CN113466304A - 一种pedot:pss水凝胶修饰电极及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种PEDOT:PSS水凝胶修饰电极及其制备方法和应用。其制备方法,包括以下步骤:(1)将含CuSO4·5H2O的乙酸水溶液滴加在印刷电极上,以‑0.4V的恒定电压电沉积,以获得均匀的铜镀层;(2)滴加稀释5%的PEDOT:PSS电解质溶液,在0.5V恒定电位下电沉积,获得PEDOT:PSS水凝胶修饰电极。本发明采用电聚合法修饰工作电极,成功构建了PEDOT:PSS水凝胶电极,水凝胶粘附力强,水凝胶电极比较稳定,可用于制备可穿戴传感器,能够有效检测汗液中尿酸的浓度变化,灵敏度高,选择性好,具有柔性,可实现对生物流体中代谢物和营养物的精确检测。
Description
技术领域
本发明涉及传感器电极技术领域,更具体的说是涉及一种PEDOT:PSS水凝胶修饰电极及其制备方法和应用。
背景技术
可穿戴传感器能够连续检测生命体征信号(心电图、呼吸频率、脉搏、皮肤水合作用等),具有巨大的应用潜力。目前的工作主要集中于检测皮肤或表皮下浅层组织中的物理信号。组织液中循环代谢物(例如尿酸和葡萄糖等)的实时追踪和检测在医疗保健领域具有重要意义,因为它可以为用户在分子水平上提供切实可行的反馈。检测组织液中的目标物往往需要植入传感器,无创型可穿戴传感器尚处于开发阶段,亟待深入研究。
设计开发无创型可穿戴生物传感器,并用其连续检测组织液(汗液、唾液或泪液)中与人体性能相关的标志物,近年来引起了研究者广泛的研究兴趣。在设计无创型可穿戴传感器方面,科学家开发了多种检测方法,例如比色法、荧光法和电化学法。其中,电化学法适用于传感界面的检测,具有灵敏度高、仪器成本低、易于与读出电子设备集成的特点。
一般的,酶促传感器凭借其高的灵敏度和选择性,用于生物分子检测。但是,酶促传感器易受环境变化(例如温度或pH值)的影响,稳定性较差。因此,研究设计非酶促电化学可穿戴传感器至关重要。
尿酸(UA)作为嘌呤代谢的最终产物,在人体血液和汗液中的浓度具有一定关系。通过实时监测汗液中尿酸的浓度,可有效降低临床环境中痛风和高尿酸血症的风险。然而,汗液中的代谢物(例如UA)浓度很低,因此设计灵敏度高、具有可穿戴性的电化学传感器用于人体汗液检测,具有重要研究价值。
发明内容
有鉴于此,本发明采用电聚合法修饰工作电极,成功构建PEDOT:PSS水凝胶电极,水凝胶粘附力强,水凝胶电极比较稳定,可用于制备可穿戴传感器,能够有效检测汗液中尿酸的浓度变化,灵敏度高,选择性好,具有柔性,可实现对生物流体中代谢物和营养物的精确检测。
为了达到上述目的,本发明采用如下技术方案:
一种PEDOT:PSS水凝胶修饰电极的制备方法,包括以下步骤:
(1)将含CuSO4·5H2O的乙酸水溶液滴加在印刷电极上,以-0.4V的恒定电压电沉积,以获得均匀的铜镀层;
(2)滴加PEDOT:PSS电解质溶液,在0.5V恒定电位下电沉积,获得PEDOT:PSS水凝胶修饰电极。
制备原理为在足够的阳极电压下,工作电极上的金属铜被氧化成铜离子,扩散到电解液中,并局部诱导PEDOT:PSS电解液凝胶化。
采用上述技术方案的有益效果:现有的技术难以将水凝胶电极直接应用于可穿戴传感器,并且水凝胶容易失水,进而引起机械、电学等性能发生改变,导致器件性能不稳定;同时高含水量增加水凝胶与其它基底或电极材料之间的键合难度。是实现其工程化应用的关键。本发明的制备方法简单,水凝胶附着性强,且具有良好的机械性能和很好的传感性能。
优选的,步骤(1)中,所述CuSO4·5H2O的浓度为0.01g mL-1,所述乙酸水溶液中乙酸与水的体积比为4:45。
优选的,步骤(1)中,电沉积的时间为230~270秒;步骤(2)中,电沉积的时间为550~650秒。
上述制备方法中参数的改变会影响水凝胶沉积的厚度及均匀程度,上述制备方法得到的水凝胶沉积均匀,且厚度一致。
本发明还公开了上述PEDOT:PSS水凝胶修饰电极在制备可穿戴传感器中的应用。
