CN112067671B - 一种葡萄糖电化学传感器及其制备方法 - Google Patents
一种葡萄糖电化学传感器及其制备方法 Download PDFInfo
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- CN112067671B CN112067671B CN202010832447.0A CN202010832447A CN112067671B CN 112067671 B CN112067671 B CN 112067671B CN 202010832447 A CN202010832447 A CN 202010832447A CN 112067671 B CN112067671 B CN 112067671B
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- transition metal
- glucose
- metal complex
- redox polymer
- aqueous solution
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Abstract
本发明提供了一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器，及其制备方法。所述葡萄糖电化学传感器的传感层包括含过渡金属配合物介质的阳离子氧化还原聚合物、葡萄糖氧化酶和交联剂。本发明的葡萄糖电化学传感器能够特异性检测葡萄糖，且其稳定电流信号与葡萄糖浓度线性相关系数高；能够排除干扰物质对葡萄糖检测的影响；还能够排除溶液中氧气浓度对葡萄糖检测的影响。
Description
技术领域
本发明涉及一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器及其制备方法。本发明属于电化学传感器领域。
背景技术
糖尿病是一种普遍的慢性疾病，是由于人体内血糖浓度的不可控所引起，它严重危害着人类的健康。如果人体内的血糖浓度持续偏高则很有可能会诱发高血糖，继而引发一系列并发症，如失明、心血管疾病、肾功能衰竭等。而过低的血糖浓度又会造成低血糖，甚至引起死亡。
到目前为止，还没有很好的医疗手段可以根治糖尿病。多数情况下，医生都是通过控制病人的血糖浓度来达到治疗的目的。而想要很好的控制血糖浓度，对血糖进行连续实时的监测是必不可少的。因此，葡萄糖传感器被研发出来用于精确的检测血糖浓度。
在众多的葡萄糖检测方法中，电化学分析方法有着一些简单和定量的操作模式，被广泛的应用在葡萄糖传感器中。这类方法有很快的响应时间和很宽的检测范围，测得的电化学信号可以转化为相应的葡萄糖浓度，能够很好的实现对葡萄糖浓度的定量分析。
然而，现有的葡萄糖电化学传感器也存在着一些问题，主要体现在：1、干扰物质会对葡萄糖检测有较大的影响；2、基于特异性高的葡萄糖氧化酶反应机理制造的葡萄糖电化学传感器在使用时，需要消耗氧气，氧气不足导致测试结果不准确。
结合对相关背景问题的了解，本发明提供了一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器及其制备方法。
本发明提供的电化学葡萄糖传感器能够特异性检测葡萄糖，且其稳定电流信号与葡萄糖浓度线性相关系数高，能排除干扰物质对葡萄糖检测的影响，能够排除溶液中氧气浓度对葡萄糖检测的影响，从而克服了现有技术的不足。
因此，本发明基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器在连续性血糖检测上具有广泛的应用价值。
发明内容
本发明涉及一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器及其制备方法，本发明提供的电化学传感器能够快速准确地连续性检测葡萄糖浓度。
为了达到上述目的，本发明采用了下列技术方案：
一种葡萄糖电化学传感器的制备方法，所述葡萄糖电化学传感器基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶，其特征在于，所述制备方法包括以下步骤：
A、将过渡金属配合物介质接枝到阳离子聚合物侧链上得到含过渡金属配合物介质的阳离子氧化还原聚合物，
B、将步骤A中得到的过渡金属配合物介质的阳离子氧化还原聚合物溶解在去离子水中，得到过渡金属配合物介质的阳离子氧化还原聚合物水溶液，
C、将步骤B中得到的过渡金属配合物介质的阳离子氧化还原聚合物水溶液、以及葡萄糖氧化酶水溶液和交联剂水溶液的溶液混合物涂布到电极表面，
