CN112206824A - 一种聚多巴胺介导的磁性双金属纳米酶的制备方法 - Google Patents
一种聚多巴胺介导的磁性双金属纳米酶的制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚多巴胺介导的磁性双金属纳米酶的制备方法。以三氯化铁为铁源,通过溶剂热法制备得四氧化三铁纳米粒子,在其表面包裹聚多巴胺薄层,介导氯钯酸钠和氯铂酸钾原位还原,钯/铂生长于聚多巴胺薄层表面,即制得本发明磁性双金属纳米酶。本发明通过采用四氧化三铁作为磁核,赋予纳米酶磁性,从而实现纳米酶的回收利用,通过聚多巴胺介导生长钯/铂,可提供丰富的钯/铂生长位点,且制得的纳米酶具有优良的稳定性和生物相容性,同时由于钯/铂双金属协同效应,制得的纳米酶具备优异的酶催化活性。
Description
技术领域
本发明属于化学合成、纳米材料领域,具体涉及一种聚多巴胺介导的磁性双金属(钯/铂)纳米酶(Fe3O4@PDA@Pd/Pt)的制备方法。
背景技术
酶是具备强效催化活性、对底物具有高度特异性的蛋白质或RNA。酶催化反应是通过酶的参与降低反应能,从而使反应正常进行的一类化学反应。该反应的特点是仅需要极少量的酶参与,即可产生大量的反应产物,从而广泛应用于医学、生物和化学领域。然而,传统的酶(蛋白质类和RNA类)因其结构特性,往往稳定性不够、催化条件严格,纳米酶因其稳定性高、耐受极端环境等优点越来越受业界的关注。
纳米酶是一类微纳米尺寸的具有催化活性的纳米粒子,一般分为金属纳米酶和非金属纳米酶。与传统的有机物酶具备对底物的高特异性不同,纳米酶往往针对不同底物也能表现出催化活性,更具有普适性。同时,纳米酶结构简单,因而合成简便,结构设计更容易实现;纳米酶尺寸小,比表面积巨大,保证了其较高的催化活性;组成成分为金属或者碳类无机物,可在极端环境下仍不发生传统酶的变性。常见的纳米酶有二氧化钛纳米粒子、氧化石墨烯、钯纳米粒子、铂纳米粒子等,此外,一些双组分纳米酶例如金/铂、钯/铂等因其双组分之间的协同效应,可大大提高纳米酶的催化活性而成为研究热点。
随着社会的发展,资源越来越枯竭,物质的回收与再利用是可持续发展的重要举措。传统酶的回收较难实现,结构简单的纳米酶通过设计添加磁性组件即可实现。四氧化三铁(Fe3O4)是最为普遍应用的磁性纳米粒子,其具备超高的顺磁性,放置于外加磁场下即可实现纳米粒子的回收,撤去外加磁场实现纳米粒子的退磁从而分散。同时四氧化三铁纳米粒子因其粗糙表面具备大量的羟基而具备较好的可修饰性,易于与纳米酶其它组件装配。基于上述情况,发明人研究开发了一种聚多巴胺介导的磁性双金属(钯/铂)纳米酶(Fe3O4@PDA@Pd/Pt),目前,尚未有Fe3O4@PDA@Pd/Pt的制备并应用的相关报道。
发明内容
本发明旨在提供一种聚多巴胺介导的磁性双金属纳米酶Fe3O4@PDA@Pd/Pt的制备方法,该制备方法具有高效和易于制备的优点,制备得到的Fe3O4@PDA@Pd/Pt的磁响应强、分散性良好,且酶催化活性优异。
为了实现上述目的,本发明采取的技术方案如下:
本发明提供了一种Fe3O4@PDA@Pd/Pt的制备方法,包括如下步骤:
首先将三氯化铁、聚乙二醇和醋酸钠溶于乙二醇中,密封高温反应,磁分离洗涤所得纳米粒子制备得Fe3O4,然后取一定量Fe3O4分散于Tris-HCl缓冲溶液中,加入盐酸多巴胺,机械搅拌下避光反应,磁分离洗涤所得纳米粒子即得到聚多巴胺包四氧化三铁纳米粒子(Fe3O4@PDA),最后取一定量Fe3O4@PDA分散于聚乙烯吡咯烷酮溶液中,加入抗坏血酸、氯钯酸钠和氯铂酸钾,加热反应,磁分离洗涤所得纳米粒子,即制得本发明磁性双金属纳米酶。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,所述三氯化铁的终浓度为10~100mg/mL。所述聚乙二醇的相对分子量为2000~20000,终浓度为10~100mg/mL。所述醋酸钠的终浓度为30~300mg/mL。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,制备Fe3O4的高温反应温度为150~300℃,反应时间为12~36h。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,所述Tris-HCl缓冲溶液的浓度为0.01~0.1M,pH为7~10。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,Fe3O4的终浓度为10~200μg/mL,直径为50~500nm。