CN113861358A - 磁性穿心莲内酯印迹聚合物及其制备方法和应用 - Google Patents
磁性穿心莲内酯印迹聚合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种磁性穿心莲内酯印迹聚合物及其制备方法和应用,制备方法包括:将穿心莲内酯和单体加入有机溶剂中预组装,再加入至含有改性的Fe3O4磁性纳米颗粒的反相微乳体系中,最后加入交联剂和引发剂,于30~60℃聚合反应25~28h,然后除去穿心莲内酯,制得磁性穿心莲内酯印迹聚合物。本发明制得的磁性穿心莲内酯印迹聚合物对穿心莲吸附速度较快,在短时间内即可达到吸附平衡,且本发明制得的聚合物具有很好的磁性,应用该聚合物提取分离穿心莲内酯时,操作更为简便,且实现了选择性分离,得到了较高的回收率。
Description
技术领域
本发明涉及分析化学技术领域,具体涉及一种磁性穿心莲内酯印迹聚合物及其制备方法和应用。
背景技术
穿心莲内酯具有广泛的临床适应症,具有抗炎、抗肿瘤、抗病毒、抗HIV和保肝等多种药理活性。目前穿心莲内酯在临床上针对不同疾病和以及不同药物剂型等方面的研究逐渐增加,因此对其制备研究也较多。有研究报道采用柱层析或大孔吸附树脂分离纯化穿心莲内酯,需大量溶剂解吸附分离后采用硅胶柱脱色,丙酮重结晶;也有报道通过集成溶剂除杂-溶剂萃取分离-柱层析-超临界流体抗溶剂结晶对穿心莲浸膏进行加工制备穿心莲内酯单体,其收率≥50%。上述工艺仍存在工业上分离纯化难度大,收率低,成品中残留较多有机物的缺点。现有技术还报道了一种穿心莲内酯的膜分离纯化工艺,但需压力设备。
分子印迹技术是以目标分子为模板,与功能单体通过非共价键或共价键结合,加入交联剂进行聚合,反应结束后洗脱模板分子,从而得到具有固定孔径大小和形状及有确定排列功能团的印迹聚合物。分子印迹聚合物具有耐酸碱、耐有机溶剂、热稳定性好、使用时间长等优点,并且具有较好的特异识别性能,从而应用于选择性富集、物质的分离等前处理中。磁性分子印迹聚合物是在Fe3O4磁性纳米颗粒表面包覆上分子印迹聚合物的特殊材料,是当前的研究热点,磁性分子印迹聚合物可通过外部磁场的磁力作用方便分离聚合物和目标化合物,能更好的应用于需求量多的目标中药化合物的分离。
但现有技术未见有将磁性纳米颗粒参与到穿心莲内酯印迹聚合物的制备中的报道,因此,制备磁性穿心莲内酯印迹聚合物是十分有意义的。
发明内容
为了解决现有技术存在的上述不足,本发明的目的是提供一种磁性穿心莲内酯印迹聚合物及其制备方法和应用,本发明通过将Fe3O4磁性纳米颗粒进行表面修饰形成壳核结构,将带有功能基团的颗粒通过共价键与聚合物单体连接并包埋到聚合物中,制得的磁性分子印迹聚合物稳定性好,不易泄露,且分离穿心莲内酯时吸附能力较强,用制备的聚合物从穿心莲提取液中纯化穿心莲内酯时方法简单,回收率高。
本发明解决上述技术问题的技术方案如下:提供一种磁性穿心莲内酯印迹聚合物的制备方法,包括以下步骤:
将穿心莲内酯和单体加入有机溶剂中预组装,再加入至含有改性的Fe3O4磁性纳米颗粒的反相微乳体系中,最后加入交联剂和引发剂,于30~60℃聚合反应25~28h,然后除去穿心莲内酯,制得磁性穿心莲内酯印迹聚合物。
本发明的有益效果为:本发明中以穿心莲内酯为模板分子,模板分子与功能单体通过共价、非共价作用形成预聚合物,然后在交联剂和引发剂的作用下功能单体发生聚合,将模板分子固定在聚合物中,最后脱除模板分子,即聚合物材料上留下与模板分子在大小、形状和官能团的方向上都互补的空穴结构。空穴不仅保留了与模板分子化学结构互补的官能团的有序排列,也维持了它的整个空间构想,所以当聚合物材料再次遇到模板分子时,可发生特异性的结合。
