CN114853922A - 一种硫辛酰基壳聚糖季铵盐及其制备方法和应用 - Google Patents
一种硫辛酰基壳聚糖季铵盐及其制备方法和应用 Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
Description
技术领域
本发明涉及日化领域及医药行业,具体是一种硫辛酰基壳聚糖季铵盐及其制备方法和应用。
背景技术
壳聚糖(chitosan)是甲壳素在碱性条件下脱去乙酰基而得到的高分子糖类化合物,化学结构式为(C6H11NO4)n,是由D-氨基葡萄糖脱去水分子后经β-1,4-糖苷键连接在一起所形成的共价聚合物。壳聚糖含量丰富,作为一种可再生、无毒副作用,生物相容性和生物可降解性良好的多糖,具有很多独特的生理、药理功能性质,如具有抑菌、抗氧化活性,被广泛应用于医药、食品、农业、日化、环保等多种行业领域中。然而,由于壳聚糖在水以及有机溶剂中的溶解性比较差,严重影响了壳聚糖的使用范围和应用价值,因此对壳聚糖的各种化学和物理修饰处理成为解决其溶解性差和活性低的有效方法和壳聚糖高值化开发利用的新热点。
硫辛酸(lipoic acid),分子式为C8H14O2S2,属于B族维生素中的一类化合物,可作为辅酶参与机体内的物质代谢中的酰基转移,能消除导致加速老化与致病的自由基,具有抗氧化、抗衰老、提高免疫、预防心血管疾病、缓解糖尿病症状等多种作用。在抗氧化食品兴起的当下,硫辛酸正在由传统的药用向食用过渡,鉴于其强大的保健功能,2004年6月日本厚劳省将其从药品改分类到食品,此外,美国、加拿大等地区都将硫辛酸列为膳食补充剂。但硫辛酸其水溶性较差,在水系体系中其抗氧化活性无法高效地表达表现出来。
壳聚糖季铵盐是一种水溶性的壳聚糖衍生物,通过将硫辛酸接枝到壳聚糖季铵盐分子链中,既可以提高硫辛酸的水溶性,便于其更高效地发挥其生物活性,也可以提高壳聚糖季铵盐的抗氧化活性。
发明内容
本发明目的是提供一种具有较强抗氧化活性的硫辛酰基壳聚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:
一种硫辛酰基壳聚糖季铵盐,硫辛酰基壳聚糖季铵盐结构式如式(1)所示,
其中,x为硫辛酰基取代度0.1-1.0,式(1)聚合度取值范围是20-4000。
一种硫辛酰基壳聚糖季铵盐的制备方法:
首先用苯甲醛通过席夫碱反应保护壳聚糖的氨基,而后直接与环氧丙基三甲基氯化铵反应得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱,而后用盐酸脱除苯甲醛的保护得到O-2-羟丙基-3-三甲基氯化铵壳聚糖,所得O-2-羟丙基-3-三甲基氯化铵壳聚糖再与硫辛酸反应即得式(1)所示产物硫辛酰基壳聚糖季铵盐;
所述苯甲醛的摩尔量为壳聚糖摩尔量的1.0-3.0倍;环氧丙基三甲基氯化铵的摩尔量为壳聚糖苯甲醛席夫碱摩尔量的1.0-3.0倍;盐酸的摩尔量为O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱摩尔量的4.0-8.0倍;硫辛酸的摩尔量为O-2-羟丙基-3-三甲基氯化铵壳聚糖摩尔量的1.0-3.0倍。
所述苯甲醛通过席夫碱反应保护壳聚糖的氨基,即实现获得壳聚糖席夫碱,所示壳聚糖苯甲醛席夫碱为将壳聚糖溶解于乙酸水溶液中,滴加入壳聚糖摩尔量1.0-3.0倍的苯甲醛乙醇溶液,在20-30℃条件下反应12-24h。经乙醇沉淀、洗涤、离心、水洗,冷冻干燥,待用。