所述盐酸多巴胺的终浓度为20~400μg/mL。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,制备Fe3O4@PDA的避光反应时间为12~36h,机械搅拌转速为200~400r/min。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,Fe3O4@PDA的终浓度为100~500μg/mL,PDA薄层厚度为5~50nm。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,所述聚乙烯吡咯烷酮溶液的浓度为0.5~5%(w/v)。所述抗坏血酸的终浓度为0.1~10mg/mL。所述氯钯酸钠的终浓度为0.1~10mM。所述氯铂酸钾的终浓度为0.1~10mM。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,制备Fe3O4@PDA@Pd/Pt的加热反应温度为50~90℃,反应时间为15~45min。
进一步的,所述Fe3O4@PDA@Pd/Pt的制备方法中,制得的Fe3O4@PDA@Pd/Pt的直径为60~1000nm。
本发明的有益效果是:
本发明通过采用四氧化三铁作为磁核,赋予纳米酶磁性,从而实现纳米酶的回收利用,通过聚多巴胺介导生长钯/铂,可提供丰富的钯/铂生长位点,且制得的纳米酶具有优良的稳定性和生物相容性,同时由于钯/铂双金属协同效应,制得的纳米酶具有稳定性和生物相容性好、催化活性高、可回收利用的优点。
附图说明
图1是本发明制备Fe3O4@PDA@Pd/Pt的原理图。
图2是本发明制备的Fe3O4@PDA@Pd/Pt的模拟结构图。
图3是本发明制备的Fe3O4@PDA@Pd/Pt透射电镜微观表征图。
图4是本发明制备的Fe3O4@PDA@Pd/Pt磁性表征图。其中a为Fe3O4,b为Fe3O4@PDA,c为Fe3O4@PDA@Pd/Pt。
图5是本发明制备的Fe3O4@PDA@Pd/Pt与传统辣根过氧化物酶(HRP)的酶催化活性对比图。其中a为TMB+H2O2,b为2×10-10M HRP+TMB+H2O2,c为2×10-11M HRP+TMB+H2O2,d为2×10-11M Fe3O4@PDA@Pd/Pt+TMB+H2O2,e为2×10-12M Fe3O4@PDA@Pd/Pt+TMB+H2O2。
具体实施方式
实施例1:100nm粒径Fe3O4@PDA@Pd/Pt的制备
一、制备Fe3O4:称取三氯化铁、聚乙二醇-3000和醋酸钠溶于乙二醇中,使之终浓度分别为10、15、60mg/mL,高压釜密封200℃反应12h,反应结束后磁分离水洗3次,烘干得Fe3O4;
二、制备Fe3O4@PDA:取Fe3O4分散于Tris-HCl缓冲溶液(0.05M,pH=8.5)中,使之终浓度分别为50μg/mL,加入盐酸多巴胺(10mg/mL)使之终浓度为50μg/mL,避光搅拌反应(250r/min)15h,反应结束后磁分离,水洗三遍后用水复溶即得Fe3O4@PDA;
三、制备Fe3O4@PDA@Pd/Pt:取一定量的Fe3O4@PDA分散于聚乙烯吡咯烷酮溶液(1%)中,使之终浓度为50μg/mL。加入抗坏血酸、氯钯酸钠和氯铂酸钾,使之终浓度分别为0.5mg/mL、0.25mM和0.5mM,65℃反应10min。反应结束后磁分离,水洗三次后水复溶即得Fe3O4@PDA@Pd/Pt。
实施例2:200nm粒径Fe3O4@PDA@Pd/Pt的制备
一、制备Fe3O4:称取三氯化铁、聚乙二醇-4000和醋酸钠溶于乙二醇中,使之终浓度分别为20、15、60mg/mL,高压釜密封200℃反应16h,反应结束后磁分离水洗3次,烘干得Fe3O4;
二、制备Fe3O4@PDA:取Fe3O4分散于Tris-HCl缓冲溶液(0.05M,pH=8.5)中,使之终浓度分别为50μg/mL,加入盐酸多巴胺(10mg/mL)使之终浓度为100μg/mL,避光搅拌反应(250r/min)20h,反应结束后磁分离,水洗三遍后用水复溶即得Fe3O4@PDA;
三、制备Fe3O4@PDA@Pd/Pt:取一定量的Fe3O4@PDA分散于聚乙烯吡咯烷酮溶液(1%)中,使之终浓度为50μg/mL。加入抗坏血酸、氯钯酸钠和氯铂酸钾,使之终浓度分别为0.5mg/mL、0.25mM和0.5mM,65℃反应15min。反应结束后磁分离,水洗三次后水复溶即得Fe3O4@PDA@Pd/Pt。
实施例3:1μm粒径Fe3O4@PDA@Pd/Pt的制备
