CN108854155B - 绿茶多酚的选择性磁性固相萃取方法 - Google Patents
绿茶多酚的选择性磁性固相萃取方法 Download PDFInfo
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Abstract
本发明公开了一种绿茶多酚的选择性磁性固相萃取方法,利用磁性固相萃取吸附剂对绿茶多酚溶液进行吸附,利用磁场力将吸附后的吸附剂分离,解吸附后得到纯化后的绿茶多酚;所述磁性固相萃取吸附剂为以磁性Fe3O4纳米粒子为核,以单宁酸为中间吸附层,以含有酰胺键的聚合物为外壳的含有酰胺键的聚合物吸附剂。本发明利用具有磁性的磁性固相萃取吸附剂对绿茶多酚溶液进行吸附,由于磁性微球表面分布了大量的酰胺键,而酰胺键对酚类物质具有选择性吸附作用,所以利用本发明的磁性微球吸附剂在实现富集的同时,也实现了对多酚的纯化,去除了非酚类杂质。
Description
技术领域
本发明属于食品和药物加工领域,具体涉及一种绿茶多酚的选择性磁性固相萃取方法。
背景技术
绿茶多酚作为绿茶叶中重要的活性成分,具有抑菌保鲜、抗氧化、延缓衰老、抗菌、抗病毒、降血脂、抗癌等功效。绿茶多酚具有优良的抗氧化作用,可通过清除活性氧簇或其反应生成稳定化合物的方式有效平衡人体内自由基,并且其金属离子鳌合能力能终止自由基链式反应。大量的体内及体外实验和流行病学资料表明,茶多酚具有抗炎、降脂、抗糖尿病和心血管疾病(CVD)预防等生物学和药理作用,在制药、生化、日化、食品以及精细化工等高科技领域具有广阔的应用前景。常用的茶多酚提取方法有大孔树脂吸附固相萃取方法,但是吸附后通常需要离心、过滤等操作才能将吸附物质和载体分离出来,操作相对麻烦。
最近发展的超顺磁性纳米材料具有高吸附容量、良好的生物相容性、优异的磁分离性能广受关注。超顺磁性纳米材料具有较高的饱和磁强度、零矫顽力,在外加磁场条件下能有效响应。通过对磁性材料进行核壳结构包裹能够提高磁性颗粒的稳定性,同时引入官能团修饰改性,可以实现其选择性地吸附目标分析物,制备得到磁性固相萃取吸附剂。磁性材料作为固相萃取的吸附剂,萃取时仅通过施加一个外部磁场即可实现吸附剂的分离,因此操作简单、省时快速、无需离心过滤等繁琐操作,避免了传统固相萃取吸附剂存在的操作繁复、柱堵塞的问题。但是传统的磁性颗粒聚合物包裹方法形成效率不高,不能有效在磁性颗粒表面包裹,造成材料浪费、环境污染。导致在对绿茶多酚进行萃取时,萃取效率不高,且提高了萃取成本。
发明内容
本发明提供了一种绿茶多酚的选择性磁性固相萃取方法,该方法利用磁性固相萃取吸附剂对绿茶多酚进行萃取,萃取效率高,操作简单,成本低。
一种绿茶多酚的选择性磁性固相萃取方法,利用磁性固相萃取吸附剂对绿茶多酚溶液进行吸附,利用磁场力将吸附后的吸附剂分离,解吸附后得到纯化后的绿茶多酚;所述磁性固相萃取吸附剂为以磁性Fe3O4纳米粒子为核,以单宁酸为中间吸附层,以含有酰胺键的聚合物为外壳的含有酰胺键的聚合物吸附剂。
作为优选,所述磁性固相萃取吸附剂由下述方法制备得到:
(1)将单宁酸溶液与四氧化三铁纳米颗粒混合,得到单宁酸包覆的磁性纳米颗粒的体系液;
(2)将单体化合物、交联剂、引发剂、乳化剂加入到步骤(1)的体系液中,进行共聚反应;所述的单体化合物为N-乙烯基吡咯烷酮和N-异丙基丙烯酰胺;
(3)反应完成,后处理得到单宁酸引导共聚包覆的磁性固相萃取多酚吸附剂。
作为优选,本发明中,富集前的绿茶多酚溶液中多酚的重量百分比含量为0.1%~10%。进一步优选为0.5%~1%。采用本发明的方法可以针对各种加工方法得到的绿茶多酚溶液进行多酚的选择性富集。绿茶多酚溶液中主要的多酚有表没食子儿茶素、表没食子儿茶素没食子酸酯、表儿茶素没食子酸酯等。
作为优选,磁性微球吸附剂的加入量为绿茶多酚总重量的3~15倍。进一步优选为5~10倍。吸附完成后,可直接采用磁铁快速的将吸附了绿茶多酚的吸附剂收集。然后经过解吸附溶剂解吸附即可,常见的解吸附溶剂为醇,比如可以为甲醇、乙醇或者异丙醇。解吸附后的吸附剂可重复利用,吸附效率基本不受影响。
