CN112876582A - 含硫醚结构的壳寡糖-半胱氨酸缀合物及其制备法和用途 - Google Patents
含硫醚结构的壳寡糖-半胱氨酸缀合物及其制备法和用途 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种含硫醚键结构的壳寡糖-半胱氨酸缀合物及其制备方法和生物活性。
背景技术
壳寡糖(Chitosan Oligosaccharides,COS)是壳聚糖经过降解后得到的聚合度为2~20,分子量≤3200Da的氨基寡糖。壳寡糖具有良好的水溶性,易于发生各类化学反应,但是其本身的抗氧化性较弱,严重阻碍了其在工业上的应用,壳寡糖分子结构中含有氨基与羟基这2个活性基团,C-2位的氨基活性最强,其次为C-6上的伯羟基,活性最低的为C-3位的仲羟基,这是因为该位置空间位阻最大。可以通过分子设计引入新的活性基团,增强壳寡糖的抗氧化效果,扩大壳寡糖的应用范围,提升其生物活性。
Click反应即点击化学,是由美国化学家巴里·夏普莱斯等人在2001年引入的一个合成概念,借助形成C-杂原子,高效的完成基团之间拼接。Click反应存在下述4大类型:①不饱和键环加成反应;②亲电杂环开环反应;③非醇醛羰基化学反应;④碳碳多重键加成反应。这一反应对药物的开发和合成具有重要的意义,其中巯基和双键之间的反应是点击化学的重要组成部分。
目前,Click反应中大部分类型已经广泛应用于壳寡糖的化学改性中,但是巯基-烯烃点击反应在壳寡糖化学改性中的研究比较少。
目前现有的由壳寡糖/壳聚糖改性得到的具有较强生物活性的衍生物的结构式为:
壳寡糖衍生物1的n大于20;壳寡糖衍生物2和3的n为2~20;其相应性能仍然有待改进。
发明内容
本发明要解决的问题是提供一种具有抗氧化活性和热稳定性能的含硫醚结构的壳寡糖-半胱氨酸缀合物极其制备方法和用途。
为了解决上述问题,本发明提供一种具有抗氧化活性和热稳定性能的含硫醚结构的壳寡糖-半胱氨酸缀合物,其具有如下结构通式Ⅰ:
结构通式Ⅰ中,n为2~20。
说明:没有取代的部分R为H。
本发明还同时提供了含硫醚结构的壳寡糖-半胱氨酸缀合物的制备方法,利用壳寡糖制备而得的N,O-烯丙基壳寡糖(N,O-烯丙基壳寡糖衍生物),将N,O-烯丙基壳寡糖溶于乙酸水溶液中,于惰性气体保护下,加入L-半胱氨酸和过硫酸钾,于室温搅拌反应10±2h,然后加入无水乙醇使产物沉淀;所述L-半胱氨酸:N,O-烯丙基壳寡糖衍生物=1~4:1(优选3:1)的质量比;每1g的N,O-烯丙基壳寡糖配用50±5mg过硫酸钾;
所得的沉淀用去离子水透析,冷冻干燥,得到含硫醚键结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys)。
作为本发明的含硫醚结构的壳寡糖-半胱氨酸缀合物的制备方法的改进:
所述壳寡糖为分子量800~1000Da,脱乙酰度85%~90%。
乙酸水溶液中,乙酸的体积浓度为1%;
每1g的N,O-烯丙基壳寡糖配用的乙酸水溶液的体积用量为40±10mL。
本发明还同时提供了上述含硫醚结构的壳寡糖-半胱氨酸缀合物的用途,其特征是:用作抗氧化剂,应用于保健品或化妆品领域。
本发明的含硫醚结构的壳寡糖-半胱氨酸缀合物较壳寡糖有更好的稳定性。
本发明通过二步反应把L-半胱氨酸引入壳寡糖分子结构中,经活性测试发现具有良好的抗氧化活性,这可能与壳寡糖和L-半胱氨酸双重协同作用有关。
本发明的壳寡糖-半胱氨酸缀合物(壳寡糖衍生物)的制备路线为:
1)、壳寡糖与烯丙基溴反应生成N,O-烯丙基壳寡糖衍生物采用文献方法制备(Solvent-free synthesis and characterization of allyl chitosanderivatives.RSC advances 2019,9(36),20968-20975)。
在碱性条件下,壳寡糖和丙烯基溴反应,在氨基和羟基上引入烯丙基,形成N,O-烯丙基壳寡糖衍生物。
图1为原料壳寡糖(COS)、中间产物N,O-烯丙基壳寡糖衍生物(COS-Bro)的红外光谱图;其中,3483cm-1处的宽峰为壳寡糖上O-H和N-H伸缩振动叠加吸收峰,2926cm-1处的特征吸收峰可归属于壳寡糖上的-CH2和乙酰基上-CH3的伸缩振动吸收峰。1624cm-1归属为酰胺Ⅰ上C=O伸缩振动,1317cm-1归属为壳寡糖上C-N键的弯曲振动吸收峰,1155cm-1为C-O-C氧桥的不对称伸缩振动峰,1079cm-1和1038cm-1处的特征吸收峰为壳寡糖上C-O的伸缩振动峰。N,O-烯丙基壳寡糖的红外光谱图显示,产物在1647cm-1的强峰和在1608cm-1处的弱峰是双键取代了两个面内弯曲特征峰,而在922cm-1处出现的新峰是由于烯烃上的C-H伸缩振动引起的特征吸收峰。
2)、含硫醚结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys)的合成。
图2为N,O-烯丙基壳寡糖衍生物(COS-Bro)、L-半胱氨酸(Cys)发明所得产物含硫醚结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys)的红外光谱图;
