CN115043958B - 一种酚酸酯化壳寡糖季铵盐及其制备方法和应用 - Google Patents
一种酚酸酯化壳寡糖季铵盐及其制备方法和应用 Download PDFInfo
- Publication number
- CN115043958B CN115043958B CN202210971112.6A CN202210971112A CN115043958B CN 115043958 B CN115043958 B CN 115043958B CN 202210971112 A CN202210971112 A CN 202210971112A CN 115043958 B CN115043958 B CN 115043958B
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- Prior art keywords
- chitosan oligosaccharide
- quaternary ammonium
- ammonium salt
- phenolic acid
- trimethyl chitosan
- Prior art date
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Images
Classifications
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Abstract
Description
技术领域
本发明涉及壳寡糖衍生物制备领域,具体涉及一种酚酸酯化N,N,N-三甲基壳寡糖季铵盐及其制备方法和应用。
背景技术
过量自由基引起氧化损伤是生命体内一种异常的生理现象,随着年龄的增加,以及某些不良生活习惯的累积,它很有可能对生物体内的生物大分子如蛋白质、脂质、核酸等造成不同程度的损伤,引发神经退行性疾病,更甚者可引发肿瘤等疾病,严重威胁着生命健康。此外,食物中自由基的积累引起过氧化,是导致食物腐烂变质的重要原因之一。因此开发可应用于医药、保健及食品保鲜等领域的新型、绿色、无毒抗氧化剂非常有必要。
壳聚糖是自然界中唯一存在的天然阳离子碱性多糖,储量丰富,其基本组成单位是氨基葡萄糖或乙酰氨基葡萄糖,根据聚合度的不同壳聚糖的分子量在几万至几百万不等。壳寡糖是壳聚糖的降解产物,一般情况下,聚合度在2-20即可被认为是壳寡糖,其分子量在几百至几千不等,与高分子量的壳聚糖相比,壳寡糖具有良好的水溶性,其生物相容性、生物降解性等生物活性也有了进一步的提高,在很多领域都有潜在的应用价值,近年来关于壳寡糖的研究越来越受到人们的关注。
化学改性是一种简便、高效并可定向改变化合物物化性质的合成手段,根据化合物自身的结构特点,通过化学修饰方法将功能基团引入分子使之具有更优异的活性从而进一步开发利用是当前的研究热点之一,壳寡糖分子中同时具有氨基基团和羟基基团,给化学修饰提供了活性位点,使得壳寡糖衍生物的制备成为可能。据报道对壳寡糖进行化学修饰,可以进一步提高壳寡糖的生物活性,修饰作为目前的主要研究方向,有望实现壳寡糖的高值化利用。
发明内容
本发明的目的是提出了一种酚酸酯化N,N,N-三甲基壳寡糖季铵盐及其制备方法和应用。
为实现上述目的,本发明所采用的技术方案为:
一种酚酸酯化N,N,N-三甲基壳寡糖季铵盐,酚酸酯化N,N,N-三甲基壳寡糖季铵盐的结构式如下述式一所示:
式一
一种酚酸酯化N,N,N-三甲基壳寡糖季铵盐的制备方法,以壳寡糖为原料,首先对其2位氨基进行季铵化,得到N,N,N-三甲基壳寡糖季铵盐,然后与酚酸反应,得到6位酯化的N,N,N-三甲基壳寡糖季铵盐酚酸衍生物。
具体为:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:称取壳寡糖分散于N-甲基吡咯烷酮中溶胀30-60分钟,而后向溶胀后的壳寡糖中加入碘化钠、氢氧化钠溶液,反应30分钟;然后在冰浴条件下滴入碘甲烷,在60℃、回流条件下继续反应2 h,得到N,N,N-三甲基壳寡糖季铵盐,其中,壳寡糖、碘化钠、氢氧化钠、碘甲烷的摩尔量比值是1:3-5:3:6-10;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:在60℃、氮气保护条件下将酚酸溶于二甲亚砜中,随后加入N,N'-羰基二咪唑活化10 - 12 h,然后加入上述步骤制备获得的N,N,N-三甲基壳寡糖季铵盐继续反应10 - 12 h,反应后得到酚酸酯化N,N,N-三甲基壳寡糖季铵盐,其中,酚酸、N,N'-羰基二咪唑、N,N,N-三甲基壳寡糖季铵盐化合物的摩尔量比值是2-3:2-6:1。
