CN105924468B - 由植酸与可溶性金属盐制备的新型水凝胶及其制备方法 - Google Patents
由植酸与可溶性金属盐制备的新型水凝胶及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种水凝胶的制备方法,所述方法包括将植酸分散液和可溶性金属盐溶液混合,经过常规后处理即可得到水凝胶。本发明的制备方法具有以下优点:反应时间短、制备方法简单和具有一定普适性。制备的水凝胶材料具有以下特点:比表面积大、三维网络结构、生物相容性好。
Description
技术领域
本发明涉及化学材料制备领域,具体而言,涉及一类水凝胶的制备方法。
背景技术
水凝胶是一种具有三维网络结构的交联高分子,可以容纳大量的水分具有良好的生物相容性、传输小分子的能力和高水合作用。水凝胶的制备方法大体可以分为两类:物理方法和化学方法。物理方法制备水凝胶是利用非化学键的相互作用力(氢键、络合、静电作用、疏水作用、范德华力等)来实现交联形成的三维交联聚合物网络。化学方法制备水凝胶是利用高分子链段间共价键的交联。根据其形成交联结构的不同可以分为两种方式,一种是在聚合的同时形成交联,一般是由多官能团的单体通过体型缩聚或者通过自由基聚合制备凝胶;另一种是先形成线性高分子,然后通过高分子之间的交联形成凝胶,如Mansur等人利用戊二醛化学交联制备的聚乙烯醇水凝胶,可以作为药物包裹和释放的载体(MansurH.S.,Sadahira C.M.,Souza A.N.,et al.Materials Science and Engineering:C,2008,28(4):539-548.)。
在目前水凝胶制的过程中,植酸通常作为一种交联剂实现苯胺、吡咯等单体的交联从而实现聚苯胺、聚吡咯导电水凝胶的制备。
本发明基于植酸与可溶性金属盐络合作用的原理,制备一类新型水凝胶。本发明制备水凝胶的方法具有以下优点:反应时间短、制备方法简单和具有一定普适性(可与不同可溶性金属盐形成水凝胶)。制备的新型水凝胶材料具有以下特点:比表面积大、三维网络结构、生物相容性好。
发明内容
根据本发明的一个方面,本发明的目的之一在于提供一种新型水凝胶的制备方法,所述方法包括以下步骤:
1)将1重量份的植酸分散在约10重量份的溶剂中形成均匀分散的植酸分散液,1重量份的可溶性金属盐分散在约10重量份的溶剂中形成可溶性金属盐溶液,然后将植酸分散液加入到反应器中,然后再向反应器中缓慢滴加可溶性金属盐溶液,所述植酸和所述可溶性金属盐的重量之比为1:0.01-1:100,反应温度为0-160℃,反应时间为1秒至1.5小时。
2)反应结束后将产物经过常规后处理,透析、用去离子水洗涤至少三次。
其中,所述可溶性金属盐自乙酸铅、乙酸锌、乙酸铬、乙酸锰、乙酸镉、硝酸锌、硝酸铅、硝酸铬、硝酸镉、硝酸铁、硝酸镍、硝酸锰、硝酸镁、氯化铁、氯化铜、氯化镁、氯化亚锑、硫酸铁、硫酸铜、硫酸铬、硫酸镉、硫酸镁、硫酸锌、硫酸铅、硝酸钴等。
所述植酸和所述可溶性金属盐的重量之比优选为1:0.05-1:50,进一步优选为1:0.1-1:10,最优选为1:1。
所述作为溶剂的有水,乙醇、丙醇中的一种或多种,优选为水。
优选地,所述可溶性金属盐选自乙酸铅、乙酸锌、乙酸铬、乙酸锰、乙酸镉、硝酸锌、硝酸铅、硝酸铬、硝酸镉、硝酸铁、硝酸镍、硝酸锰、硝酸镁、氯化铁、氯化铜、氯化镁、氯化亚锑、硫酸铁、硫酸铜、硫酸铬、硫酸镉、硫酸镁、硫酸锌、硫酸铅;进一步优选为乙酸铅、乙酸锌、乙酸铬、乙酸锰、乙酸镉、硝酸锌、硝酸铅、硝酸铬、硝酸镉、硝酸铁、硝酸镍、硫酸铁、硫酸铜、硫酸铬、硫酸镉;最优选乙酸铅、乙酸锌、乙酸锰、硝酸铅、硝酸铁、乙酸锰、乙酸镉。
