、西瓜枯萎病菌和芦笋茎枯病菌)为测试菌种,比较了菊糖原料和衍生物的抑菌活性。结果表明,菊糖本身没有抑菌活性,而所有菊糖衍生物都具有较强的抑真菌活性。季膦盐类菊糖衍生物的抑菌效果更为显著。对于季膦盐类菊糖衍生物,季膦盐上的烷基链越长,相应的菊糖衍生物的抑菌活性就越高。对于链长相同的C-6-(2-三环己基膦)-氯乙酰菊糖衍生物(TCHPAIL)和C-6-(2-三苯基膦)-氯乙酰菊糖衍生物(TPhPAIL)两种菊糖衍生物,TPhPAIL的抑菌活性要强于前者,表明季膦盐上取代基的吸电子能力越强,抑菌活性越高。对于卤代苯类菊糖衍生物,卤素的种类以及卤素在苯环上的取代位置影响衍生物的抑菌活性,氯元素的抑菌作用强于氟元素,且对位取代作用强于邻位取代。
[Abstract]:As a kind of natural plant polysaccharides, inulin has good physical and chemical properties and physiological functions. It is a cheap and biocompatible renewable biological resource. At present, chrysanthemum is widely used in food, feed, health products, chemical industry, bioenergy, medicine and other industries, which has great scientific significance for the development and utilization of the potential value of inulin as a renewable biological resource. The development of chrysanthemum in China is relatively late. Although chrysanthemum has been widely used in food processing industry, the research in some fields is still in its infancy and still has a great space for development. In this paper, a series of chrysanthemum derivatives were designed and synthesized by chemical modification of natural chrysanthemum, referring to the domestic and foreign research hot spots, and combining with the knowledge of this profession, so that they have different biological activities. It provides a theoretical reference for realizing the high value utilization of inulin. In this paper, the fructose was first reacted with chloroacetyl chloride to form the intermediate of chloracetyl chrysanthemum, and then the nucleophilic substitution reaction between the compounds containing different nitrogen or phosphorus and the acetyl group of CAIL was carried out, and the active group was introduced into the chrysosaccharide molecule. Quaternary ammonium salt chrysanthemum derivatives, quaternary phosphine inulin derivatives and halogenated benzenes were synthesized for the first time. The synthetic method has the advantages of simplicity, high efficiency, mild reaction conditions, single product and easy separation. The structures of the new compounds were identified by IR and NMR. The antioxidation activity of quaternary ammonium salt inulin derivatives and the bacteriostatic activity of quaternary phosphine salts and halogenated benzene inulin derivatives were studied. The scavenging ability of hydroxyl radical DPPH radical and superoxide anion radical was tested for quaternary ammonium salt inulin derivatives. The results showed that quaternary ammonium salt modified chrysanthemum derivatives could significantly improve the antioxidant activity of inulin .2-imidazole-chloroacetyl chrysanthemum and its scavenging ability to hydroxyl radical and superoxide anion radical. At the concentration of 0.4 mg/mL, the scavenging rate of hydroxyl radical reached 84.6, and at 1.6 mg/mL, the scavenging rate of superoxide anion radical reached 67.8%, which was much higher than that of DPPH free radical scavenging ability of dimethylethylamine N-dimethylethylamine and chloroacetyl cinnamate (DMDAAILL). When the concentration was 1.6 mg/mL, the concentration reached 80.7. The fungicidal activity of the derivatives of phosphine salts and halogenated benzenes was tested by mycelium growth rate method. Three common agricultural pathogenic fungi (cucumber anthracnose, watermelon Fusarium wilt and asparagus stem blight) were selected as test strains to compare the bacteriostatic activity of raw materials and derivatives of inulin. The results showed that chrysanthemum had no antimicrobial activity and all of the chrysanthemum derivatives had strong fungicidal activity. The bacteriostatic effect of Quaternary phosphine salt inulin derivatives was more obvious. The longer the alkyl chain in the quaternary phosphine salt, the higher the antimicrobial activity of the corresponding inulin derivative. The antibacterial activity of TPhPAIL and TPhPAIL, two kinds of chrysanthemum derivatives with the same chain length, were stronger than that of the former, indicating that the higher the electron absorption ability of the substituents on the ternary phosphine salt, the stronger the bacteriostatic activity of TPhPAIL, two kinds of chrysanthemum derivatives, TPhPAIL, which have the same chain length, and C-6-Phosphine 2-triphenylphosphine chloroacetyl chrysanthemum derivatives (TPhPAIL) have stronger bacteriostatic activity than the former. The antimicrobial activity was higher. For halogenated benzenes, the species of halogens and the substitution position of halogens on benzene rings affect the bacteriostatic activity of the derivatives. The bacteriostatic effect of chlorine is stronger than that of fluorine, and the para-substitution is stronger than ortho-substitution.
【学位授予单位】：烟台大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O629.12

【参考文献】