所述步骤(1)中将壳寡糖分散至N-甲基吡咯烷酮中所得溶胀溶液中壳寡糖浓度为7% - 10%。
所述向溶胀后壳寡糖中加入氢氧化钠水溶液,其中,氢氧化钠水溶液的浓度为15%。
所述步骤(1)反应后产物用无水乙醇与无水乙醚体积比为1:1的混合溶液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐。
所述步骤(2)中将酚酸溶于二甲亚砜中所得溶液中酚酸浓度为20%-30%。
一种酚酸酯化N,N,N-三甲基壳寡糖季铵盐的应用,所述酚酸酯化N,N,N-三甲基壳寡糖季铵盐在食品、保健品、医药或日化领域中作为抗氧化剂的应用。
本发明所具有的优点:
(1)本发明酚酸酯化N,N,N-三甲基壳寡糖季铵盐以壳寡糖的氨基和羟基为活性位点通过化学修饰引入季铵盐基团和酚羟基基团,使这些活性基团以壳寡糖为主体发挥抗氧化活性的同时,还保留了壳寡糖无毒、可降解、生物相容性好等优势。实验结果证明酚酸酯化N,N,N-三甲基壳寡糖季铵盐抗氧化活性显著提高,扩大了应用范围,提升了其应用前景,具有很大的应用潜力;
(2)天然酚酸来源丰富,简单易得,在合成工艺上,本发明实验步骤简单,操作简便,原料广泛,且产物合成产率较高,可以广泛应用于食品、保健品、医药及日化等领域。
附图说明
图1为本发明实施例提供的酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成路线图。
图2为本发明实施例提供的壳寡糖的红外光谱图;3395 cm-1处为壳寡糖上OH的伸缩振动吸收峰,2924 cm-1处为CH的伸缩振动吸收峰,1582 cm-1处为壳寡糖上NH2的特征吸收峰,1415 cm-1处为壳寡糖上CH2的弯曲振动吸收峰,1084 cm-1处为壳寡糖上C-O的伸缩振动吸收峰。
图3为本发明实施例提供的N,N,N-三甲基壳寡糖季铵盐的红外光谱图;与壳寡糖红外谱图相比,在1472 cm-1及1644 cm-1处出现新的特征吸收峰,归属于壳寡糖引入季铵基团后出现的特征吸收,证明N,N,N-三甲基壳寡糖季铵盐的成功合成。
图4为本发明实施例提供的没食子酸酯化N,N,N-三甲基壳寡糖季铵盐的红外光谱图;与N,N,N-三甲基壳寡糖季铵盐红外谱图相比,在1713 cm-1处出现新的特征吸收峰,归属于羟基和羧基反应后生成的酯键的特征吸收,同时,在1555 cm-1处出现新的特征吸收峰,及在730、796cm-1附近出现的特征吸收峰归属于引入的苯环基团的特征吸收,证明没食子酸酯化N,N,N-三甲基壳寡糖季铵盐的成功合成。
图5为本发明实施例提供的阿魏酸酯化N,N,N-三甲基壳寡糖季铵盐的红外光谱图;与N,N,N-三甲基壳寡糖季铵盐红外谱图相比,1727 cm-1处为酯基C=O双键的特征吸收峰,1120、1256cm-1处为酯基C-O-C的特征吸收峰,同时在1508 cm-1及在715、845 cm-1处出现的新的特征吸收峰为苯环基团的特征吸收,这证明阿魏酸酯化N,N,N-三甲基壳寡糖季铵盐的成功合成。
图6为本发明实施例提供的对香豆酸酯化N,N,N-三甲基壳寡糖季铵盐的红外光谱图;与N,N,N-三甲基壳寡糖季铵盐红外谱图相比,与N,N,N-三甲基壳寡糖季铵盐红外谱图相比,1734 cm-1处为酯基C=O双键的特征吸收峰,1131、1216cm-1处为酯基C-O-C的特征吸收峰,同时在1506 cm-1及在833 cm-1处出现的新的特征吸收峰为苯环基团的特征吸收,这证明对香豆酸酯化N,N,N-三甲基壳寡糖季铵盐的成功合成。
图7为本发明实施例提供的咖啡酸酯化N,N,N-三甲基壳寡糖季铵盐的红外光谱图;与N,N,N-三甲基壳寡糖季铵盐红外谱图相比,1748 cm-1处为酯基C=O双键的特征吸收峰,1285cm-1处为酯基C-O-C的特征吸收峰,同时在1554 cm-1及在766、822 cm-1处出现的新的特征吸收峰为苯环基团的特征吸收,这证明咖啡酸酯化N,N,N-三甲基壳寡糖季铵盐的成功合成。