D、待水分蒸发后置入真空干燥箱中干燥，得到含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器。
进一步的，本发明的葡萄糖电化学传感器的制备方法，其中步骤A中得到的过渡金属配合物介质的阳离子氧化还原聚合物化学结构式如下所示：
其中，M为过渡金属；
L为过渡金属配合物中的配体，选自二联咪唑和二联吡啶类衍生物；
x，y，z为分子中碳氢链的长度。
进一步的，本发明的葡萄糖电化学传感器的制备方法，其中步骤A中所用的过渡金属M为铁、钴、钌、锇和钒中的一种或多种。
进一步的，本发明的葡萄糖电化学传感器的制备方法，其中步骤A中所用的过渡金属配合物中的配体L为N,N′-二甲基-2,2′-联咪唑、2,2′-联吡啶、4,4′-二甲基 -2,2′-联吡啶、4,4′-二甲氧基-2,2′-联吡啶和4,4′-二氯-2,2′-联吡啶中的一种或多种。
进一步的，本发明的葡萄糖电化学传感器的制备方法，其中步骤A中使用的阳离子氧化还原聚合物选自侧链带有氨基的壳聚糖、N-羧甲基壳聚糖、O-羧甲基壳聚糖、羟丙基壳聚糖、N-马来酰化壳聚糖的天然高分子，和聚赖氨酸、聚烯丙基胺、聚乙烯亚胺、聚精氨酸的合成高分子中的一种或多种。
进一步的，本发明的葡萄糖电化学传感器的制备方法，其中步骤A中过渡金属配合物介质通过4-20个共价键接枝到阳离子聚合物侧链上，即4≤x+y+z≤20。
进一步的，本发明的葡萄糖电化学传感器的制备方法，其中步骤C中使用的交联剂选自戊二醛、聚乙二醇二缩水甘油醚和京尼平中的一种或多种；其中京尼平的结构式为：
进一步的，本发明的葡萄糖电化学传感器的制备方法，其中步骤C中，所述溶液混合物通过将步骤A中得到的过渡金属配合物介质的阳离子氧化还原聚合物水溶液、葡萄糖氧化酶水溶液和交联剂水溶液在0-45℃下，混合45分钟-2天得到。
进一步的，本发明的葡萄糖电化学传感器的制备方法，其特征在于所述溶液混合物通过将1-20mg/mL的过渡金属配合物介质的阳离子氧化还原聚合物水溶液、1-10mg/mL的葡萄糖氧化酶水溶液、1-10mg/mL的交联剂水溶液混合得到，使得溶液混合物中过渡金属配合物介质的阳离子氧化还原聚合物、葡萄糖氧化酶和交联剂的质量比为1：(0.1-5)：(0.01-0.5)。
本发明还涉及由上述方法制备得到的葡萄糖电化学传感器。
根据本发明方法制备的葡萄糖电化学传感器取得了以下有益效果：
1.本发明的葡萄糖电化学传感器能够特异性检测葡萄糖，且其稳定电流信号与葡萄糖浓度线性相关系数高。
2.本发明的葡萄糖电化学传感器能排除干扰物质对葡萄糖检测的影响。
3.本发明的葡萄糖电化学传感器能够排除溶液中氧气浓度对葡萄糖检测的影响。
附图说明
图1基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器在0mM、5mM、10mM、15mM葡萄糖的PBS溶液中的氧化还原曲线。
图2基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器在10mM葡萄糖的PBS溶液中的时间电流曲线。
图3基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器在10mM葡萄糖的PBS溶液中的时间电流曲线。随着溶液中氧气浓度的变化，信号值变化较小。
图4基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器在5mM、10mM、15mM、20mM葡萄糖的PBS溶液中的时间电流曲线。随着葡萄糖浓度的增加，电流信号值也增加；且葡萄糖浓度和电流信号值呈比较好的线性关系。
具体实施方式
下面结合附图，对本发明作详细的说明。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明做进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
实施例1：一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器制备方法，包括以下步骤：
1)将1mmol乙烯基咪唑、1mmol 11-巯基十一烷酸和12mg引发剂偶氮二异丁腈加入到5mL的乙醇中，70℃过夜反应。反应完全后降至室温，将所得溶液缓慢滴加到50mL去离子水中沉淀。过滤，滤饼在烘箱中烘干。
2)将1.5mmol的步骤1)中的产物和1mmol的Os-(bpy)2Cl加入到5mL的乙醇中，回流反应三天。反应完全后，冷却至室温，缓慢滴加到50mL去离子水中。过滤，收集滤液。滤液在烘箱中干燥得到产物。
