CN111772642B - 一种透气柔性表皮电化学传感器及其制备方法、应用 - Google Patents
一种透气柔性表皮电化学传感器及其制备方法、应用 Download PDFInfo
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Abstract
本发明公开一种透气柔性表皮电化学传感器及其制备方法、应用，主要自下而上的多孔柔性基底层和电化学传感器构成；所述多孔聚酰亚胺薄膜具有一定的抗卷曲功能，能够与皮肤共形，具有良好的皮肤贴合性，同时具有良好的透气性，有利于于汗液蒸发，防止皮肤刺激，避免检测物质积累，提高检测准确度。所述多孔聚酰亚胺薄膜制备方法无需高温高压，对制膜设备的要求简单，具有高效、成本低、一步到位、无模板等优点；本发明的传感器具有透气，柔性、皮肤贴合性好等优点，长期佩戴对皮肤无刺激，可以用于可穿戴柔性表皮电子设备。
Description
技术领域
本发明属于电化学传感器领域，特别是涉及一种透气柔性电化学传感器及其制备方法、应用。
背景技术
随着材料和制造技术的发展，可穿戴柔性表皮传感器引起了学术界和工业界的广泛关注，这些可穿戴柔性表皮传感器可以用于连续监测健康数据，其监测内容包括皮肤温度，心电信号，肌电信号，以及生理活动中的各种物质的浓度等等，目前研究人员在可穿戴柔性表皮传感器也已经取得了一定的成果。
虽然柔性表皮传感器能够很好地应用于人体健康数据监测方面，但是为了提高信号精度，实时检测数据，传感器与皮肤需要时刻保持紧密接触，所以除了不同的传感性能，其透气性问题作为最基本的要求也是必不可少的。然而目前大多数表皮检测传感器都是建立在固体聚合物及之上，如聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯和聚酰亚胺等，而皮肤时刻在与外界进行气体交换、汗液排出，此类聚合物结构致密，缺乏有效的透气性，若长期佩戴以上述聚合物为基底的传感器，则会阻碍皮肤汗液的蒸发和有机成分的释放挥发，从而导致皮肤炎症，影响穿戴舒适性；此外，对于以体液(如汗液、细胞间液等)为检测物质的柔性表皮传感器，在基底缺乏透气性的情况下会引起检测物质的累积，影响传感器检测结果。
发明内容
本发明目的在于克服现有技术的不足，提出一种透气柔性电化学表皮传感器，实现传感器与皮肤之间的长期贴合，解决传感器贴片与皮肤的粘合问题和长时间贴附所引起的皮肤不适问题，同时消除由于检测物质长期累积无法及时散发所引起检测不准确问题。
本发明为所要解决的技术问题提出的技术方案之一是多孔聚酰亚胺薄膜在电化学传感器基底的应用。
第二个技术方案是一种透气柔性表皮电化学传感器，其包括多孔柔性基底层和电化学传感器。
包含辅助电极、工作电极、参比电极，该传感器通过在工作电极上固化特异性修饰材料，实现对待测物的特异性测量。
多孔柔性基底层选择多孔聚酰亚胺柔性材料，与皮肤共形贴合，用于可穿戴柔性表皮电子设备。
多孔柔性基底层，用于体液蒸发，防止皮肤刺激
透气柔性表皮电化学传感器，主要由自下而上的透气基底层和电化学电极层构成；所述透气性基底层采用多孔聚酰亚胺薄膜；电化学电极利用印刷技术将电极制作在透气型柔性基底上。
为了使柔性表皮传感器的透气性能够满足皮肤新陈代谢的要求，我们提出以多孔聚酰亚胺基底柔性表皮电化学传感器，利用印刷技术制备柔性电化学传感器，该方式所制备的传感器有良好的透气性，可用于体液(如汗液、细胞间质液等)的蒸发，防止皮肤刺激，同时所采用的多孔聚酰亚胺的制备方式具有简单、高效、成本低、一步到位、无模板等优点。
第三个技术方案是透气型柔性表皮传感器制备方法，如下：
a)首先制备聚合物承载基底，以聚二甲基硅氧烷为例，先对清洁的玻璃片进行氧等离子体机处理，然后在玻璃片上旋涂聚二甲基硅氧烷，之后将聚二甲基硅氧烷高温固化后在氧等离子体机处理。