图8为本发明实施例提供的原儿茶酸酯化N,N,N-三甲基壳寡糖季铵盐的红外光谱图;与N,N,N-三甲基壳寡糖季铵盐红外谱图相比,1748 cm-1处为酯基C=O双键的特征吸收峰,1287cm-1处为酯基C-O-C的特征吸收峰,同时在1555 cm-1及在764、852 cm-1处出现的新的特征吸收峰为苯环基团的特征吸收,这证明原儿茶酸酯化N,N,N-三甲基壳寡糖季铵盐的成功合成。
图9为本发明实施例提供的芥子酸酯化N,N,N-三甲基壳寡糖季铵盐的红外光谱图;与N,N,N-三甲基壳寡糖季铵盐红外谱图相比,1730 cm-1处为酯基C=O双键的特征吸收峰,1129、1206、1275 cm-1处为酯基C-O-C的特征吸收峰,同时在1504 cm-1及在723、828 cm-1处出现的新的特征吸收峰为苯环基团的特征吸收,这证明芥子酸酯化N,N,N-三甲基壳寡糖季铵盐的成功合成。
具体实施方式
以下实施例是对本发明的进一步说明,但本发明不局限于本实施方式中的制备方法和用途。
本发明首先制备得到N,N,N-三甲基壳寡糖季铵盐,然后通过不同酚酸,获得不同结构的酚酸酯化N,N,N-三甲基壳寡糖季铵盐。本发明获得的衍生物在壳寡糖的2位氨基和6位羟基同时引入了活性基团,经过抗氧化活性测试发现,酚酸酯化N,N,N-三甲基壳寡糖季铵盐具有很好的抗氧化活性。此外,衍生物制备过程易于操作,产率较高易于大规模产业化,有望广泛推广至食品、保健品、医药及日化等领域。
实施例1
(1)N,N,N-三甲基壳寡糖季铵盐的合成:将0.02 mol 壳寡糖(分子量为2000Da左右)分散于50 mL的N-甲基吡咯烷酮中溶胀1 h,而后向溶胀后壳寡糖溶液中加入碘化钠9g、15%的氢氧化钠水溶液30 mL,在冰浴条件下搅拌反应30分钟;随后在冰浴条件下向反应体系中滴入30 mL碘甲烷,滴加完毕后在60℃、回流条件下继续反应2 h;最后用无水乙醇与无水乙醚的体积比为1:1混合液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:将0.5993 g没食子酸溶于5 mL二甲亚砜中,随后加入0.5166 g N,N'-羰基二咪唑活化12 h,然后加入0.50 g N,N,N-三甲基壳寡糖季铵盐,于60℃、氮气保护条件下反应12 h,用无水乙醇与无水乙醚体积比为1:1混合液沉淀并洗涤,即得到没食子酸酯化N,N,N-三甲基壳寡糖季铵盐。
实施例2
与实施例1不同之处在于:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:将0.02 mol 壳寡糖(分子量为2000Da左右)分散于60 mL的N-甲基吡咯烷酮中溶胀30分钟,而后向溶胀后壳寡糖溶液中加入碘化钠9 g、15%的氢氧化钠水溶液30 mL,在冰浴条件下搅拌反应30分钟;随后在冰浴条件下向反应体系中滴入17 mL碘甲烷,滴加完毕后在60℃、回流条件下继续反应2 h;最后用无水乙醇与无水乙醚的体积比为1:1混合液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:将0.6186 g阿魏酸溶于5 mL二甲亚砜中,随后加入1.0331 g N,N'-羰基二咪唑活化12 h,然后加入0.50 g N,N,N-三甲基壳寡糖季铵盐,于60℃、氮气保护条件下反应12 h,用无水乙醇与无水乙醚体积比为1:1混合液沉淀并洗涤,即得到阿魏酸酯化N,N,N-三甲基壳寡糖季铵盐。
实施例3
与实施例1不同之处在于:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:将0.02 mol 壳寡糖(分子量为2000Da左右)分散于60 mL的N-甲基吡咯烷酮中溶胀1 h,而后向溶胀后壳寡糖溶液中加入碘化钠12g、15%的氢氧化钠水溶液30 mL,在冰浴条件下搅拌反应30分钟;随后在冰浴条件下向反应体系中滴入30 mL碘甲烷,滴加完毕后在60℃、回流条件下继续反应2 h;最后用无水乙醇与无水乙醚的体积比为1:1混合液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:将0.7845 g对香豆酸溶于5 mL二甲亚砜中,随后加入0.7748 g N,N'-羰基二咪唑活化12 h,然后加入0.50 g N,N,N-三甲基壳寡糖季铵盐,于60℃、氮气保护条件下反应12 h,用无水乙醇与无水乙醚体积比为1:1混合液沉淀并洗涤,即得到对香豆酸酯化N,N,N-三甲基壳寡糖季铵盐。