在聚合过程中,加入改性的Fe3O4磁性纳米颗粒后可通过外部磁场的磁力作用方便分离聚合物和目标化合物,能更好的应用于需求量多的目标化合物的分离。
在上述技术方案的基础上,本发明还可以做如下改进:
进一步,穿心莲内酯和单体的摩尔比为1:1~1:3,穿心莲内酯与交联剂的摩尔比为1:20~1:40,引发剂与单体的摩尔比为1:5~1:10。
进一步,单体为丙烯酰胺(AM)、丙烯酸(AA)或甲基丙烯酸(MAA)。
进一步,有机溶剂为乙腈、乙醇或二氯甲烷。
进一步,交联剂为N,N’-亚甲基双丙烯酰胺(MBA)、已二醇二甲基丙烯酸酯(EGDMA)或季戊四醇三丙烯酸酯(PETA)。
进一步,引发剂为偶氮二异丁腈(AIBN)。
进一步,穿心莲内酯和改性的Fe3O4磁性纳米颗粒的摩尔比为0.5~0.8:5~6。
进一步,改性的Fe3O4磁性纳米颗粒通过以下方法制备得到:
(1)将乳化剂OP-10、正丁醇和环己烷混合,形成反相微乳体系;
(2)将铁盐和亚铁盐混合溶于水中,并调节混合溶液pH值为10.5~11.5,然后加入步骤(1)反相微乳体系中,于室温反应0.5~1.5h;
(3)步骤(2)反应结束后,向该反应体系中加入硅烷偶联剂,于45~55℃反应4~6h,制得。
本发明的有益效果为:先通过乳化剂OP-10为表面活性剂、正丁醇为助表面活性剂,环己烷为连续相,水/铁盐溶液作为分散相,然后在碱性条件下,使得纳米水核与油相的界面发生水解来制备Fe3O4磁性纳米颗粒,然后加入硅烷偶联剂对Fe3O4磁性纳米颗粒进行改性得到改性的Fe3O4磁性纳米颗粒。硅烷偶联剂可以使Fe3O4表面性能增强,与有机分子聚合效果良好,能够更好的与单体、模板分子进行聚合,增强聚合物的稳定性和选择性。在制备过程中,并没有去除反应体系,因此,所得的改性的Fe3O4磁性纳米颗粒是改性的Fe3O4磁性纳米颗粒和反相微乳体系的混合物,直接将该混合物用于后续反应。
进一步,乳化剂OP-10和正丁醇的质量体积比为30~35:40~50(g/ml),正丁醇和环己烷的体积比为40~50:100。
进一步,铁盐和亚铁盐的摩尔比为1.7:1~2:1。
进一步,硅烷偶联剂为KH570。
进一步,步骤(2)反应结束后制得Fe3O4磁性纳米颗粒,KH57与Fe3O4磁性纳米颗粒的摩尔比为1:2~2.5。
上述制得的磁性穿心莲内酯印迹聚合物在分离提取穿心莲提取液中穿心莲内酯中的应用。
进一步地,采用上述制得的磁性穿心莲内酯印迹聚合物分离提取穿心莲提取液中穿心莲内酯的具体过程如下:将磁性穿心莲内酯印迹聚合物加入穿心莲提取液中进行搅拌反应,然后进行磁性分离,将分离产物用洗脱液洗脱,即将穿心莲内酯从穿心莲提取液中分离出来。
进一步地,搅拌速率为200~300rmp,搅拌反应时间为20~120min。
进一步地,磁性穿心莲内酯印迹聚合物与洗脱剂的质量体积比为1:0.1~1:0.5(w/v)。
进一步地,洗脱剂为体积分数为10%~30%的乙酸/乙醇溶液,即乙酸体积占乙酸乙醇混合液总体积的10%~30%。
进一步地,洗脱时间为30min~120min。
本发明具有以下有益效果:
采用反相微乳液法制备Fe3O4磁性纳米颗粒,然后采用硅烷偶联剂对Fe3O4磁性纳米颗粒进行表面改性制得复合磁性纳米颗粒即改性的Fe3O4磁性纳米颗粒,复合磁性纳米颗粒结合穿心莲内酯印迹聚合物的制备过程,形成了对穿心莲内酯具有特异性识别选择性的核-壳型磁性分子印迹聚合物,在萃取分离时,直接将磁性穿心莲内酯印迹聚合物加入到溶液中,分离时,利用外接磁铁将磁性分子印迹聚合物吸附到底部,达到快速分离富集的效果。
本发明采用反相微乳法合成磁性穿心莲内酯分子印迹聚合物,可以很好的实现聚合的可控性,且具有更宽的单体选择范围,原料易得,实施条件比较温和,此外,可以使印迹位点形成于表面,很好的提高印迹位点与模板分子的结合速度,提高聚合物的吸附分离效率。