b)将前驱体聚酰胺酸PAA溶液与添加剂混合搅拌形成铸膜液，将铸膜液经脱泡后，在相对湿度为40％-60％的条件下旋涂在载有聚二甲基硅氧烷基底的玻璃板上，自然晾干后将其浸入凝固液进行固化、成孔，之后取出自然晾干，经热亚胺化或化学亚胺化处理得到多孔聚酰亚胺薄膜。具体的，添加剂为丙三醇、四氢呋喃、二氯甲烷、三氯甲烷、邻苯二甲基二丁酯中的一种，比例占前驱体PAA溶液质量分数的5％-30％，凝固液为甲醇、无水乙醇、乙二醇中的一种或多种混合，旋涂的聚酰亚胺薄膜厚度在10-50μm，浸入凝固浴的时间为0.5-2h，以保证凝固液与铸膜液中的溶剂充分交换。
c)利用氧等离子体机处理多孔聚酰亚胺基底，采用印刷的方式在基底上打印传感器电极，之后进行表面功能化处理。
本发明具有如下优点：
1、电化学传感器制作在多孔聚酰亚胺基底上，聚酰亚胺作为柔性材料具有一定的抗弯曲和抗拉伸的功能，能够与皮肤共形贴合，具有一定的抗变形的能力，可以用于可穿戴柔性表皮电子设备。
2、电化学传感器采用多孔聚酰亚胺薄膜为基底，满足皮肤透气性的要求，减少了可穿戴设备在长期佩戴过程中所引起的不适；同时待测物质的及时挥发，保证了传感器检测的准确程度。
3、多孔聚酰亚胺薄膜的制备，可以通过调节体系中稀释剂的种类、聚合物浓度、凝固浴时间，实现结构的多样性和可控性；成膜过程中所需控制参数少，因此制备过程重复性好，微孔结构的控制精确性高；制备的材料具有较高的孔隙率，同时保持结构的完整和强度；无需高温高压，对制膜设备的要求简单、成本低、原料易得、对环境友好。
附图说明
图1是本发明透气柔性表皮电化学传感器的整体结构示意图；
图2是本发明所制备的多孔聚酰亚胺薄膜正反面光学显微镜图像：
a-多孔聚酰亚胺薄膜正面光学显微镜图像
b-多孔聚酰亚胺薄膜反面光学显微镜图像
附图标记：
1.1：参比电极
1.2：工作电极
1.3：辅助电极
2：信号线
3：多孔聚酰亚胺基底。
具体实施方式
下面结合实施例和附图对本发明的透气柔性电化学传感器做出详细说明，但本发明不以任何形式受限于实施例内容。实施例中所述实验方法如无特殊说明，均为常规方法；如无特殊说明，所述实验试剂和材料，均可从商业途径获得。
实施例1：下面以透气柔性葡萄糖传感器为实施例做出详细说明。
如图1所示，采用本发明方法所制备的透气柔性葡萄糖传感器，整个传感器制作在与人体皮肤表皮共形贴合的多孔聚酰亚胺膜3上，用于连续监测人体血糖浓度。传感器由参比电极1.1、工作电极1.2和辅助电极1.3组成，所述的参比电极1.1、工作电极1.2和辅助电极1.3分别通过信号线2连接外部设备。
所述的参比电极1.1、工作电极1.2和辅助电极1.3共同构成对体液(如汗液、细胞间质液等)中葡萄糖浓度进行检测的电化学传感器，可在外部设备的控制下实现对葡萄糖浓度的原位、实时采集。
将传感器与皮肤粘合好后，即可进行葡萄糖浓度的检测：这里的检测体系是传感器中的参比电极1.1、工作电极1.2和辅助电极1.3共同形成的电化学传感器，如图1所示，给工作电极1.2加上相对于参比电极1.1为-0.2V的电压，并使得工作电极1.2与辅助电极1.3之间形成测量回路，葡萄糖氧化酶特异性催化葡萄糖的分解，在恒电势下电化学反应中电子的转移速率即电化学反应中的电流与待测液中葡萄糖的浓度成正比，通过检测该电流(即1.2与1.3之间的电流)的大小就可以获得待测液中葡萄糖的浓度。
本实施例中所制作的葡萄糖传感器基于多孔聚酰亚胺基底3，其作用是使所述的参比电极1.1、工作电极1.2和辅助电极1.3与皮肤紧密相连并随着皮肤的形变而形变，避免了由于相对运动使电极与皮肤脱离而导致的检测不连续，同时满足皮肤透气性的要求，减少了可穿戴设备在长期佩戴过程中所引起的不适；使得体液得到及时挥发，保证了葡萄糖检测的准确程度。
透气柔性葡萄糖传感器的具体制作过程是：