所述O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱为将氨基保护的壳聚糖分散于异丙醇中,在50-60℃条件下溶胀1-3h,而后加入壳聚糖苯甲醛席夫碱摩尔量1.0-3.0倍的环氧丙基三甲基氯化铵,在70-90℃条件下回流反应24-48h,经乙醇沉淀、洗涤,冷冻干燥,水透析,即得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱待用。
所述O-2-羟丙基-3-三甲基氯化铵壳聚糖为将O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱加入到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱摩尔量4.0-8.0倍的稀盐酸水溶液中,20-30℃条件下反应48-72h。而后用氢氧化钠水溶液调整pH至中性,水透析,冷冻干燥后,即得到O-2-羟丙基-3-三甲基氯化铵壳聚糖待用。
所述O-2-羟丙基-3-三甲基氯化铵壳聚糖与O-2-羟丙基-3-三甲基氯化铵壳聚糖摩尔量1.0-3.0倍的硫辛酸在1-乙基-(3-二甲基氨基丙基)碳酰二亚胺/N-羟基琥珀酰亚胺的催化下,20-40℃反应24-48h,水透析,冷冻干燥后,用乙醇洗涤固体,再冷冻干燥,即得到硫辛酰基壳聚糖季铵盐。
一种硫辛酰基壳聚糖季铵盐的应用,所述式(1)所示的硫辛酰基壳聚糖季铵盐在制备抗氧化剂中的应用。
本发明所具有的优点:
本发明所得硫辛酰基壳聚糖季铵盐是O-季铵化壳聚糖与硫辛酸在催化剂作用下得到的。所得硫辛酰基壳聚糖季铵盐在制备以及生物活性方面都表现出了很好的优势,具体为:
(1)本发明制备的硫辛酰基壳聚糖季铵盐生物活性得到极大提高,例如:抗氧化活性。
(2)本发明合成步骤简单、所需设备及原料易得、成本较低、易于推广,而且本产品产率较高,可达60%以上。本发明所得产品可广泛用于生物、医药、食品、化工等领域。
附图说明
图1为壳聚糖的红外光谱图。
图2为本发明实施例提供壳聚糖苯甲醛席夫碱的红外谱图,从图2可知与壳聚糖原料相比,1642.48cm-1处的吸收峰为C=N键的吸收峰,1580.46、1452.48、756.37、693.53cm-1处为苯环的吸收峰,表明壳聚糖苯甲醛席夫碱已合成成功。
图3为本发明实施例提供O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱的红外谱图,与壳聚糖苯甲醛席夫碱相比,1476.25cm-1处的吸收峰为季铵盐的吸收峰,表明O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱已合成成功。
图4为本发明实施例提供O-2-羟丙基-3-三甲基氯化铵壳聚糖的红外谱图,与图3相比,1642.48cm-1处C=N键的吸收峰消失,1580.46、1452.48、756.37、693.53cm-1处苯环的吸收峰消失,表明O-2-羟丙基-3-三甲基氯化铵壳聚糖已合成成功。
图5为本发明实施例提供硫辛酰基壳聚糖季铵盐的红外谱图,其与图4O-2-羟丙基-3-三甲基氯化铵壳聚糖相比,2927.35和2865.75cm-1处的吸收峰为硫辛酰基上饱和C-H的吸收峰,1727.40和1646.26cm-1处的吸收峰为酯羰基和酰胺羰基的吸收峰,因此可以证明硫辛酰基通过与部分壳聚糖分子反应连入到了壳聚糖结构中,硫辛酰基壳聚糖季铵盐合成成功。
具体实施方式
下面结合符合和实施例对本发明作进一步的解释说明。
本发明首先用苯甲醛通过席夫碱反应保护壳聚糖的氨基,而后直接与环氧丙基三甲基氯化铵反应得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱,反应物用盐酸脱除苯甲醛的保护得到O-2-羟丙基-3-三甲基氯化铵壳聚糖,所得O-2-羟丙基-3-三甲基氯化铵壳聚糖再与硫辛酸反应即得硫辛酰基壳聚糖季铵盐。