其中,COS-Bro-Cys在1647cm-1和722cm-1处的C=C特征吸收峰明显消失,在1515cm-1出现了羧基上的C-O特征吸收峰,且强度明显增强,在622cm-1处产生了S-C弱尖峰,这些峰值的变化证明了目标产物的形成。
图3为壳寡糖和COS-Bro-Cys的热重图。
对于壳寡糖,第一阶段失重在30~100℃,热失重率为7%;第二阶段失重主要在180~327℃,热失重率为52%,在第二热分解区间出现了最快降解速率的温度Tmax=207℃。与壳寡糖相比,COS-Bro-Cys也有两个阶段的热失重阶段,在100℃之间的第一阶段,失重率约为4%;在180~327℃第二个热分解区间,COS-Bro-Cys的失重率为79%,最大失重率在Tmax=226℃。以上分析得知,COS-Bro-Cys较原料壳寡糖,其热稳定性明显提高。
本发明制备所得的含硫醚结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys),具有良好的抗氧化活性和热稳定性。
综上所述,本发明提供一种基于巯基-烯点击反应的壳寡糖衍生物的制备方法,并为提高壳寡糖的抗氧化活性提供一条新途径。以巯基-烯烃点击反应为理论依据,通过亚结构拼接,成功在壳寡糖的氨基和羟基引入硫醇类结构的化合物,从而制备具有良好抗氧化活性的N,O-硫醚壳寡糖衍生物。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细说明。
图1为原料壳寡糖(COS)、中间产物N,O-烯丙基壳寡糖衍生物(COS-Bro)的红外光谱图;
图2为N,O-烯丙基壳寡糖衍生物(COS-Bro)、L-半胱氨酸和本发明所得产物含硫醚结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys)的红外光谱图;
图3为壳寡糖和COS-Bro-Cys的热重图;
A:失重百分数;B:质量变化率。
图4壳寡糖和N,O硫醚壳寡糖的DPPH自由基清除活性。
图5壳寡糖和N,O硫醚壳寡糖的羟自由基清除活性。
图6壳寡糖和N,O硫醚壳寡糖的ABTS自由基清除活性。
图7壳寡糖和N,O硫醚壳寡糖对Fe3+的还原力。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
乙酸水溶液(1%)中,乙酸的体积浓度为1%。
以下案例中,所用的N,O-烯丙基壳寡糖衍生物为:
由分子量800~1000Da,脱乙酰度85%~90%的壳寡糖制备,为非完全取代,因此R’为H或烯丙基,n为2-20,在壳寡糖的羟基和氨基上都引入了烯丙基。
实施例1、
称取1g N,O-烯丙基壳寡糖溶于40mL乙酸水溶液(1%)中,磁力搅拌,直到完全溶解,连接氮气装置,使反应体系充满氮气,后加入1g L-半胱氨酸和50mg过硫酸钾,室温搅拌10h,然后加入过量的无水乙醇(约200ml)使产物沉淀,抽滤使固液分离。
将得到的固体沉淀溶于少量水后用纤维素透析袋(截留分子量500)在去离子水中透析48h,冷冻干燥(-60℃干燥24小时),得到含硫醚键结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys)。终产物的得率为46%,取代度为0.32。
含硫醚键结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys):
含硫醚键结构的壳寡糖-半胱氨酸缀合物得率的计算公式为
含硫醚键结构的壳寡糖-半胱氨酸缀合物取代度计算公式为
其中X为取代度。
实施例2、
将实施例1中L-半胱氨酸的质量由“1g”更改为“2g”,其余均等同于实施例1。终产物的得率为66%,取代度为0.54。
实施例3、
将实施例1中L-半胱氨酸的质量由“1g”更改为“3g”,其余均等同于实施例1。终产物的得率为82%,取代度为0.67。
实施例4、
将实施例1中L-半胱氨酸的质量由“1g”更改为“4g”,其余均等同于实施例1。终产物的得率为82%,取代度为0.69。
比较实施例1~4,当N,O-烯丙基壳寡糖与L-半胱氨酸质量比由1:1上升至1:3时,取代度由0.32上升至0.67,得率由46%上升至82%。继续增大二者的质量比,得率和取代度均没有显著提高。因此,该反应的质量比为1:3时,是反应的最佳比值。
实施例2~实施例4的产物结构式,同实施例1。
将实施例3得到的含硫醚键结构的壳寡糖-半胱氨酸缀合物(COS-Bro-Cys)用于抗氧化活性分析。通过测定壳寡糖衍生物对DPPH自由基、羟基自由基和ABTS自由基的清除率,以及还原力来评价其抗氧化活性。
实验1、DPPH自由基清除率的测定
参考文献方法(Jie Xu,Li-Li Xu,Qin-Wei Zhou,Shu-Xian Hao,Tao Zhou,Hu-Jun Xie.Enhanced in vitro antioxidant activity of polysaccharides fromEnteromorpha prolifera by enzymatic degradation,Journal of Food Biochemistry2016,40,275–283.)