本发明的磁性固相萃取多酚吸附剂利用单宁酸引导N-乙烯基吡咯烷酮、N-异丙基丙烯酰胺单体的自由基共聚包覆,具有Fe3O4磁性微粒的内核,以及单体共聚交联形成的外壳。
通常磁性颗粒包覆采用磁性颗粒与单体混合物直接共聚,然后将混合物粉碎得到包覆的磁性颗粒。该方法有大量的聚合物存在溶液中,与磁性颗粒表面结合的聚合物较少,聚合物不能有效在磁性颗粒表面形成壳层结构,造成原料大量浪费。为了克服这个困难,本发明中利用单宁酸与磁铁和聚合物单体同时具有的强亲和作用,实现单宁酸导向的共聚包覆,定向形成壳层结构,极大提高包覆效率。
制备过程中首先将单宁酸选择性包覆于四氧化三铁纳米颗粒表面,形成单宁酸包覆的磁性纳米颗粒。然后利用磁性纳米颗粒表面包覆的单宁酸与共聚单体的强氢键作用引导单体富集在磁性纳米颗粒表面。再引发单体自由基共聚,利用吸附在表面的单体使共聚优先发生与磁性纳米颗粒表面,高效率包覆磁性颗粒形成多酚吸附壳层。
作为优选,所述的单宁酸通过酚羟基共价配合作用与四氧化三铁牢固结合,使用的单宁酸的量相对于磁铁的质量比为0.01-0.5:1,优先选择0.05-0.2:1。
作为优选,所述的单体为N-乙烯基吡咯烷酮和N-异丙基丙烯酰胺,所用的摩尔比为1:(0.1-10),优先选择1:(0.1-1)。
作为优选,所述的引发剂、交联剂与单体化合物的摩尔比为(0.1-1):(0.1-1):1。
作为优选,所述单宁酸与单体化合物的质量摩尔比为1:(0.1~5)(g/mol)。
所述单宁酸溶液的溶剂为水或醇。
所述的共聚反应为乳化的自由基聚合反应,所述的引发剂为偶氮二异丁腈或过氧化苯甲酰,所述的反应溶剂为水或醇的水溶液优先采用水为溶剂,所述的交联剂为乙二醇二甲基丙烯酸酯等。
所述醇可选择常见的甲醇、乙醇或者异丙醇。
所述的乳化剂为十二烷基苯磺酸钠、十二烷基硫酸钠、季铵盐等,优先采用十二烷基苯磺酸钠。
本发明相对于现有磁性固相萃取剂制备方法具有如下优点:
(1)本发明采用磁性固相萃取吸附剂,其制备时采用单宁酸导向共聚包覆,包覆效率更好,共聚单体利用率高。
(2)本发明采用的磁性固相萃取剂多酚吸附效率高,磁性响应较高、磁性富集分离简便。
(3)本发明采用的磁性固相萃取吸附剂,其采用的单宁酸、共聚单体,原料来源广泛、价格便宜、制作工艺简便,适用于工业化生产应用
综上所述,本发明利用具有磁性的磁性固相萃取吸附剂对绿茶多酚溶液进行吸附,由于磁性微球表面分布了大量的酰胺键,而酰胺键对酚类物质具有选择性吸附作用,所以利用本发明的磁性微球吸附剂在实现富集的同时,也实现了对多酚的纯化,去除了非酚类杂质。
而且,吸附后可借助磁铁将吸附剂收集,方便而快速;且可通过简单的可溶性溶剂进行解吸附,富集效率大大提高。本发明制备磁性固相萃取吸附剂的原料来源广泛、价格便宜、制作工艺简便,适用于工业化生产应用。
另外,本发明的吸附剂解吸附后,经过简单的处理,吸附剂可以重新套用,降低了吸附剂的使用成本。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
40毫克四氧化三铁纳米颗粒与含2毫克单宁酸的水溶液(1mmol/mL)搅拌混合(搅拌时间10min),将单宁酸包覆于磁性颗粒表面(TLC监测单宁酸全部吸附)。然后依次加入1.2毫升水、N-乙烯基吡咯烷酮(1.33毫摩尔)、N-异丙基丙烯酰胺(0.67毫摩尔)、乙二醇二甲基丙烯酸酯(0.16毫摩尔)、偶氮二异丁腈(0.05毫摩尔)、十二烷基苯磺酸钠(1毫克),充氮气保护。置于热振荡反应器上加热至60摄氏度振荡反应1小时,除去上清液,用乙醇洗涤3次,再用水洗涤5次,得到磁性固相萃取剂颗粒。
实施例2
40毫克四氧化三铁纳米颗粒与含3毫克单宁酸的水溶液(1mmol/mL)搅拌混合(搅拌时间10min),将单宁酸包覆于磁性颗粒表面(TLC监测单宁酸全部吸附)。然后依次加入1.2毫升水、N-乙烯基吡咯烷酮(1.33毫摩尔)、N-异丙基丙烯酰胺(0.8毫摩尔)、乙二醇二甲基丙烯酸酯(0.16毫摩尔)、偶氮二异丁腈(0.05毫摩尔)、十二烷基苯磺酸钠(1.5毫克),充氮气保护。置于热振荡反应器上加热至60摄氏度振荡反应1小时,除去上清液,用乙醇洗涤3次,再用水洗涤5次,得到磁性固相萃取剂颗粒,即磁性固相萃取吸附剂。