上述所得硫辛酰基壳聚糖季铵盐具有DPPH自由基清除能力和还原能力。
硫辛酰基壳聚糖季铵盐的合成路线如下:
其中,x为硫辛酰基取代度0.1-1.0,式(1)聚合度取值范围是20-4000。
实施例1
本实施例按以上合成路线合成目标化合物硫辛酰基壳聚糖季铵盐。
1)壳聚糖苯甲醛席夫碱的制备:3.22g壳聚糖(参见图1,平均聚合度n取值范围是20-1000)溶于100mL 2%乙酸水溶液中,搅拌至全溶后,加入150mL的无水乙醇获得壳聚糖溶液。而后量取6.13mL苯甲醛溶于50mL无水乙醇中,滴加入上述壳聚糖溶液中。室温下搅拌反应12h。而后用800mL无水乙醇沉淀、洗涤、水洗、离心,冷冻干燥,得到壳聚糖苯甲醛席夫碱(参见图2)3.92g,备用。
2)O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱的制备:2.49g壳聚糖苯甲醛席夫碱(参见图2)于40mL异丙醇中,55℃条件下搅拌溶胀2h。而后加入4.55g环氧丙基三甲基氯化铵,在80℃条件下反应24h。反应后用400mL无水乙醇沉淀、洗涤,水透析,冷冻干燥,得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱(参见图3)2.85g,备用。
3)O-2-羟丙基-3-三甲基氯化铵壳聚糖的制备:4.01g O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱(参见图3)加到200mL 0.5M的盐酸水溶液中,室温下搅拌反应48h。反应结束后,用1M氢氧化钠调节pH至中性,水透析,真空冷冻干燥,即得O-2-羟丙基-3-三甲基氯化铵壳聚糖(参见图4)2.42g,备用。
4)硫辛酰基壳聚糖季铵盐的制备:0.78g O-2-羟丙基-3-三甲基氯化铵壳聚糖(参见图4)于25mL去离子水中。1.54g硫辛酸溶于9mL N,N-二甲基甲酰胺中,加入1.44g 1-乙基-(3-二甲基氨基丙基)碳酰二亚胺,室温下搅拌反应0.5h,再于冰浴下加入0.86g N-羟基琥珀酰亚胺继续反应1h,同时加入10mL二甲基亚砜。将硫辛酸的活化溶液滴加入O-2-羟丙基-3-三甲基氯化铵壳聚糖水溶液中,室温下反应24h。水透析,冷冻干燥,乙醇洗涤,冷冻干燥,得到目标产物式(1)所示的硫辛酰基壳聚糖季铵盐(参见图5)。
实施例2
与实施例1不同之处在于:
1)壳聚糖苯甲醛席夫碱的制备:3.22g壳聚糖(参见图1,平均聚合度n取值范围是20-2000)溶于100mL 2%乙酸水溶液中,搅拌至全溶后,加入150mL无水乙醇。而后量取2.04mL苯甲醛溶于50mL无水乙醇中,滴加入上述壳聚糖溶液中。室温下搅拌反应24h。而后用1000mL无水乙醇沉淀、洗涤、水洗、离心,冷冻干燥,得到壳聚糖苯甲醛席夫碱(参见图2)3.46g,备用。
2)O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱的制备:2.49g壳聚糖苯甲醛席夫碱(参见图2)于50mL异丙醇中,50℃条件下搅拌溶胀3h。而后加入1.52g环氧丙基三甲基氯化铵,在80℃条件下反应48h。而后用500mL无水乙醇沉淀、洗涤,水透析,冷冻干燥,得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱(参见图3)2.66g,备用。
3)O-2-羟丙基-3-三甲基氯化铵壳聚糖的制备:4.01g O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱(参见图3)加到100mL 0.5M的盐酸水溶液中,室温下搅拌反应72h。反应结束后,用1M氢氧化钠调节pH至中性,水透析,真空冷冻干燥,即得O-2-羟丙基-3-三甲基氯化铵壳聚糖(参见图4)2.51g,备用。