优选的,所述传感器用于检测汗液中的尿酸浓度变化。电极表面尿酸发生氧化反应失两个电子变成了氧化态结构,其氧化还原过程机理如下:
经由上述的技术方案可知,与现有技术相比,本发明提提供了一种PEDOT:PSS水凝胶修饰电极,由于电极材料对于可穿戴传感器的电化学传感性能具有决定性作用,而导电聚合物PEDOT:PSS水凝胶可加工性强,机械强度高,导电性良好。并且,水凝胶比表面积大,柔性好,对于构建柔性传感器具有重要的研究价值。采用此电极制备的可穿戴传感器具有以下优点:
1、可有效检测汗液中的尿酸,灵敏度高,选择性强。
2、该可穿戴传感器具有一定的柔性、长期稳定性和形变稳定性。
3、该可穿戴传感器可以有效检测健康受试者在禁食和富含嘌呤的饮食后汗液中的UA浓度变化。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图。
图1附图为PEDOT:PSS水凝胶修饰电极的制备流程图;
图2附图为PEDOT:PSS水凝胶表征图谱,其中,(A)为PEDOT:PSS水凝胶修饰电极放大200倍的扫描电镜图像,B为PEDOT:PSS水凝胶修饰电极放大500倍的扫描电镜图像;(C)PEDOT:PSS水凝胶的热重曲线;(D)PEDOT:PSS水凝胶的傅立叶变换红外光谱图;(E)CPE/PEDOT:PSS水凝胶电极在5.0mM含0.1M KCl的[Fe(CN)6]3-/4-溶液中以不同扫描速率(20-200mV s-1)进行的CV曲线;(F)CPE/PEDOT:PSS电极扫描速率与氧化还原电流峰值平方根的线性图;
图3附图为PEDOT:PSS水凝胶修饰电极构建的电化学性能表征图谱,其中,(A)为裸印刷电极(蓝线)和CPE/PEDOT:PSS水凝胶修饰电极(红线)在5.0mM含0.1M KCl的[Fe(CN)6]3-/4-溶液中的EIS图;(B)为裸印刷电极(蓝线)和CPE/PEDOT:PSS修饰电极(红线)在PBS溶液(0.2M,pH 7)中对0.5mM尿酸的DPV图;(C)为不同电位下CPE/PEDOT:PSS修饰电极对0.1mMUA的i-t曲线;(D)为CPE/PEDOT:PSS修饰电极在不同pH的PBS溶液中对0.2mM UA的DPV响应;(E)为CPE/PEDOT:PSS修饰电极在搅拌PBS(0.2M,pH7)溶液中对2-250μM尿酸的i-t响应,应用电压为0.4V;(F)UA传感器的相关线性校准图;
图4附图为CPE/PEDOT:PSS可穿戴传感器对50μM的UA、50μM酒精(EA)、4mM的乳酸(LA)、10μM的抗坏血酸(AA)和100μM葡萄糖(Glu)的i-t曲线;
图5附图为CPE/PEDOT:PSS修饰电极的稳定性和重现性检测图谱;其中,(A)为CPE/PEDOT:PSS修饰电极在PBS溶液(0.2M,pH 7)中的CV图,每10分钟记录一次;(B)为CPE/PEDOT:PSS修饰电极存储25天内,其在含有0.2mM UA的PBS溶液(0.2M,pH 7)中的安培电流变化与存储时间的关系曲线;(C)为同一片CPE/PEDOT:PSS修饰电极对0.2mM UA分别测定十次得到的安培电流响应信号的变化(测量次数编号为1-10),误差棒代表三次测量值的标准差;(D)为相同的条件下制备得到的九片CPE/PEDOT:PSS修饰电极分别对0.2mM UA安培电流响应信号变化(电极编号为1-9);
图6附图为CPE/PEDOT:PSS水凝胶修饰电极在不同情况下的实物图和安培电流信号图;其中,(A)为弯曲前;(B)为90°向外弯曲后;(C)为90°向内弯曲;
图7附图为CPE/PEDOT:PSS可穿戴传感器的实际样品检测图谱;其中,(A)为1-4号健康受试者在禁食和富含嘌呤的饮食后汗液中的UA浓度变化图;(B)为电化学传感器测定的UA浓度与酶联免疫试剂盒测定浓度的相关性;
图8附图为用酶联免疫法分析汗液中UA浓度的相关线性校准图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