实施例4
与实施例1不同之处在于:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:将0.02 mol 壳寡糖(分子量为2000Da左右)分散于50 mL的N-甲基吡咯烷酮中溶胀1 h,而后向溶胀后壳寡糖溶液中加入碘化钠15g、15%的氢氧化钠水溶液30 mL,在冰浴条件下搅拌反应30分钟;随后在冰浴条件下向反应体系中滴入30 mL碘甲烷,滴加完毕后在60℃、回流条件下继续反应2 h;最后用无水乙醇与无水乙醚的体积比为1:1混合液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:将0.8609 g咖啡酸溶于5 mL二甲亚砜中,随后1.5497 g 加入N,N'-羰基二咪唑活化10 h,然后加入0.50 g N,N,N-三甲基壳寡糖季铵盐,于60℃、氮气保护条件下反应10 h,用无水乙醇与无水乙体积比为醚1:1混合液沉淀并洗涤,即得到咖啡酸酯化N,N,N-三甲基壳寡糖季铵盐。
实施例5
与实施例1不同之处在于:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:将0.02 mol 壳寡糖(分子量为2000Da左右)分散于50 mL的N-甲基吡咯烷酮中溶胀1 h,而后向溶胀后壳寡糖溶液中加入碘化钠12g、15%的氢氧化钠水溶液30 mL,在冰浴条件下搅拌反应30分钟;随后在冰浴条件下向反应体系中滴入23 mL碘甲烷,滴加完毕后在60℃、回流条件下继续反应2 h;最后用无水乙醇与无水乙醚的体积比为1:1混合液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:将0.4910 g原儿茶酸溶于5 mL二甲亚砜中,随后加入0.7748 g N,N'-羰基二咪唑活化10 h,然后加入0.50 g N,N,N-三甲基壳寡糖季铵盐,于60℃、氮气保护条件下反应12 h,用无水乙醇与无水乙醚体积比为1:1混合液沉淀并洗涤,即得到原儿茶酸酯化N,N,N-三甲基壳寡糖季铵盐。
实施例6
与实施例1不同之处在于:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:将0.02 mol 壳寡糖(分子量为2000Da左右)分散于50 mL的N-甲基吡咯烷酮中溶胀1 h,而后向溶胀后壳寡糖溶液中加入碘化钠9g、15%的氢氧化钠水溶液30 mL,在冰浴条件下搅拌反应30分钟;随后在冰浴条件下向反应体系中滴入30 mL碘甲烷,滴加完毕后在60℃、回流条件下继续反应2 h;最后用无水乙醇与无水乙醚的体积比为1:1混合液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:将0.7143 g芥子酸溶于5 mL二甲亚砜中,随后加入0.5166 g N,N'-羰基二咪唑活化12 h,然后加入0.50 g N,N,N-三甲基壳寡糖季铵盐,于60℃、氮气保护条件下反应12 h,用无水乙醇与无水乙醚体积比为1:1混合液沉淀并洗涤,即得到芥子酸酯化N,N,N-三甲基壳寡糖季铵盐。
应用例1
抗氧化活性测定
1)清除超氧阴离子抗氧化能力的测定:分别测定壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐的清除超氧阴离子能力并做对比(表1)。操作过程如下:
将实施例中实验用壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐分别真空冷冻干燥至恒重后作为测试样品,称取样品制备初始浓度为10 mg/mL的溶液,配制pH = 8 的Tris-HCl (称三羟甲基氨基甲烷0.9691g,加入0.4 mL浓盐酸,用去离子水溶解并定容至500 mL)缓冲溶液,配制NADH(称取0.0366 g还原性辅酶Ⅰ,用Tris-HCl缓冲溶液定容至100 mL)溶液,配制NBT(称取0.0245 g硝基四氮唑蓝,用Tris-HCl缓冲溶液定容至100 mL)溶液,配制PMS(称取0.0018 g吩嗪硫酸甲酯,用Tris-HCl缓冲溶液定容至100 mL)溶液,分别取初始浓度为10 mg/mL的待测溶液0.030、0.060、0.120、0.240 mL,然后分别加入0.5 ml NADH、0.5 mL NBT和0.5 mL PMS溶液,在试管中混匀后室温下避光反应5分钟,在560 nm处测定吸光度,对照组用等体积Tris-HCl缓冲液代替NADH溶液,空白组用等体积去离子水代替待测样品。(注:被测样品均测三次,取平均值)。超氧阴离子自由基清除能力计算公式如下:
2)清除超氧阴离子抗氧化能力的测定结果:
表1 壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐的清除超氧阴离子能力(%)
3)清除羟自由基抗氧化能力的测定:分别测定壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐的清除羟自由基能力并做对比(表2)。操作过程如下:
将实施例中实验用壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐分别真空冷冻干燥至恒重后作为测试样品,称取样品制备初始浓度为10 mg/mL的溶液,配制pH = 7.4的磷酸(称取41.58 g 一水合磷酸氢二钠、5.2887 g二水合磷酸二氢钠,用1000 mL去离子水定容)缓冲液,配制番红花T溶液(称取0.036 g番红花T,用磷酸缓冲液定容至100 mL),配制EDTA-Fe缓冲液(称取0.0556 g七水合硫酸亚铁及0.1489gEDTANa2,用去离子水定容至100mL),配制3%过氧化氢溶液(量取10 mL30%过氧化氢溶液,用磷酸缓冲液定容至100 mL)。分别取初始浓度为10 mg/mL的待测溶液0.045、0.090、0.180、0.360、0.720 mL,然后分别加入0.5 mL EDTA-Fe溶液,1.0 mL磷酸缓冲液,1.0 mL番红花T溶液和1.0 mL3%过氧化氢溶液,在试管中混匀后在37℃条件下下避光反应30分钟,在520 nm处测定吸光度,对照组用等体积去离子水代替待测样品溶液并用等体积去离子水代替EDTA-Fe溶液,空白组用等体积去离子水代替待测样品溶液。(注:被测样品均测三次,取平均值)。羟自由基清除能力计算公式如下:
4)清除羟自由基抗氧化能力的测定结果:
表2 壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐的清除羟自由基能力(%)
5)还原能力的测定:分别测定壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N, N-三甲基壳寡糖季铵盐的还原能力并做对比(表3)。操作过程如下:
将实施例中实验用壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐分别真空冷冻干燥至恒重后作为测试样品,称取样品制备初始浓度为10 mg/mL的溶液,配制磷酸缓冲液(称取3.58 g十二水合磷酸氢二钠、6.24 g磷酸二氢钠,用去离子水定容至250 mL),配制铁氰化钾溶液(称取0.5 g铁氰化钾,用磷酸缓冲液定容至50mL),配制三氯乙酸溶液(称取0.05 g氯化铁溶液,用磷酸缓冲液定容至50 mL),分别取初始浓度为10 mg/mL的待测溶液0.030、0.060、0.120、0.240、0.480 mL, 然后分别加入0.5 mL铁氰化钾溶液,在50℃条件下反应20分钟,而后加入0.5 mL三氯乙酸溶液,离心取0.75 mL上清液加入0.6 mL去离子水和0.15 mL三氯化铁溶液,避光反应10分钟后在700 nm处测吸光度。
6)还原能力的测定结果:
表3 壳寡糖、N,N,N-三甲基壳寡糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐的还原能力(%)