本发明制得的磁性穿心莲内酯印迹聚合物对穿心莲吸附速度较快,在短时间(60min)内即可达到吸附平衡,且本发明制得的聚合物具有很好的磁性,应用该聚合物提取分离穿心莲内酯时,操作更为简便,且实现了选择性分离,得到了较高的回收率,以提取液中穿心莲内酯单体计,回收率达80%以上。
附图说明
图1为Fe3O4颗粒(a)和Fe3O4-KH570(b)、MMIPs(c)的红外谱图;
图2是Fe3O4颗粒(a)和MMIPs(b)的XRD图;
图3是MMIPs外磁场分离前后对比图;
图4是Fe3O4颗粒(a)和MMIPs(b)的热重曲线图;
图5是MMIPs和MNIPs的吸附能力曲线图;
图6是MMIPS的吸附平衡曲线图。
具体实施方式
以下所举实例只用于解释本发明,并非用于限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1:
一种磁性穿心莲内酯印迹聚合物(MMIPs)的制备方法,包括以下步骤:
(1)将32g乳化剂OP-10、45ml正丁醇和100ml环己烷混合均匀后,加入到装有机械搅拌、球形冷凝管和Ar2导管的三口烧瓶中;
(2)将3.5mmol FeCl3·6H2O和2.1mmol FeSO4·7H2O溶于50ml去离子水中,加入到步骤(1)中的三口烧瓶中,再滴加6ml浓氨水至pH为11后于25℃反应1h,该过程制得Fe3O4颗粒;
(3)步骤(2)反应结束后,向反应体系中加入2ml KH570,50℃反应5h;
(4)将0.6mmol穿心莲内酯和0.6mmol单体AM溶于50ml 60%乙醇溶液中,室温搅拌5h后,加入到步骤(3)经KH570改性后的体系中,搅拌10min,再加入18mmol交联剂MBA和0.086mmol偶氮二异丁腈(AIBN),于35℃反应26h;
(5)将步骤(4)所得产物用无水乙醇-乙酸(无水乙醇和乙酸的体积比为9:1)洗脱液超声清洗4次,每次30min,以除去模板分子和未反应的试剂,然后在60℃条件下真空干燥24h,制得磁性穿心莲内酯印迹聚合物,记为MMIPs。
实施例2:
与实施例1不同之处为将实施例1中的单体AM替换为AA,其余与实施例1一致。
实施例3:
与实施例1不同之处为将实施例1中的单体AM替换为MAA,其余与实施例1一致。
实施例4:
与实施例1不同之处为穿心莲内酯与单体的摩尔比为1:2即单体的加入量为1.2mmol,其余与实施例1一致。
实施例5:
与实施例1不同之处为穿心莲内酯与单体的摩尔比为1:3即单体的加入量为1.8mmol,其余与实施例1一致。
实施例6:
与实施例1不同之处为将实施例1中的交联剂MBA替换为EGDMA,穿心莲内酯与单体的摩尔比为1:2,其余与实施例1一致。
实施例7:
与实施例1不同之处为将实施例1中的交联剂MBA替换为PETA,穿心莲内酯与单体的摩尔比为1:2,其余与实施例1一致。
实施例8:
与实施例1不同之处为穿心莲内酯与交联剂的摩尔比为1:20即交联剂的加入量为12mmol,其余与实施例1一致。
实施例9:
与实施例1不同之处为穿心莲内酯与交联剂的摩尔比为1:40即交联剂的加入量为24mmol,其余与实施例1一致。
实施例10:
与实施例1不同之处为引发剂AIBN与单体的摩尔比为1:10。
实施例11:
与实施例1不同之处为引发剂AIBN与单体的摩尔比为1:5。
实施例12:
与实施例1不同之处为单体AM的加入量为1.2mmol,交联剂MBA的加入量为18mmol,引发剂AIBN的加入量为0.12mmol,其余与实施例1一致。
对比例1:
(1)将32g乳化剂OP-10、45ml正丁醇和100ml环己烷混合均匀后,加入到装有机械搅拌、球形冷凝管和Ar2导管的三口烧瓶中;
(2)将3.5mmol FeCl3·6H2O和2.1mmol FeSO4·7H2O溶于50ml去离子水中,加入到步骤(1)中的三口烧瓶中,再滴加6ml浓氨水至pH为11后于25℃反应1h;
(3)步骤(2)反应结束后,向反应体系中加入2ml KH570,50℃反应5h;
(4)将1.2mmol单体AM溶于60%乙醇溶液中,室温搅拌5h后,加入到步骤(3)经KH570改性后的体系中,搅拌10min,再加入18mmol交联剂MBA和0.12mmol偶氮二异丁腈(AIBN),于35℃反应26h,得到未加穿心莲内酯的磁性分子聚合物;
(5)将步骤(4)所得产物用无水乙醇-乙酸(无水乙醇和乙酸的体积比为9:1)洗脱液超声清洗4次,每次30min,除去未反应的试剂,然后在60℃条件下真空干燥24h,制得的样品记为MNIPs。
实验例1:聚合物表征检测
采用傅里叶红外光谱仪检测本发明制得的磁性穿心莲内酯分子印迹聚合物,检测结果如图1所示,由图1可知,1436cm-1为C-H弯曲振动特征峰,1538cm-1为N-H变形振动特征峰,3388cm-1为N-H伸缩振动特征峰,这些谱峰来自功能单体AM和交联剂MBA,表明在Fe3O4表面成功聚合上聚合物。
图2为磁性穿心莲内酯分子印迹聚合物的X-射线衍射(XRD)图,从图2中看出,MMIPs在2θ为30.33°、35.45°、43.62°、53.60°、57.20°、62.77°处出现了Fe3O4的六个特征衍射峰,说明此材料保持了Fe3O4的晶型特征。
制得的磁性穿心莲内酯分子印迹聚合物用外加磁场进行分离,结果见图3,从图3中看出,MMIPS在外界磁场下具有良好的分离效果。
图4为磁性穿心莲内酯分子印迹聚合物的热重曲线,由图4可知,在制成MMIPs后,其稳定性相比于Fe3O4有所下降,在200~400℃范围内出现失重,其原因是磁性微球表面聚合物受热分解所致。
实验例2:吸附实验
1、分别称取6份实施例12制得的MMIPs 10mg,置于六支10ml试管中,分别加入5ml穿心莲内酯溶液(含量为0.5mg/ml),200rmp搅拌,然后测定20min、40min、60min、90min、120min、150min时磁性穿心莲内酯分子印迹聚合物的吸附量Q(mg/g),得出磁性聚合物吸附平衡的时间(表1和图6)。从图6中可以看出MMIPs在1h能达到吸附平衡,说明吸附时间较短,能较好的应用于穿心莲内酯的分离。
表1吸附平衡数据
2、分别对实施例1-11制得的MMIPs进行上述的吸附实验,吸附时间为60min,测定不同单体、穿心莲内酯与单体的反应摩尔比、不同交联剂、穿心莲内酯与交联剂的摩尔比、引发剂AIBN与单体的摩尔比对吸附结果的影响,其具体影响见下表:
表2不同单体制备得到的MMIP吸附试验结果
表3穿心莲内酯与单体的反应摩尔比考察情况
表4不同交联剂考察情况
表5穿心莲内酯与交联剂的摩尔比考察结果
表6引发剂AIBN与单体的摩尔比考察结果
3、称取实施例12制得的MMIPs 10mg,对比例制得的MNIPs 10mg,分别将MMIPs和MNIPs置于10ml试管中,分别加入5ml图5所示不同浓度的穿心莲内酯乙醇溶液,搅拌1h后磁性分离,用HPLC测定浓度,再结合前后溶液中穿心莲内酯的浓度变化,计算出吸附量Q(mg/g)(表7)。从图5可以看出,随穿心莲内酯浓度的升高,MMIPs与MNIPs的吸附量不断增加,当浓度增加到一定数值时,MMIPS和MNIPS的吸附量增加缓慢,趋于稳定,说明聚合物的吸附达到饱和;并且在整个范围内,相同质量下MMIPs的吸附量都高于MINPs,这说明成功制备了对目标分子穿心莲内酯存在特异的结合位点的MMIPs,对穿心莲内酯具有特异的识别能力。