制备PEDOT:PSS水凝胶修饰电极
使用辰华电化学工作站660E,采用碳印刷电极(CPE)(购于青岛波碳科技有限公司)作为三电极系统。其中,工作电极和对电极为碳,参比电极是银/氯化银,稀释至原溶液的5%,原溶液是购买的CleviosTM PH1000。
具体步骤:
(1)将100μL含CuSO4·5H2O(0.01g mL-1)(阿拉丁)的乙酸(国药)和水的混合溶液(4:45v/v)滴加在印刷电极上,以-0.4V的恒定电压电沉积250秒,以获得均匀的铜镀层;
(2)滴加100μL稀释至5%的PEDOT:PSS电解质溶液(CleviosTM PH1000,贺利事电子材料,固含量1.1-1.3%),在0.5V恒定电位下电沉积600秒,获得PEDOT:PSS水凝胶修饰电极。
PEDOT:PSS水凝胶修饰电极的性能表征
1.PEDOT:PSS水凝胶表征
为了证明沉积的材料为水凝胶而不是PEDOT:PSS薄膜,使用扫描电子显微镜(SEM)表征了PEDOT:PSS水凝胶的微观结构,如图2A所示。图2A显示了PEDOT:PSS水凝胶的三维交联的多孔形态,图2B中显示了PEDOT:PSS水凝胶中平均孔径约为50μm。
如图2C所示,通过热重法(TG)测定PEDOT:PSS水凝胶的含水量为95.2%。水凝胶的高含水量得益于多孔的三维网络。PEDOT:PSS水凝胶的化学结构采用FT-IR光谱研究,如图2D所示,波数为1207cm-1的S-O键证实了在PEDOT:PSS水凝胶中磺酸盐的存在。
由于PEDOT:PSS水凝胶具有多孔结构,因此具有较大的比表面积。同时,电活性面积也会相应增大。利用Randles-Sevcik方程计算了修饰电极的电活性面积。
Ip=(2.69×105)n3/2 ACD1/2υ1/2 (1)
其中υ为扫描速率(V s-1),D为分析物的扩散系数(cm2 s-1),7.6×10-6cm2 s-1(T=298K),C为分析物浓度,A为工作电极电活性面积(cm2),n为转移分子的电子数。如图2E所示,在5.0mM含0.1M KCl的[Fe(CN)6]3-/4-溶液中,以不同扫描速率(20-200mV s-1)测量CV响应来研究电活性表面积。通过绘制峰值电流与扫描速率的平方根的线性关系图(图2F),并将上述值代入式(1)中,发现电活性表面积为0.6985cm2,是裸碳丝网印刷电极面积(0.1256cm2)的5.56倍。
2.PEDOT:PSS水凝胶修饰电极构建的电化学性能表征
采用电化学阻抗谱(EIS)对PEDOT:PSS水凝胶修饰电极的制备过程进行了电化学表征。如图3A所示,CPE/PEDOT:PSS的阻抗(图3A,红线)比裸CPE上的阻抗(图3A,蓝线)小得多,这归因于导电聚合物水凝胶修饰电极优异的电子转移特性。这一结果进一步证实了PEDOT:PSS水凝胶修饰电极的成功构建。
由于尿酸(UA)具有电活性,其氧化还原机理如下:
采用DPV测试UA的电化学响应,如图3B所示。显然,裸CPE在0.5mM UA存在时只出现一个相对较弱的氧化峰(蓝线,峰电位为0.5V)。而在相同的UA浓度下,PEDOT:PSS水凝胶修饰电极的峰值电流明显增大,并且峰值电位向负值(0.41V)移动,这可以归因于PEDOT:PSS水凝胶优异的催化活性和较大的比表面积。
3.PEDOT:PSS水凝胶修饰电极的实验条件优化
为了获得最佳的UA传感性能,对i-t应用电位进行了优化。如图3C所示,当施加的电势在0.4V左右时,所构建的传感器对UA产生的响应最大,在此电势下背景噪声是可以接受的。因此,采用0.4V作为以下安培测量的最佳应用电位。同时通过使用DPV探究在人体汗液pH条件下对尿酸的电流响应,如图3D所示,可以观察到pH的改变并没有对电流信号产生较大影响,因此证明该传感器可以在可接受的汗液pH范围内对尿酸进行检测。
4.PEDOT:PSS水凝胶修饰电极的电化学传感性能表征
(1)高灵敏度