优选地,所述步骤1)中的反应温度优选为0-120℃,更进一步优选为0-60℃。
优选地,所述步骤1)中的反应时间优选为1秒至80分钟,进一步优选为1秒至60分钟。
优选地,根据本发明的制备方法,所述方法不使用任何单体、有机溶剂、交联剂等。
根据本发明的一个方面,本发明的目的之一在于提供一类新型水凝胶材料,所述新型水凝胶材料由以上制备方法制得。
有益效果
本发明基于植酸与可溶性金属盐络合作用的原理,制备一类新型水凝胶。本发明制备水凝胶的方法具有以下优点:反应时间短、制备方法简单和具有一定普适性(可与不同可溶性金属盐形成水凝胶)。制备的新型水凝胶材料具有以下特点:比表面积大、三维网络结构、生物相容性好。
附图说明
图1为根据本发明的实施例1中制备的硝酸铁水凝胶的透射电子显微镜照片(TEM)。
图2为根据本发明的实施例1中制备的硝酸铁水凝胶的扫描电子显微镜照片(SEM)。
图3为根据本发明的实施例1至6中制备的水凝胶的数码照片,其中照片中从左至右依次是实施例2、3、1、4、5和6中制备的水凝胶。
图4为根据本发明的测试实施例1中用方波伏安法采用不同阶段根据本实施例制备的硝酸铁水凝胶修饰的电极对检测液的检测结果图。
具体实施方式
本发明的发明人对植酸与可溶性金属盐制备水凝胶进行了细致的研究,基于植酸与可溶性金属盐络合作用的原理,将植酸溶液与可溶性金属盐溶液混合制备一类新型水凝胶,获得了预期的效果。
本发明先制备了植酸溶液和可溶性金属盐溶液,然后在水溶液中混合制备,获得了结构性能稳定的水凝胶。本发明的特点是:制备条件温和易控,制备过程简单快捷,对制备新型的水凝胶的方法具有一定的普适性。
根据本发明的制备方法不同于以往制备水凝胶的常规方法,在本发明的制备方法中不需要使用任何单体、有机溶剂、交联剂等,仅仅采用植酸与可溶性金属盐两种反应物即可获得具有理想物化性质的水凝胶产品。
在根据本发明的制备方法中所述植酸和所述可溶性金属盐的重量之比为1:0.01-1:100,当所述植酸和所述可溶性金属盐的重量之比为大于1:0.01,即所述可溶性金属盐的重量比小于0.01时,由于可溶性金属盐含量过小,不能有效形成水凝胶;而当所述植酸和所述可溶性金属盐的重量之比为小于1:100,即所述可溶性金属盐的重量比大于100时,所述可溶性金属盐含量过高,造成反应瞬间发生,而无法控制水凝胶的物化性质。
此外,在根据本发明的制备方法中反应温度为0-160℃,反应时间为1秒至1.5小时。当反应温度小于0℃或反应时间小于1秒时,或者反应温度超过160℃,均不能形成结构稳定的水凝胶产品。
以下实施例仅是作为本发明的实施方案的例子列举,并不对本发明构成任何限制,本领域技术人员可以理解在不偏离本发明的实质和构思的范围内的修改均落入本发明的保护范围。
在下文中,将参照附图详细地描述本公开的优选的实施方式。在描述之前,应当了解在说明书和所附权利要求中使用的术语,并不应解释为局限于一般及辞典意义,而是应当基于允许发明人为最好的解释而适当定义术语的原则,基于对应于本发明技术层面的意义及概念进行解释。因此,在此的描述仅为说明目的的优选实例,而并非是意指限制本发明的范围,因而应当了解的是,在不偏离本发明的精神和范围下可以做出其他等同实施和修改。
实施例1:硝酸铁水凝胶的制备