首先将7cm*5cm的玻璃片用无水乙醇或丙酮等有机溶液清洗，清除表面异物；利用100W的氧等离子体机处理玻璃片30s，在玻璃片上用匀胶机以500rpm旋涂45s的聚二甲基硅氧烷，之后将聚二甲基硅氧烷基底放在95℃的加热板上加热60min，利用100W的氧等离子体机处理聚二甲基硅氧烷基底30s，得到的聚二甲基硅氧烷基底用于支撑制作多孔聚酰亚胺薄膜。
取15g前驱体聚酰胺酸PAA溶液与烧杯中，加入其质量分数25％的邻苯二甲酸二丁酯，在磁力搅拌机下充分搅拌2小时，得到铸膜液；铸膜液采用真空抽气方式脱泡30min，将铸膜液在温度25℃，相对湿度为40％-60％的条件下旋涂在载有聚二甲基硅氧烷基底的玻璃板上，转速为1000-2000rmp，自然晾干6分钟后将其浸入无水乙醇凝固液中30min，进行固化、成孔，之后取出自然晾干，放入马弗炉中热亚胺化，按照100℃/1h、200℃/5h的程序阶梯式升温固化。待温度降到室温后，得到厚度为10μm聚酰亚胺多孔薄膜。
利用100W的氧等离子体机处理多孔聚酰亚胺基底30s，之后是葡萄糖传感器的制作，首先利用喷墨打印的方式在多孔聚酰亚胺基底3上打印一层金属银，然后利用三氯化铁溶液对银电极进行氯化处理，得到参比电极1.1和辅助电极1.3，接着用喷墨打印的方式在多孔聚酰亚胺基底上打印一层金属金作为工作电极1.2的基底电极，然后再在金属金上用喷墨打印的方式修饰一层石墨烯和一层铂纳米颗粒，然后固定葡萄糖氧化酶构成工作电极1.2，将多孔聚酰亚胺基底从承载基底上剥离即完成整个透气柔性葡萄糖传感器的制作。
以下为实施例2至5的关键工艺参数，其他步骤同实施例1：
本发明公开和揭示的所有组合可以通过借鉴本文公开内容产生，尽管本发明的组合已通过详细实施过程进行了描述，但是本领域技术人员明显能在不脱离本发明内容、精神和范围内对本发明所述的装置进行拼接或改动，或增减某些部件，更具体地说，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容之中。
Claims (4)
1.一种透气柔性表皮电化学传感器，其包括多孔柔性基底层和电化学传感器；电化学传感器包含辅助电极、工作电极、参比电极，该传感器在工作电极上固化特异性修饰材料；多孔柔性基底层选择多孔聚酰亚胺柔性材料，与皮肤共形贴合，用于可穿戴柔性表皮电子设备；
所述透气柔性表皮电化学传感器的制备方法，包括如下步骤：
a)首先制备聚合物承载基底，先对清洁的玻璃片进行氧等离子体机处理，然后在玻璃片上旋涂聚二甲基硅氧烷，之后将聚二甲基硅氧烷高温固化后再氧等离子体机处理；
b)将前驱体聚酰胺酸PAA溶液与添加剂混合搅拌形成铸膜液，将铸膜液经脱泡后，在相对湿度为40％-60％的条件下旋涂在载有聚二甲基硅氧烷基底的玻璃板上，自然晾干后将其浸入凝固液进行固化、成孔，之后取出自然晾干，经热亚胺化或化学亚胺化处理得到多孔聚酰亚胺薄膜；
添加剂比例占前驱体PAA溶液质量分数的5％-30％，旋涂的聚酰亚胺薄膜厚度在10-50μm，浸入凝固浴的时间为0.5-2h，以保证凝固液与铸膜液中的溶剂充分交换；
c)利用氧等离子体机处理多孔聚酰亚胺基底，采用印刷方式在基底上打印传感器电极，
之后进行表面功能化处理。
2.根据权利要求1所述的透气柔性表皮电化学传感器，其特征在于，凝固液为甲醇、无水乙醇、乙二醇中的一种或任意两种的混合溶液。
3.根据权利要求1所述的透气柔性表皮电化学传感器，其特征在于，添加剂为丙三醇、四氢呋喃、二氯甲烷、三氯甲烷、邻苯二甲基二丁酯中的一种。
4.根据权利要求1所述的透气柔性表皮电化学传感器，其特征在于，所述热亚胺化方法包括在温度为90-150℃下保持0.5-2小时、在大于200℃至300℃下保持3-7小时。
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