进行测定。
由图4可知,壳寡糖和N,O-硫醚壳寡糖都展示出了与浓度正相关的DPPH自由基清除活性,相较于壳寡糖,COS-Bro-Cys的DPPH自由基清除能力有了大幅度提升。当COS-Bro-Cys剂量为0.02mg/mL时,清除率为42.80%,远高于壳寡糖的5.46%。COS和COS-Bro-Cys清除DPPH自由基的IC50值分别为0.66和0.031mg/mL,原料壳寡糖的DPPH自由基清除的IC50值是COS-Bro-Cys的21.2倍。
实验2、羟基自由基清除率的测定
参考文献方法(Mei-Jia Shi,Xiaoyi Wei,Jie Xu,Bing-Jie Chen,De-Yin Zhao,Shuai Cui,Tao Zhou.Carboxymethylated Degraded Polysaccharides fromEnteromorpha prolifera:Preparation and in Vitro Antioxidant Activity.FoodChemistry 2017,215,76–83.)进行测定。
由图5可知,COS和COS-Bro-Cys在浓度为1.0mg/mL时的清除率分别为25.27%和32.36%,IC50值分别为1.41和1.22mg/mL。
实验3、ABTS自由基清除率的测定
参考文献方法(Xiaoli Liu,Qixing Jiang,Wenshui Xia.One-step procedurefor enhancing the antibacterial and antioxidant properties of apolysaccharide polymer:Kojic acid grafted onto chitosan.International Journalof Biological Macromolecules 2018,113,1125-1133.)进行测定。
由图6可知,壳寡糖(COS)和N,O-硫醚壳寡糖也都表现出良好的ABTS自由基清除活性且与浓度呈正相关。在其测试浓度范围内COS-Bro-Cys清除率快速上升,当COS-Bro-Cys浓度为0.1mg/mL,其清除率达到83.85%,已经超过了对ABTS自由基的半数清除率。COS和COS-Bro-Cys对ABTS自由基清除率的IC50值分别为2.89和0.047mg/mL,说明COS-Bro-Cys的ABTS自由基清除能力比COS强得多。COS对ABTS清除率在浓度1mg/mL时也仅为15.23%,仍未达到半数清除率。
实验4、还原力的测定
参考文献方法(Yen G,Chen H.Antioxidant activity of various teaextracts in relation to their antimutagenicity[J].Journal of Agricultural andFood Chemistry,1995,43:27-32.)进行测定。
由图7可知,COS、COS-Bro-Cys和Vc的还原力大小为:Vc﹥COS-Bro-Cys﹥COS。
壳寡糖衍生物对三种自由基都表现出良好的清除能力,它们对DPPH、羟基和ABTS自由基的清除活性远强于壳寡糖(表1)。
表1.壳寡糖和壳寡糖衍生物的自由基清除活性(IC50(mg/mL))
将实施例1、实施例2所得产物以及壳寡糖衍生物1~壳寡糖衍生物3按照上述方法进行检测,就ABTS自由基的半数清除浓度(IC50)而言:实施例1所得的COS-Bro-Cys的IC50约为0.15mg/mL,实施例2所得的COS-Bro-Cys的IC50为0.09mg/mL。而壳寡糖衍生物1~壳寡糖衍生物3的IC50效果最佳的仅约为1mg/mL。
最后,还需要注意的是,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (4)
2.如权利要求1所述的含硫醚结构的壳寡糖-半胱氨酸缀合物的制备方法,利用壳寡糖制备而得的N,O-烯丙基壳寡糖,其特征是:
将N,O-烯丙基壳寡糖溶于乙酸水溶液中,于惰性气体保护下,加入L-半胱氨酸和过硫酸钾,于室温搅拌反应10±2h,然后加入无水乙醇使产物沉淀;所述L-半胱氨酸:N,O-烯丙基壳寡糖衍生物=1~4:1的质量比;每1g的N,O-烯丙基壳寡糖配用50±5mg过硫酸钾;
所得的沉淀用去离子水透析,冷冻干燥,得到含硫醚键结构的壳寡糖-半胱氨酸缀合物COS-Bro-Cys。
3.如权利要求2所述的含硫醚结构的壳寡糖-半胱氨酸缀合物的制备方法,所述壳寡糖为分子量800~1000Da,脱乙酰度85%~90%。
4.如权利要求1所述的含硫醚结构的壳寡糖-半胱氨酸缀合物的用途,其特征是:用作抗氧化剂。
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