室温下,取1ml植酸分散在10ml的水中,1g的硝酸铁溶于10ml的水中。将上述溶液摇匀。在上述溶液中,先取1ml的植酸溶液加入到5ml的离心管中,再取1ml的硝酸铁溶液缓慢加入到植酸溶液中,反应时间大约为3-8秒。之后就可得到植酸和硝酸铁制备的水凝胶。制备出的水凝胶装入透过分子量8000的透析袋中,用去离子水洗涤。
实施例2:乙酸铅水凝胶的制备
室温下,取1ml植酸分散在10ml的水中,1g的乙酸铅溶于10ml的水中。将上述溶液摇匀。在上述溶液中,先取1ml的植酸溶液加入到5ml的离心管中,再取1ml的乙酸铅溶液缓慢加入到植酸溶液中。在25℃的条件瞬时反应完成,反应时间大约为3-8秒。之后就可得到植酸和乙酸铅制备的水凝胶。制备出的水凝胶装入透过分子量8000的透析袋中,用去离子水洗涤。
实施例3:乙酸锌水凝胶的制备
室温下,取1ml植酸分散在10ml的水中,1g的乙酸锌溶于10ml的水中。将上述溶液摇匀。在上述溶液中,先取1ml的植酸溶液加入到5ml的离心管中,再取1ml的乙酸锌溶液缓慢加入到植酸溶液中。在25℃的条件瞬时反应完成,反应时间大约为3-8秒。之后就可得到植酸和乙酸锌制备的水凝胶。制备出的水凝胶装入透过分子量8000的透析袋中,用去离子水洗涤。
实施例4:乙酸锰水凝胶的制备
室温下,取1ml植酸分散在10ml的水中,1g的乙酸锰溶于10ml的水中。将上述溶液摇匀。在上述溶液中,先取1ml的植酸溶液加入到5ml的离心管中,再取1ml的乙酸锰溶液缓慢加入到植酸溶液中。在25℃的条件瞬时反应完成,反应时间大约为3-8秒。之后就可得到植酸和乙酸锰制备的水凝胶。制备出的水凝胶装入透过分子量8000的透析袋中,用去离子水洗涤。
实施例5:硝酸铅水凝胶的制备
室温下,取1ml植酸分散在10ml的水中,1g的硝酸铅溶于10ml的水中。将上述溶液摇匀。在上述溶液中,先取1ml的植酸溶液加入到5ml的离心管中,再取1ml的硝酸铅溶液缓慢加入到植酸溶液中。在25℃的条件瞬时反应完成,反应时间大约为3-8秒。之后就可得到植酸和硝酸铅制备的水凝胶。制备出的水凝胶装入透过分子量8000的透析袋中,用去离子水洗涤。
实施例6:乙酸镉水凝胶的制备
室温下,取1ml植酸分散在10ml的水中,1g的乙酸镉溶于10ml的水中。将上述溶液摇匀。在上述溶液中,先取1ml的植酸溶液加入到5ml的离心管中,再取1ml的乙酸镉溶液缓慢加入到植酸溶液中。在25℃的条件瞬时反应完成,反应时间大约为3-8秒。之后就可得到植酸和乙酸镉制备的水凝胶。制备出的水凝胶装入透过分子量8000的透析袋中,用去离子水洗涤。
测试实施例1:
(1)取20μl实施例1制备的硝酸铁水凝胶均匀的滴涂在玻碳电极表面,在37℃烘箱里烘干30min,使其在玻碳电极表面形成均匀的薄膜。
(2)将带有硝酸铁水凝胶薄膜的电极在去离子水中浸泡10min,去除多余的物质,得到硝酸铁水凝胶修饰的电极。
(3)再利用电沉积技术对硝酸铁水凝胶修饰的电极电镀上金颗粒,通过循环伏安法在HAuCl4溶液从0.2V到-1.0V扫描10圈,之后再用去离子水冲洗3次。
(4)50μL的200μg·mL-1的常用的癌症标志物细胞角蛋白19(CYFRA21-1)的捕获抗体(anti-CYFRA21-1)溶液在4℃条件下在硝酸铁水凝胶修饰的玻碳电极上孵化过夜。电极表面多余的抗体用超纯水清洗掉。
(5)使用30μL的1%的牛血清白蛋白(BSA)溶液封闭1小时,以消除非特异性吸附。
(6)电极用超纯水将过量牛血清白蛋白冲洗后,用人血清样品(含有癌症标志物细胞角蛋白19(CYFRA21-1),由首师大附属医院提供)在37℃下孵育超过45min。未反应的人血清使用超纯水清洗掉,在37℃下,孵育超过45min。