一、制备Fe3O4:称取三氯化铁、聚乙二醇-10000和醋酸钠溶于乙二醇中,使之终浓度分别为40、35、80mg/mL,高压釜密封200℃反应20h,反应结束后磁分离水洗3次,烘干得Fe3O4;
二、制备Fe3O4@PDA:取Fe3O4分散于Tris-HCl缓冲溶液(0.05M,pH=8.5)中,使之终浓度分别为200μg/mL,加入盐酸多巴胺(50mg/mL)使之终浓度为500μg/mL,避光搅拌反应(250r/min)30h,反应结束后磁分离,水洗三遍后用水复溶即得Fe3O4@PDA;
三、制备Fe3O4@PDA@Pd/Pt:取一定量的Fe3O4@PDA分散于聚乙烯吡咯烷酮溶液(1%)中,使之终浓度为200μg/mL。加入抗坏血酸、氯钯酸钠和氯铂酸钾,使之终浓度分别为2mg/mL、1mM和2mM,65℃反应25min。反应结束后磁分离,水洗三次后水复溶即得Fe3O4@PDA@Pd/Pt。
如图4所示,三种纳米粒子在外加磁场下1min内即可实现较好的磁分离,3min可完全磁分离。
如图5所示,本发明制备的Fe3O4@PDA@Pd/Pt在2×10-12M浓度下即可达到较好的催化性能,而HRP需要2×10-10M方可达到。在同等物质的量浓度下。Fe3O4@PDA@Pd/Pt的酶催化活性约为HRP的100倍。
以上所述仅表达了本发明的优选实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形、改进及替代,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种聚多巴胺介导的磁性双金属纳米酶的制备方法,其特征在于,首先将三氯化铁、聚乙二醇和醋酸钠溶于乙二醇中,密封高温反应,磁分离洗涤所得纳米粒子制备得四氧化三铁纳米粒子,然后取一定量四氧化三铁纳米粒子分散于Tris-HCl缓冲溶液中,加入盐酸多巴胺,机械搅拌下避光反应,磁分离洗涤所得纳米粒子即得到聚多巴胺包四氧化三铁纳米粒子,最后取一定量聚多巴胺包四氧化三铁纳米粒子分散于聚乙烯吡咯烷酮溶液中,加入抗坏血酸、氯钯酸钠和氯铂酸钾,加热反应,磁分离洗涤所得纳米粒子,即制得磁性双金属纳米酶。
2.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述三氯化铁的终浓度为10~100mg/mL;所述聚乙二醇的相对分子量为2000~20000,终浓度为10~100mg/mL。
3.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述醋酸钠的终浓度为30~300mg/mL;所述Fe3O4的终浓度为20~200μg/mL,直径为50~500nm;所述盐酸多巴胺的终浓度为20~400μg/mL。
4.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述制备Fe3O4的高温反应温度为150~300℃,反应时间为12~36h。
5.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述Tris-HCl缓冲溶液的浓度为0.01~0.1M,pH为7~10。
6.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述制备Fe3O4@PDA的避光反应时间为12~36h,机械搅拌转速为200~400r/min。
7.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述Fe3O4@PDA的终浓度为100~500μg/mL,PDA薄层厚度为5~50nm。
8.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述聚乙烯吡咯烷酮溶液的浓度为0.5~5%(w/v);所述抗坏血酸的终浓度为0.1~10mg/mL;所述氯钯酸钠的终浓度为0.1~10mM;所述氯铂酸钾的终浓度为0.1~10mM。
9.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述制备Fe3O4@PDA@Pd/Pt的加热反应温度为50~90℃,反应时间为15~45min。
10.根据权利要求1所述的一种聚多巴胺介导的磁性双金属纳米酶制备方法,其特征在于,所述制得的Fe3O4@PDA@Pd/Pt的直径为60~1000nm。
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