本文選題：菊糖 + 化學(xué)修飾�。� 參考：《煙臺大學(xué)》2017年碩士論文

【摘要】：菊糖是作為一種天然的植物性多糖,本身具有良好的理化性質(zhì)和生理功能,是一種廉價(jià)易得、生物相容的可再生生物資源。目前,菊糖被廣泛應(yīng)用于食品、飼料、保健品、化工、生物能源以及醫(yī)藥等行業(yè)中,對菊糖這種可再生生物資源潛在價(jià)值的開發(fā)與利用具有重大的科學(xué)意義。我國菊糖的開發(fā)起步較晚,雖然菊糖已經(jīng)在食品加工業(yè)得到廣泛應(yīng)用,但是,在某些領(lǐng)域的研究處于起步階段,仍然具有很大的發(fā)展空間。本文以天然菊糖為原料,參考國內(nèi)外的研究熱點(diǎn),并結(jié)合本專業(yè)的知識,通過對菊糖進(jìn)行針對性的化學(xué)修飾,設(shè)計(jì)、合成了一系列的菊糖衍生物,使之具有不同的生物活性,為實(shí)現(xiàn)菊糖的高值化利用提供理論參考。本文以菊糖為骨架,首先將菊糖與氯乙酰氯反應(yīng)生成氯乙酰菊糖(CAIL)中間體,然后通過不同含氮或磷的化合物與CAIL的乙�；l(fā)生親核取代反應(yīng),將活性基團(tuán)引入菊糖分子。首次合成了季銨鹽類菊糖衍生物、季膦鹽類菊糖衍生物和鹵代苯類菊糖衍生物。合成方法具有簡單、高效,反應(yīng)條件溫和,產(chǎn)物單一,易于分離等優(yōu)點(diǎn)。然后采用紅外光譜法、核磁共振光譜法對新合成的化合物進(jìn)行結(jié)構(gòu)鑒定。繼而研究了季銨鹽類菊糖衍生物的抗氧化活性和季膦鹽類、鹵代苯類菊糖衍生物的抑菌活性。對季銨鹽類菊糖衍生物進(jìn)行了羥自由基、DPPH自由基和超氧陰離子自由基的清除能力測試。測試結(jié)果表明季銨鹽改性菊糖衍生物可以明顯提高菊糖的抗氧化活性。2-咪唑-氯乙酰菊糖(IAIL)對羥自由基和超氧陰離子自由基的清除能力最強(qiáng),其在濃度為0.4 mg/mL時(shí)對羥自由基的清除率達(dá)到84.6%,在1.6 mg/mL時(shí),對超氧陰離子自由基的清除率達(dá)到67.8%,均遠(yuǎn)高于菊糖;2-(N,N-二甲基癸胺)-氯乙酰菊糖(DMDAAIL)對DPPH自由基的清除能力最強(qiáng),在濃度為1.6 mg/mL時(shí),達(dá)到80.7%。對季膦鹽類和鹵代苯類菊糖衍生物采用菌絲生長速率法進(jìn)行了抑真菌活性測試。選用三種農(nóng)業(yè)常見致病真菌(黃瓜炭疽病菌、西瓜枯萎病菌和蘆筍莖枯病菌)為測試菌種,比較了菊糖原料和衍生物的抑菌活性。結(jié)果表明,菊糖本身沒有抑菌活性,而所有菊糖衍生物都具有較強(qiáng)的抑真菌活性。季膦鹽類菊糖衍生物的抑菌效果更為顯著。對于季膦鹽類菊糖衍生物,季膦鹽上的烷基鏈越長,相應(yīng)的菊糖衍生物的抑菌活性就越高。對于鏈長相同的C-6-(2-三環(huán)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)兩種菊糖衍生物,TPhPAIL的抑菌活性要強(qiáng)于前者,表明季膦鹽上取代基的吸電子能力越強(qiáng),抑菌活性越高。對于鹵代苯類菊糖衍生物,鹵素的種類以及鹵素在苯環(huán)上的取代位置影響衍生物的抑菌活性,氯元素的抑菌作用強(qiáng)于氟元素,且對位取代作用強(qiáng)于鄰位取代。
[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.
【學(xué)位授予單位】：煙臺大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O629.12

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 馬戎;戴玉梅;;季銨鹽改性茶皂素的合成與性能研究[J];日用化學(xué)工業(yè);2016年03期

2 李文星;黃輝;李好;;我國農(nóng)藥使用監(jiān)管現(xiàn)狀及對策研究[J];農(nóng)藥科學(xué)與管理;2015年08期

3 熊政委;;菊糖的生理功能的研究進(jìn)展[J];食品安全導(dǎo)刊;2015年18期

4 江鎮(zhèn)海;;我國吡啶在農(nóng)藥中的應(yīng)用和發(fā)展前景[J];今日農(nóng)藥;2015年02期

5 陳書攀;何國慶;謝衛(wèi)忠;孫咪娜;;菊粉對面團(tuán)流變性及面條質(zhì)構(gòu)的影響[J];中國食品學(xué)報(bào);2014年07期

6 馮大偉;張洪霞;劉廣洋;靳志明;劉勝一;衣悅濤;;不同品種菊芋對黃河三角洲土壤鹽脅迫的響應(yīng)研究[J];核農(nóng)學(xué)報(bào);2013年11期

7 王海東;吳文華;;牛蒡菊糖生理功能研究進(jìn)展[J];安徽農(nóng)業(yè)科學(xué);2013年27期

8 左華江;溫婉華;吳丁財(cái);符若文;;高分子抗菌劑的研究現(xiàn)狀[J];化工進(jìn)展;2013年03期

9 延秀銀;王小晉;劉桂花;常宏宏;魏文瓏;;季銨鹽、季膦鹽類高分子抗菌劑的研究進(jìn)展[J];廣州化學(xué);2012年04期

10 熊政委;董全;;菊糖的生理功能和在食品中應(yīng)用的研究進(jìn)展[J];食品工業(yè)科技;2012年20期

相關(guān)博士學(xué)位論文 前3條

1 李琬聰;菊芋中不同聚合度天然菊糖的分離純化及生物活性研究[D];中國科學(xué)院煙臺海岸帶研究所;2015年

2 于濟(jì)洋;菊芋全粉特性及功能強(qiáng)化機(jī)理與作用研究[D];沈陽農(nóng)業(yè)大學(xué);2014年

3 郭占勇;水溶性殼聚糖衍生物的取代基團(tuán)及氨基正電性對抑菌活性的影響[D];中國科學(xué)院研究生院（海洋研究所）;2007年

相關(guān)碩士學(xué)位論文 前7條

1 周金燕;甜菊糖甜味特性與食品應(yīng)用研究[D];江南大學(xué);2011年

2 張建平;菊芋菊糖的提取純化及其生物活性研究[D];天津科技大學(xué);2009年

3 丁紅梅;黑曲霉內(nèi)切菊粉酶生產(chǎn)菊芋低聚果糖工藝及應(yīng)用研究[D];西南大學(xué);2008年

4 宮薩蕾特（Consolate Nsabimana）;酶法制備菊糖高果糖漿及其應(yīng)用[D];江南大學(xué);2005年

5 閆位娟;菊粉酶的分離純化及固定化研究[D];廣西師范大學(xué);2005年

6 江山;新型高分子抗菌劑及抗菌材料的研究[D];浙江大學(xué);2003年

7 王海寬;天然食物抗氧化特性的化學(xué)和生物學(xué)評價(jià)[D];東北農(nóng)業(yè)大學(xué);2001年

，

本文編號：1892927