3)将1mmol 2)中得到的产物溶于去离子水中，加入28mg EDC(二氯乙烷) 和16mgNHS(N-羟基琥珀酰亚胺)活化羧基，加入0.468g聚烯丙基胺，室温反应2天。将该体系透析，冻干，得到产物。
4)将7.8μL3)中所得产物的水溶液(10mg/mL)、16μL葡萄糖氧化酶水溶液(10mg/mL)和6μL聚乙二醇二缩水甘油醚水溶液(2.5mg/mL)混合后，室温交联2天。
5)将该凝胶体系滴加到电极表面，待水分蒸发后，置入真空环境中2天，得到目标电极。
测试制备的电极在0、5mM、10mM、15mM葡萄糖的PBS溶液(磷酸盐缓冲溶液)中的氧化还原曲线，结果如图1所示。该电极的氧化还原峰在250mV以下，远低于干扰物质对乙酰氨基酚和抗坏血酸等催化氧化所需要的电压。故该电极有较好的抗干扰能力。
实施例2：一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器制备方法，包括以下步骤：
1)将1mmol乙烯基咪唑、1mmol 16-巯基十六烷基酸和12mg引发剂偶氮二异丁腈加入到5mL的丙酮中，45℃过夜反应。反应完全后降至室温，该溶液缓慢滴加到50mL去离子水中沉淀。过滤，滤饼在烘箱中烘干。
2)将1.7mmol的步骤1)中的产物和1mmol的Rh-(二甲基-bpy)2Cl加入到 5mL的乙醇中，回流反应三天。反应完全后，冷却至室温，缓慢滴加到50mL去离子水中。过滤，收集滤液。滤液在烘箱中干燥得到产物。
3)将1mmol 2)中得到的产物溶于去离子水中，加入28mg EDC和16mg NHS 活化羧基，加入0.641g聚乙烯亚胺，室温反应2天。将该体系透析，冻干，得到产物。
4)将10μL的3)中得到的产物的水溶液(5mg/mL)、2μL葡萄糖氧化酶水溶液(10mg/mL)和1μL戊二醛(2mg/mL)混合后，45℃交联40min。
5)将该凝胶体系滴加到电极表面，待水分蒸发后，置入真空环境中2天，得到目标电极。
测试制备的电极在10mM葡萄糖的PBS溶液中的时间电流曲线，结果如图2 所示。该电极在10mM的葡萄糖PBS溶液中的响应较好，加入葡萄糖后，电极能够在10秒内就能够有响应信号。
实施例3：一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器制备方法，包括以下步骤：
1)将1mmol丙烯基咪唑、1mmol 1巯基丙酸和12mg引发剂偶氮二异丁腈加入到5mL的1,4-二氧六环中，75℃反应12h。反应完全后降至室温，该溶液缓慢滴加到50mL去离子水中沉淀。过滤，滤饼在烘箱中烘干。
2)将1.5mmol的步骤1)中的产物和1mmol的Ru-(bpy)2Cl加入到5mL的乙醇中，回流反应三天。反应完全后，冷却至室温，缓慢滴加到50mL去离子水中。过滤，收集滤液。滤液在烘箱中干燥得到产物。
3)将1mmol 2)中得到的产物溶于去离子水中，加入28mg EDC和16mg NHS 活化羧基，加入0.78g聚赖氨酸，室温反应2天。将该体系透析，冻干，得到产物。
4)将7.8μL的3)中得到的产物的水溶液(10mg/mL)、16μL葡萄糖氧化酶水溶液(10mg/mL)和6μL京尼平水溶液(2.5mg/mL)混合后，40℃交联2天。
5)将该凝胶体系滴加到电极表面，待水分蒸发后，置入真空环境中2天，得到目标电极。
测试制备的电极在10mM葡萄糖的PBS溶液中不同气体氛围下的时间电流曲线，结果如图3所示。随着溶液中气体氛围的变化，信号值变化较小。该结果说明制备的电极对测试环境中的氧气浓度变化不敏感。
实施例4：一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器制备方法，包括以下步骤：
1)将1mmol乙烯基咪唑、1mmol 4-巯基氢化肉桂酸和12mg引发剂偶氮二异丁腈加入到5mL的N,N-二甲基甲酰胺中，80℃反应8h。反应完全后降至室温，该溶液缓慢滴加到50mL去离子水中沉淀。过滤，滤饼在烘箱中烘干。
2)将2mmol的步骤1)中的产物和1mmol的Os-(二甲氧基-bpy)2Cl加入到 5mL的乙醇中，回流反应三天。反应完全后，冷却至室温，缓慢滴加到50mL去离子水中。过滤，收集滤液。滤液在烘箱中干燥得到产物。
3)将1mmol 2)中得到的产物溶于去离子水中，加入28mg EDC和16mg NHS 活化羧基，加入0.645g聚乙烯亚胺，室温反应2天。将该体系透析，冻干，得到产物。
4)将7μL的3)中得到的产物的水溶液(15mg/mL)、2μL葡萄糖氧化酶水溶液(8mg/mL)和2μL聚乙二醇二缩水甘油醚水溶液(2mg/mL)混合后，室温交联2天。
5)将该凝胶体系滴加到电极表面，待水分蒸发后，置入真空环境中2天，得到目标电极。