4)硫辛酰基壳聚糖季铵盐的制备:0.78g O-2-羟丙基-3-三甲基氯化铵壳聚糖(参见图4)于20mL去离子水中。0.51g硫辛酸溶于3mL N,N-二甲基甲酰胺中,加入0.48g 1-乙基-(3-二甲基氨基丙基)碳酰二亚胺,室温下搅拌反应1h,再于冰浴下加入0.29g N-羟基琥珀酰亚胺继续反应1h,同时加入5mL二甲基亚砜。将硫辛酸的活化溶液滴加入O-2-羟丙基-3-三甲基氯化铵壳聚糖水溶液中,室温下反应48h。水透析,冷冻干燥,乙醇洗涤,冷冻干燥,得到目标产物式(1)所示的硫辛酰基壳聚糖季铵盐(参见图5)。
实施例3
与实施例1不同之处在于:
1)壳聚糖苯甲醛席夫碱的制备:3.22g壳聚糖(参见图1,平均聚合度n取值范围是20-4000)溶于100mL 2%乙酸水溶液中,搅拌至全溶后,加入150mL无水乙醇。而后量取4.09mL苯甲醛溶于50mL无水乙醇中,滴加入上述壳聚糖溶液中。室温下搅拌反应12h。而后用900mL无水乙醇沉淀、洗涤、水洗、离心,冷冻干燥,得到壳聚糖苯甲醛席夫碱(参见图2)3.72g,备用。
2)O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱的制备:2.49g壳聚糖苯甲醛席夫碱(参见图2)于50mL异丙醇中,60℃条件下搅拌溶胀1h。而后加入3.03g环氧丙基三甲基氯化铵,在70℃条件下反应48h。而后用500mL无水乙醇沉淀、洗涤,水透析,冷冻干燥,得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱(参见图3)2.69g,备用。
3)O-2-羟丙基-3-三甲基氯化铵壳聚糖的制备:4.01g O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱(参见图3)加到150mL 0.5M的盐酸水溶液中,室温下搅拌反应48h。反应结束后,用1M氢氧化钠调节pH至中性,水透析,真空冷冻干燥,即得O-2-羟丙基-3-三甲基氯化铵壳聚糖(参见图4)2.35g,备用。
4)硫辛酰基壳聚糖季铵盐的制备:0.78g O-2-羟丙基-3-三甲基氯化铵壳聚糖(参见图4)于30mL去离子水中。1.03g硫辛酸溶于6mL N,N-二甲基甲酰胺中,加入0.96g 1-乙基-(3-二甲基氨基丙基)碳酰二亚胺,室温下搅拌反应1h,再于冰浴下加入0.58g N-羟基琥珀酰亚胺继续反应2h,同时加入6mL二甲基亚砜。将硫辛酸的活化溶液滴加入O-2-羟丙基-3-三甲基氯化铵壳聚糖水溶液中,室温下反应48h。水透析,冷冻干燥,乙醇洗涤,冷冻干燥,得到目标产物式(1)所示的硫辛酰基壳聚糖季铵盐(参见图5)。
应用例1
清除DPPH自由基能力的测定:
分别将壳聚糖以及实施例1中制备的O-2-羟丙基-3-三甲基氯化铵壳聚糖和硫辛酰基壳聚糖季铵盐经去离子水溶解配制成10mg/mL相应母液样品,再经过去离子水稀释按照表1中记载配制不同样品浓度,而后分别取表1中配制的不同浓度的样品溶液1mL、DPPH2mL(配制DPPH:称取35.49mg DPPH加无水乙醇定溶至500mL),于试管中加塞振摇混匀,放置20min后,测定样品在517nm处的吸光度,空白组将采用1mL蒸馏水代替供试样品,对照组将采用2mL无水乙醇替代2mL DPPH(注:被测样品均测三次,取平均值)。
清除DPPH自由基能力(%)=1-[(A样品517nm-A对照517nm)/A空白517nm]×100
表1,不同浓度的样品的清除DPPH自由基的能力(%)
应用例2
还原能力的测定:
分别将壳聚糖以及实施例1中制备的O-2-羟丙基-3-三甲基氯化铵壳聚糖和硫辛酰基壳聚糖季铵盐经去离子水溶解配制成10mg/mL相应母液样品,经过去离子水稀释按照表2记载的不同样品浓度,分别取表2记载不同浓度样品各取1mL、铁***溶液1mL(配制磷酸缓冲液:分别取14.33g Na2HPO4·12H2O、24.96g NaH2PO4·2H2O,加水定溶至1000mL;配制铁***:1g铁***加磷酸缓冲液定容至100mL),加入至各试管中混匀,在50℃水浴中反应20min后,加三氯乙酸溶液1mL(配制三氯乙酸:10g三氯乙酸加磷酸缓冲液定容至100mL)终止反应。在3000r/min转速下离心,取上清液1.5mL,再加入去离子水1.2mL、氯化铁溶液0.3mL(配制氯化铁溶液:0.1g氯化铁加磷酸缓冲液定容至100mL),于试管中加塞振摇混匀,避光放置10min后,测定各样品在700nm处的吸光度。吸光度越高,还原能力越强。
表2,不同浓度的样品的还原能力
实验结果:本发明所合成的硫辛酰基壳聚糖季铵盐与壳聚糖的DPPH自由基清除能力和还原能力如表1和2所示,本发明所合成的O-2-羟丙基-3-三甲基氯化铵壳聚糖的DPPH自由基清除能力和还原能力与壳聚糖相当,都比较弱。硫辛酸的引入,增强了衍生物的DPPH自由基清除能力和还原能力,并且随着浓度的增加,DPPH自由基和还原能力随之增强,在最大测试浓度1.6mg/mL浓度下最强,硫辛酰基壳聚糖季铵盐的DPPH自由基是O-2-羟丙基-3-三甲基氯化铵壳聚糖的10倍,说明硫辛酸是一种高效的抗氧化活性基团。
Claims (5)
2.一种权利要求1所述的硫辛酰基壳聚糖季铵盐的制备方法,其特征在于:
首先用苯甲醛通过席夫碱反应保护壳聚糖的氨基,而后直接与环氧丙基三甲基氯化铵反应得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱,而后用盐酸脱除苯甲醛的保护得到O-2-羟丙基-3-三甲基氯化铵壳聚糖,所得O-2-羟丙基-3-三甲基氯化铵壳聚糖再与硫辛酸反应即得式(1)所示产物硫辛酰基壳聚糖季铵盐;
所述苯甲醛的摩尔量为壳聚糖摩尔量的1.0-3.0倍;环氧丙基三甲基氯化铵的摩尔量为壳聚糖苯甲醛席夫碱摩尔量的1.0-3.0倍;盐酸的摩尔量为O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱摩尔量的4.0-8.0倍;硫辛酸的摩尔量为O-2-羟丙基-3-三甲基氯化铵壳聚糖摩尔量的1.0-3.0倍。
3.按权利要求2所述的硫辛酰基壳聚糖季铵盐的制备方法,其特征在于:所述O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱为将氨基保护的壳聚糖分散于异丙醇中,在50-60℃条件下溶胀1-3h,而后加入壳聚糖苯甲醛席夫碱摩尔量1.0-3.0倍的环氧丙基三甲基氯化铵,在70-90℃条件下回流反应24-48h,经乙醇沉淀、洗涤,冷冻干燥,水透析,即得到O-2-羟丙基-3-三甲基氯化铵壳聚糖苯甲醛席夫碱待用。
4.按权利要求2所述的硫辛酰基壳聚糖季铵盐的制备方法,其特征在于:所述O-2-羟丙基-3-三甲基氯化铵壳聚糖与O-2-羟丙基-3-三甲基氯化铵壳聚糖摩尔量1.0-3.0倍的硫辛酸在1-乙基-(3-二甲基氨基丙基)碳酰二亚胺/N-羟基琥珀酰亚胺的催化下,20-40℃反应24-48h,水透析,冷冻干燥后,用乙醇洗涤固体,再冷冻干燥,即得到硫辛酰基壳聚糖季铵盐。
5.一种权利要求1所述的硫辛酰基壳聚糖季铵盐的应用,其特征在于:所述式(1)所示的硫辛酰基壳聚糖季铵盐在制备抗氧化剂中的应用。
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