(7)以包含5.0mM[Fe(CN)6]4-/3-和0.1M KCl的0.01M磷酸缓冲盐溶液(PBS)(pH7.0)为检测液,用方波伏安法分别对上述各个步骤得到的样品检测电流响应信号。
图4为用方波伏安法采用不同阶段根据本实施例制备的硝酸铁水凝胶修饰的电极对检测液的检测结果,其中曲线a为步骤(2)中得到的硝酸铁水凝胶修饰的电极的电流响应曲线,电流大约为340μA,曲线b为步骤(3)中得到的沉积了金纳米颗粒后的电极,峰电流升高为360μA,这是由于金纳米颗粒具有良好的导电性,曲线c为孵化了捕获抗体(anti-CYFRA21-1)后的电极的电流响应曲线,曲线d为牛血清白蛋白(BSA)溶液封闭1小时后的电极的电流响应曲线,以及曲线e为含有CYFRA21-1的人血清样品孵育后的电极的电流响应曲线。
采用传统ELISA标准做平行检测试验,计算根据本发明的所述硝酸铁水凝胶修饰的电极测得的实验数据的可靠性,即与ELISA标准方法得到的测量结果的偏差。注:由于每次测量会不可避免地存在误差,通常测量误差在±5%以内均是允许的。
对血清样品的检测结果如下表1所示:
表1
采用根据本发明制备的硝酸铁水凝胶修饰的电极测量得到人血清样品中CYFRA21-1的浓度与采用ELISA标准做平行检测试验得到的浓度相比,相对误差在±5%以内,证明采用根据本发明制备的硝酸铁水凝胶修饰的电极的电化学方法可以准确高效地实现对癌症标志物细胞角蛋白19的检测。
根据本发明制备出的水凝胶在电化学生物免疫传感器的构建中具有突出的优势:1)固定抗体、酶等分子。导电水凝胶具有高度连续的网络结构,其巨大的比表面能够固定大量的生物分子,同时这些材料具有良好的生物相容性,能够提供适宜固定蛋白的微环境,尽可能保持生物分子的活性;(2)促进电极表面的电子转移。导电水凝胶具有良好的导电性,将这些材料修饰在电极表面,会增强电子在电极界面的传输,进而提高电信号强度及传感器灵敏度。(3)稳定性好。导电水凝胶具有稳定性好、易制备及性能可控等特点,且在电化学传感时能够起到信号放大作用及消除传感器检测误差的作用。
根据本发明的制备方法条件简便,不需要外接昂贵的仪器。以往报道的水凝胶的制备方法是由单体、交联剂、引发剂相互作用反应,制备过程繁琐。根据本发明的制备植酸与金属离子的水凝胶未在相关文献见过报道。根据本发明的制备方法得到的水凝胶属于物理水凝胶,在外界条件的改变下(如施加一定的外力)会发生凝胶与溶胶的转变。基于这种性质的变化可以把它均匀的滴涂在电极的表面,实现在电化学生物传感器中的应用。
Claims (2)
1.一种水凝胶的制备方法,所述方法包括以下步骤:
1)将1重量份的植酸分散在10重量份的溶剂中形成均匀分散的植酸分散液,1重量份的可溶性金属盐分散在10重量份的溶剂中形成可溶性金属盐溶液,然后将植酸分散液加入到反应器中,然后再向反应器中缓慢滴加可溶性金属盐溶液,所述植酸和所述可溶性金属盐的重量之比为1:0.1-1:10,反应温度为0-60℃,反应时间为1秒至60分钟;
2)反应结束后将产物经过常规后处理,透析、用去离子水洗涤至少三次;
其中,所述可溶性金属盐选自乙酸铅、乙酸锌、乙酸锰、硝酸铅、硝酸铁、乙酸镉;
所述溶剂为水。
2.根据权利要求1所述的制备方法,其特征在于,所述植酸和所述可溶性金属盐的重量之比为1:1。
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