测试制备的电极在0、5mM、10mM、15mM、20mM葡萄糖的PBS溶液中的时间电流曲线，结果如图4所示。随着葡萄糖浓度的增加，电流信号值也增加。且葡萄糖浓度和电流信号值呈比较好的线性关系。该结果表明，制备的电极能够较好的测试在0-20mM的葡萄糖浓度范围内的葡萄糖浓度。
实施例5：一种基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器制备方法，包括以下步骤：
1)将1mmol丙烯基咪唑、1mmol巯基乙酸和12mg引发剂偶氮二异丁腈加入到5mL的甲醇中，65℃过夜反应。反应完全后降至室温，该溶液缓慢滴加到50mL去离子水中沉淀。过滤，滤饼在烘箱中烘干。
2)将1.5mmol的步骤1)中的产物和1mmol的Os-(二氯-bpy)2Cl加入到5mL 的乙醇中，回流反应三天。反应完全后，冷却至室温，缓慢滴加到50mL去离子水中。过滤，收集滤液。滤液在烘箱中干燥得到产物。
3)将1mmol 2)中得到的产物溶于去离子水中，加入28mg EDC和16mg NHS 活化羧基，加入壳聚糖水溶液(含壳聚糖0.806g)，室温反应2天。将该体系透析，冻干，得到产物。
4)将5μL的3)中得到的产物的水溶液(10mg/mL)、2μL葡萄糖氧化酶水溶液(5mg/mL)和3μL聚乙二醇二缩水甘油醚水溶液(3mg/mL)混合后，室温交联2天。
5)将该凝胶体系滴加到电极表面，待水分蒸发后，置入真空环境中2天，得到目标电极。
Claims (8)
1.一种葡萄糖电化学传感器的制备方法，所述葡萄糖电化学传感器基于含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶，其特征在于包括以下步骤：
A、将过渡金属配合物与含氮杂环化合物和端巯基烷基酸反应合成含过渡金属配合物的短链接枝分子；所述端巯基烷基酸为巯基乙酸、巯基丙酸、4-巯基氢化肉桂酸、11-巯基十一烷酸、16-巯基十六烷基酸中的一种或多种；所述含氮杂环化合物为乙烯基咪唑、丙烯基咪唑的一种或多种，
B、将此短链分子接枝到阳离子聚合物侧链上得到结构式如下所示的过渡金属配合物介质的阳离子氧化还原聚合物，
其中，M为过渡金属；
L为过渡金属配合物中的配体，选自二联咪唑和二联吡啶类衍生物；
x为阳离子氧化还原聚合物分子侧链上碳氢链的长度；
y为端巯基烷基酸分子上碳氢链的长度；
z为与过渡金属配合物接枝的乙烯基含氮杂环化合物上碳氢链的长度；
并且4≤x+y+z≤20，
C、将步骤B中得到的过渡金属配合物介质的阳离子氧化还原聚合物溶解在去离子水中，得到过渡金属配合物介质的阳离子氧化还原聚合物水溶液，
D、将步骤C中得到的过渡金属配合物介质的阳离子氧化还原聚合物水溶液、以及葡萄糖氧化酶水溶液和交联剂水溶液的溶液混合物涂布到电极表面，
E、待水分蒸发后置入真空干燥箱中干燥，得到含过渡金属配合物介质的阳离子氧化还原聚合物水凝胶的葡萄糖电化学传感器。
2.根据权利要求1所述的制备方法，其特征在于步骤A中所用的过渡金属M为铁、钴、钌、锇和钒中的一种或多种。
3.根据权利要求1或2所述的制备方法，其特征在于步骤A中所用的过渡金属配合物中的配体L为N,N′-二甲基-2,2′-联咪唑、2,2′-联吡啶、4,4′-二甲基-2,2′-联吡啶、4,4′-二甲氧基-2,2′-联吡啶和4,4′-二氯-2,2′-联吡啶中的一种或多种。
4.根据权利要求1或2所述的制备方法，其特征在于步骤B中使用的阳离子氧化还原聚合物选自侧链带有氨基的壳聚糖、N-羧甲基壳聚糖、O-羧甲基壳聚糖、羟丙基壳聚糖和N-马来酰化壳聚糖的天然高分子，和聚赖氨酸、聚烯丙基胺、聚乙烯亚胺、聚精氨酸的合成高分子中的一种或多种。
5.根据权利要求1或2所述的制备方法，其特征在于步骤D中使用的交联剂选自戊二醛、聚乙二醇二缩水甘油醚和京尼平中的一种或多种。
6.根据权利要求1或2所述的制备方法，其特征在于步骤D中，所述溶液混合物通过将步骤B中得到的过渡金属配合物介质的阳离子氧化还原聚合物水溶液、葡萄糖氧化酶水溶液和交联剂水溶液在0-45℃下，混合45分钟-2天得到。
7.根据权利要求6所述的制备方法，其特征在于所述溶液混合物通过将1-20mg/mL的过渡金属配合物介质的阳离子氧化还原聚合物水溶液、1-10mg/mL的葡萄糖氧化酶水溶液、1-10mg/mL的交联剂水溶液混合得到，使得溶液混合物中过渡金属配合物介质的阳离子氧化还原聚合物、葡萄糖氧化酶和交联剂的质量比为1：(0.1-5)：(0.01-0.5)。
8.根据权利要求1-7中任一项方法制备的葡萄糖电化学传感器。
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