PEDOT:PSS水凝胶修饰电极在氧化电压为0.4V,磁性搅拌的条件下连续加入不同浓度的UA,记录电极在人工汗液(PBS 7)中的安培响应。如图3E所示,该传感器对尿酸的检测浓度范围为2-250μM,如图3F所示,线性方程为I(μA)=0.11C(μM)+1.6(R2=0.9994)。该传感器的最低检测限为1.2μM(SN-1=3)。灵敏度高,线性范围宽,可应用于实际汗液检测。
(2)选择性
通过特异性测试来测试人类汗液中存在的其他典型干扰物种的影响。如图4所示,尿酸传感器的性能不受酒精、抗坏血酸、尿酸、乳酸和葡萄糖的影响,这些浓度值通常存在于汗液中。结果表明,该传感器对人体汗液中UA具有较好的选择性。
(3)稳定性
由于水凝胶材料在溶液中吸水膨胀,容易从电极表面脱落。因此,通过在PBS(0.2M,pH 7)中每隔10分钟进行CV测量来表征电极物质的稳定性,如图5A所示。经过9个循环后,CV信号几乎与初始值重合。此外,通过测量三个PEDOT:PSS修饰电极,在25天内检测对0.2mM UA传感器的长期稳定性也进行了评估。如图5B所示,25天后UA传感器保持了95%以上的初始信号响应,表明传感器优异的长期存储稳定性。
(4)重现性
通过使用同一片电极对0.2mM UA分别测定十次得到的安培电流响应信号的变化,如图5C所示,相对标准偏差(RSD)值为1.52%。并在相同的实施例1的条件下制备九片CPE/PEDOT:PSS修饰电极,分别测得对0.2mM UA安培电流响应信号变化,如图5D所示,9种电极测得信号的RSD为1.72%。这些结果显示了该传感器的高重现性。
(5)机械稳定性
为了研究柔性传感器的机械稳定性,图6显示了在空白PBS(0.2M,pH 7)溶液中以及在(A)弯曲前,(B)90°向外弯曲后和(C)90°向内弯曲后的安培响应。这些数据表明,反复变形后的电化学性能没有明显的差异,这证明了该传感器的机械稳定性良好。
5.柔性可穿戴传感器的实际样品检测
为了评估该传感器对于实际汗液的检测能力,我们在健康受试者中进行了嘌呤饮食控制研究。如图7A所示,对于过夜禁食(n=4)的受试者,在食用富含嘌呤的饮食后汗液UA水平均升高。并且我们将该传感器所测数据与商用酶联免疫试剂盒所得数据进行了对比(试剂盒线性如图8所示),所得校准曲线如图7B所示,相关系数为0.987,这表明该传感器测量实际汗液的可靠性。
本说明书中各个实施例采用递进的方式描述,每个实施例重点说明的都是与其他实施例的不同之处,各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言,由于其与实施例公开的方法相对应,所以描述的比较简单,相关之处参见方法部分说明即可。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (6)
1.一种PEDOT:PSS水凝胶修饰电极的制备方法,其特征在于,包括以下步骤:
(1)将含CuSO4·5H2O的乙酸水溶液滴加在印刷电极上,以-0.4V的恒定电压电沉积,以获得均匀的铜镀层;
(2)滴加PEDOT:PSS电解质溶液,在0.5V恒定电位下电沉积,获得PEDOT:PSS水凝胶修饰电极。
2.根据权利要求1所述的一种PEDOT:PSS水凝胶修饰电极的制备方法,其特征在于,步骤(1)中,所述CuSO4·5H2O的浓度为0.01g mL-1,所述乙酸水溶液中乙酸与水的体积比为4:45。
3.根据权利要求1所述的一种PEDOT:PSS水凝胶修饰电极的制备方法,其特征在于,步骤(1)中,电沉积的时间为230~270秒;步骤(2)中,电沉积的时间为550~650秒。
4.根据权利要求1-3任一项所述的PEDOT:PSS水凝胶修饰电极的制备方法制备得到的PEDOT:PSS水凝胶修饰电极。
5.如权利要求4所述的一种PEDOT:PSS水凝胶修饰电极在制备可穿戴传感器中的应用。
6.如权利要求5所述的一种PEDOT:PSS水凝胶修饰电极在制备可穿戴传感器中的应用,其特征在于,所述传感器用于检测汗液中的尿酸浓度变化。
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