实施例3
40毫克四氧化三铁纳米颗粒与含5毫克单宁酸的水溶液(1mmol/mL)搅拌混合(搅拌时间10min),将单宁酸包覆于磁性颗粒表面(TLC监测单宁酸全部吸附)。然后依次加入1.2毫升水、N-乙烯基吡咯烷酮(1.33毫摩尔)、N-异丙基丙烯酰胺(0.8毫摩尔)、乙二醇二甲基丙烯酸酯(0.16毫摩尔)、偶氮二异丁腈(0.05毫摩尔)、十二烷基苯磺酸钠(1毫克),充氮气保护。置于热振荡反应器上加热至60摄氏度振荡反应1小时,除去上清液,用乙醇洗涤3次,再用水洗涤5次,得到磁性固相萃取剂颗粒。
实施例1~3得到的磁性固相萃取剂FT-IR测试数据显示出3300-3500cm-1的N-H伸缩振动峰,1653cm-1特征的酰胺羰基峰。表明酰胺单体成功包覆上了磁性颗粒。磁性测试磁滞回线显示磁性固相萃取剂无剩磁,饱和磁化率为15.0emu/g,表明磁性固相萃取剂为超顺磁性具有优异的磁响应特性。
多酚吸附性能测定数据:使用25g实施例1~3制备得到的磁性固相萃取剂吸附绿茶多酚溶液(浓度为0.5%,1kg,其中主要的多酚有表没食子儿茶素、表没食子儿茶素没食子酸酯、表儿茶素没食子酸酯),吸附解吸附后总多酚含量(纯度)从74%分别升至92%、91%、92%,纯度显著提高。
上述测定过程中,具体吸附解吸附过程为:将设定量的磁性固相萃取剂投入到绿茶多酚溶液中,搅拌15分钟,吸附结束,利用磁铁将吸附后的磁性微球吸附剂收集,洗涤,然后将吸附后的磁性微球吸附剂置于乙醇中,多酚溶于乙醇中,利用磁铁分离解吸附后的磁性微球吸附剂或者直接过滤,乙醇溶液浓缩即得到富集后的绿茶多酚;洗涤后的吸附剂可直接晾干后回用。
回收套用实验:
利用实施例1制备得到的磁性微球吸附剂,分别对三批浓度为1%绿茶多酚提取液(总多酚纯度为74%)进行富集,回用三次后,得到的绿茶多酚的纯度均在90%以上(分别为91%、91%、90%),吸附剂富集能力没有明显下降。
Claims (4)
1.一种绿茶多酚的选择性磁性固相萃取方法,其特征在于,利用磁性固相萃取吸附剂对绿茶多酚溶液进行吸附,利用磁场力将吸附后的吸附剂分离,解吸附后得到纯化后的绿茶多酚;所述磁性固相萃取吸附剂为以磁性Fe3O4纳米粒子为核,以单宁酸为中间吸附层,以含有酰胺键的聚合物为外壳的含有酰胺键的聚合物吸附剂;
所述磁性固相萃取吸附剂由下述方法制备得到:
(1)将单宁酸溶液与四氧化三铁纳米颗粒混合,得到单宁酸包覆的磁性纳米颗粒的体系液;
(2)将单体化合物、交联剂、引发剂、乳化剂加入到步骤(1)的体系液中,进行共聚反应;所述的单体化合物为N-乙烯基吡咯烷酮和N-异丙基丙烯酰胺;
(3)反应完成,后处理得到单宁酸引导共聚包覆的磁性固相萃取多酚吸附剂;
所述的N-乙烯基吡咯烷酮和N-异丙基丙烯酰胺的摩尔比为1:
(0.1-10);所述单宁酸与磁铁的质量比为(0.01-0.5):1;所述单宁酸与单体化合物的质量摩尔比为1:(0.1~5)(g/mol);
所述的引发剂为偶氮二异丁腈或过氧化苯甲酰;所述的交联剂为乙二醇二甲基丙烯酸酯;所述的乳化剂为十二烷基苯磺酸钠、十二烷基硫酸钠、季铵盐中的一种或多种;
所述的引发剂、交联剂与单体化合物的摩尔比为(0.1-1):(0.1-1):1。
2.根据权利要求1所述的绿茶多酚的选择性磁性固相萃取方法,其特征在于,所述单宁酸溶液的溶剂以及聚合反应的溶剂为醇或水。
3.根据权利要求1所述的绿茶多酚的选择性磁性固相萃取方法,其特征在于,富集前的绿茶多酚溶液中多酚的重量百分比含量为0.1%~10%。
4.根据权利要求1所述的绿茶多酚的选择性磁性固相萃取方法,其特征在于,磁性微球吸附剂的加入量为绿茶多酚总重量的3~15倍。
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