本发明所合成的N,N,N-三甲基壳聚糖季铵盐、酚酸酯化N,N,N-三甲基壳寡糖季铵盐清除超氧阴离子能力如表1所示,清除羟基自由基抗氧化活性如表2所示,还原能力如表3所示。酚酸作为一种广泛存在于植物中的天然次级代谢产物,储量丰富,通过实验设计以形成酯键的方式将酚酸引入N,N,N-三甲基壳寡糖季铵盐,得到抗氧化活性显著提高的壳寡糖季铵盐,极大地提高了壳寡糖的抗氧化活性,实验结果表明,没食子酸、阿魏酸、对香豆酸、咖啡酸、原儿茶酸及芥子酸酯化N,N,N-三甲基壳聚糖季铵盐的超氧阴离子清除能力、羟自由基清除能力及还原能力相较于壳寡糖及壳寡糖季铵盐有了明显提高,该类衍生物在食品、保健品、医药及日化等领域有广大的应用价值。
Claims (6)
1.一种酚酸酯化N,N,N-三甲基壳寡糖季铵盐,其特征在于:酚酸酯化N,N,N-三甲基壳寡糖季铵盐的结构式如下述式一所示:
式一
具体制备方法为:
以壳寡糖为原料,首先对其2位氨基进行季铵化,得到N,N,N-三甲基壳寡糖季铵盐,然后与酚酸反应,得到6位酯化的N,N,N-三甲基壳寡糖季铵盐酚酸衍生物;
具体步骤为:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:称取壳寡糖分散于N-甲基吡咯烷酮中溶胀30-60分钟,而后向溶胀后的壳寡糖中加入碘化钠、氢氧化钠溶液,反应30分钟;然后在冰浴条件下滴入碘甲烷,在60℃、回流条件下继续反应2 h,得到N,N,N-三甲基壳寡糖季铵盐,其中,壳寡糖、碘化钠、氢氧化钠、碘甲烷的摩尔量比值是1:3-5:3:6-10;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:在60℃、氮气保护条件下将酚酸溶于二甲亚砜中,随后加入N,N'-羰基二咪唑活化10 - 12 h,然后加入上述步骤制备获得的N, N,N-三甲基壳寡糖季铵盐继续反应10 - 12 h,反应后得到酚酸酯化N,N,N-三甲基壳寡糖季铵盐,其中,酚酸、N,N'-羰基二咪唑、N,N,N-三甲基壳寡糖季铵盐化合物的摩尔量比值是2-3:2-6:1。
2.一种按权利要求1所述的酚酸酯化N,N,N-三甲基壳寡糖季铵盐的制备方法,其特征在于:以壳寡糖为原料,首先对其2位氨基进行季铵化,得到N,N,N-三甲基壳寡糖季铵盐,然后与酚酸反应,得到6位酯化的N,N,N-三甲基壳寡糖季铵盐酚酸衍生物;
具体步骤为:
(1)N,N,N-三甲基壳寡糖季铵盐的合成:称取壳寡糖分散于N-甲基吡咯烷酮中溶胀30-60分钟,而后向溶胀后的壳寡糖中加入碘化钠、氢氧化钠溶液,反应30分钟;然后在冰浴条件下滴入碘甲烷,在60℃、回流条件下继续反应2 h,得到N,N,N-三甲基壳寡糖季铵盐,其中,壳寡糖、碘化钠、氢氧化钠、碘甲烷的摩尔量比值是1:3-5:3:6-10;
(2)酚酸酯化N,N,N-三甲基壳寡糖季铵盐的合成:在60℃、氮气保护条件下将酚酸溶于二甲亚砜中,随后加入N,N'-羰基二咪唑活化10 - 12 h,然后加入上述步骤制备获得的N, N,N-三甲基壳寡糖季铵盐继续反应10 - 12 h,反应后得到酚酸酯化N,N,N-三甲基壳寡糖季铵盐,其中,酚酸、N,N'-羰基二咪唑、N,N,N-三甲基壳寡糖季铵盐化合物的摩尔量比值是2-3:2-6:1。
3.按权利要求2所述酚酸酯化N,N,N-三甲基壳寡糖季铵盐的制备方法,其特征在于:所述步骤(1)中将壳寡糖分散至N-甲基吡咯烷酮中所得溶胀溶液中壳寡糖浓度为7% - 10%;
所述向溶胀后壳寡糖中加入氢氧化钠溶液,其中,氢氧化钠溶液的浓度为15%。
4.按权利要求2或3所述酚酸酯化N,N,N-三甲基壳寡糖季铵盐的制备方法,其特征在于:所述步骤(1)反应后产物用无水乙醇与无水乙醚体积比为1:1的混合溶液沉淀并洗涤,抽滤冻干得到N,N,N-三甲基壳寡糖季铵盐。
5.按权利要求2所述酚酸酯化N,N,N-三甲基壳寡糖季铵盐的制备方法,其特征在于:所述步骤(2)中将酚酸溶于二甲亚砜中所得溶液中酚酸浓度为20%-30%。
6.一种权利要求1所述的酚酸酯化N,N,N-三甲基壳寡糖季铵盐非诊断非治疗目的的应用,其特征在于:所述酚酸酯化N,N,N-三甲基壳寡糖季铵盐在食品、保健品、医药或日化领域中作为抗氧化剂的应用。
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