表7吸附能力数据
实验例3:分离纯化工艺
将实施例12制得的MMIPs用于穿心莲提取液的纯化工艺,具体过程如下:
将100mg MMIPs加入50ml穿心莲的乙醇提取液(含穿心莲内酯5.2g/L)中,250rmp搅拌反应60min,然后利用磁铁进行磁性分离,分离得到的产物采用50ml体积分数为10%的乙酸/乙醇溶液在250rmp搅拌洗脱120min,即完成将穿心莲内酯从穿心莲提取液中分离出来。洗脱液经加热浓缩后,静置析晶,过滤得到粗品,粗品用水洗涤,然后用乙醇加热溶解,静置重结晶,得到穿心莲内酯成品。
对比例:采用大孔吸附树脂从穿心莲提取液中分离纯化穿心莲内酯,具体过程如下:
将50ml穿心莲内酯的乙醇提取液(含穿心莲内酯5.2g/L)加到经预处理的D-101树脂层析柱中,用60%乙醇水溶液以1倍柱体积每小时的流速进行洗脱。洗脱液经加热浓缩后,静置析晶,过滤得到粗品,粗品用水洗涤,然后加热溶解,静置重结晶,得到穿心莲内酯成品。
将本发明分离纯化工艺所得的成品和对比例所得的成品用液相色谱法检测,本发明纯化工艺所得的穿心莲内酯回收率达81%以上,产品纯度大于99%,而对比例回收率为70.9%,纯度为98%,具体见表8。
表8 2种纯化工艺试验结果
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种磁性穿心莲内酯印迹聚合物的制备方法,其特征在于,包括:
将穿心莲内酯和单体加入有机溶剂中预组装,再加入至含有改性的Fe3O4磁性纳米颗粒的反相微乳体系中,最后加入交联剂和引发剂,于30~60℃聚合反应25~28h,然后除去穿心莲内酯,制得磁性穿心莲内酯印迹聚合物。
2.根据权利要求1所述的磁性穿心莲内酯印迹聚合物的制备方法,其特征在于,穿心莲内酯和单体的摩尔比为1:1~1:3,穿心莲内酯与交联剂的摩尔比为1:20~1:40,引发剂与单体的摩尔比为1:5~1:10。
3.根据权利要求1所述的磁性穿心莲内酯印迹聚合物的制备方法,其特征在于,单体为丙烯酰胺、丙烯酸或甲基丙烯酸;交联剂为N,N’-亚甲基双丙烯酰胺、已二醇二甲基丙烯酸酯或季戊四醇三丙烯酸酯;引发剂为偶氮二异丁腈。
4.根据权利要求1所述的磁性穿心莲内酯印迹聚合物的制备方法,其特征在于,有机溶剂为乙腈、乙醇或二氯甲烷。
5.根据权利要求1所述的磁性穿心莲内酯印迹聚合物的制备方法,其特征在于,穿心莲内酯和改性的Fe3O4磁性纳米颗粒的摩尔比为0.5~0.8:5~6。
6.根据权利要求1或5所述的磁性穿心莲内酯印迹聚合物的制备方法,其特征在于,改性的Fe3O4磁性纳米颗粒通过以下方法制备得到:
(1)将乳化剂、正丁醇和环己烷混合,形成反相微乳体系;
(2)将铁盐和亚铁盐混合溶于水中,并调节混合溶液pH值为10.5~11.5,然后加入步骤(1)反相微乳体系中,于室温反应0.5~1.5h;
(3)步骤(2)反应结束后,向该反应体系中加入硅烷偶联剂,于45~55℃反应4~6h,制得。
7.根据权利要求6所述的磁性穿心莲内酯印迹聚合物的制备方法,其特征在于,乳化剂为OP-10,硅烷偶联剂为KH570。
8.权利要求1~7任一项所述的制备方法制得的磁性穿心莲内酯印迹聚合物。
9.权利要求8所述的磁性穿心莲内酯印迹聚合物在分离提取穿心莲提取液中穿心莲内酯中的应用。
10.根据权利要求1所述的应用,其特征在于,将磁性穿心莲内酯印迹聚合物加入穿心莲提取液中进行搅拌反应,然后进行磁性分离,将分离产物用洗脱液洗脱即可。
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