CN111551601A - 一种啶虫脒分子印迹电化学传感器的制备方法 - Google Patents

一种啶虫脒分子印迹电化学传感器的制备方法 Download PDF

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CN111551601A
CN111551601A CN202010626009.9A CN202010626009A CN111551601A CN 111551601 A CN111551601 A CN 111551601A CN 202010626009 A CN202010626009 A CN 202010626009A CN 111551601 A CN111551601 A CN 111551601A
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刘本志
马玉荣
崔立强
王敏
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Abstract

一种啶虫脒分子印迹电化学传感器的制备方法，是以处理过的丝网印刷碳电极作为基底，采用石墨烯修饰丝网印刷碳电极，在亚甲基蓝和啶虫脒的酸性硫酸钠溶液中电聚合形成分子印迹聚合物制得，并用异丁醇/乙酸溶液去除模板，得到对啶虫脒选择性响应的分子印迹电化学传感器。这种方法制备出的分子印迹电化学传感器对啶虫脒的检出限为1.7×10‑7 mol/L，线性范围为1×10‑6 mol/L‑2×10‑5 mol/L。本发明中提供的方法制备出的分子印迹电化学传感器具有良好的稳定性和选择性，而且制备方法简单实用。

Description

一种啶虫脒分子印迹电化学传感器的制备方法
技术领域
本发明涉及的是电化学传感器领域，具体涉及的是啶虫脒分子印迹电化学传感器的制备方法。
背景技术
啶虫脒是属氯化烟碱类化合物，其化学名称为N-(N-氰基-乙亚胺基)-N-甲基-2-氯吡啶-5-甲胺。啶虫脒是一种高效、广谱、机制新颖的杀虫剂，对害虫具有触杀、胃毒和内吸作用． 但在农作物以及施药环境中如残留过量，会造成环境中水体及土壤的污染和对人畜的毒害。
用于啶虫脒检测的方法主要有气相色谱法、高效液相色谱法、高效液相色谱-质谱法和荧光分析法等。这些方法具有很高的精确度和灵敏度，可以根据所测对象的性质选择某一种方法进行测量。但是它们都不同程度存在着操作复杂、费时费力、成本高等缺点。研究快速、便捷、低成本的啶虫脒检测方法具有重要意义。
分子印迹技术是一种制备对模板分子具有识别性能的聚合物的技术。分子印迹聚合物（MIPs）对模板分子的识别具有特异识别性、构效预定性和广泛实用性等特点。分子印迹聚合物具有化学稳定性好、选择性高和容易制备等特点。分子印迹电化学传感器就是将电化学传感器检测快速、操作简单的优势与分子印迹技术相结合，可用于对啶虫脒的选择性检测。
发明内容
发明目的：本发明的目的是提供一种啶虫脒分子印迹电化学传感器简易的制备方法，这种方法可用于解决分子印迹电化学传感器的制备过程复杂，稳定性差等问题。
技术方案：本发明采用如下的技术方案。
这种啶虫脒分子印迹电化学传感器的制备方法是以处理过的丝网印刷碳电极作为基底，采用石墨烯修饰丝网印刷碳电极，亚甲基蓝和啶虫脒的酸性硫酸钠溶液作为电解质，利用循环伏安法聚合形成分子印迹聚合物制得，这种方法制备出的分子印迹电化学传感器对啶虫脒的检出限为1.7×10-7 mol/L，线性范围为1×10-6 mol/L-2×10-5 mol/L，具体制备方法包括以下步骤：
步骤一：将丝网印刷碳电极依次用丙酮，乙醇和去离子水中分别超声洗涤数分钟。然后将电极在K3Fe(CN)6中扫描，得到可逆的循环伏安峰，证明电极处理好。
步骤二：将石墨烯分散到混酸溶液（HNO3 : H2SO4=1:3）中回流完成对石墨烯表面的羧基化修饰；然后，过滤、洗涤、烘干；将获得的产物超声分散得到悬浮液；取2μL-10μL悬浮液滴涂到处理好的丝网印刷碳电极表面，形成均匀分散层，自然晾干，得到石墨烯修饰电极。
步骤三：将亚甲基蓝和啶虫脒溶解在酸性硫酸钠溶液中，混合均匀，亚甲基蓝和啶虫脒的摩尔比为1:3-6:3。
步骤四：将步骤三中混合好的溶液作为电解质溶液，然后将石墨烯修饰的电极置于混合溶液中，采用循环伏安法进行电化学聚合形成分子印迹聚合物，用异丁醇/乙酸溶液洗脱啶虫脒后，得到啶虫脒的分子印迹电化学传感器。
上述方案中，酸性硫酸钠溶液的pH为1-5。
上述方案中电化学聚合方法为循环伏安法，电压范围：0.1V-1.2V，扫描速率:30mV/s-100mV/s，扫描周期: 20圈-80圈。。
上述方案中异丁醇/乙酸溶液浓度为1:1-6:1。
上述方法制备的啶虫脒分子印迹电化学传感器可用于水体中啶虫脒的定量检测。
具体实施方式
实施例1
丝网印刷碳电极预处理
将丝网印刷碳电极依次用丙酮，乙醇和去离子水中分别超声洗涤数分钟。然后将电极于K3Fe(CN)6中扫描，得到可逆的循环伏安峰，证明电极处理好。
实施例2
石墨烯修饰丝网印刷碳电极
将石墨烯分散到混酸溶液（HNO3 : H2SO4=1:3）中回流完成对石墨烯表面的羧基化修饰；然后，过滤、洗涤、烘干；将获得的产物超声分散得到悬浮液；取2μL-10μL悬浮液滴涂到处理好的丝网印刷碳电极表面，形成均匀分散层，自然晾干，得到石墨烯修饰电极。
实施例3
配制聚合溶液
以啶虫脒作为模板分子，亚甲基蓝作为功能单体，充分溶解在酸性硫酸钠溶液中，亚甲基蓝和啶虫脒的摩尔比为1:3-6:3。
实施例4
电化学聚合
将石墨烯修饰的丝网印刷碳电极置于所制得的聚合溶液中进行电聚合，工作电极为石墨烯修饰的丝网印刷碳电极，参比电极为Ag/AgCl电极，辅助电极为铂丝电极；电压范围：0.1V-1.2V，扫描速率: 30mV/s-100mV/s，扫描周期: 20圈-80圈。
实施例5
将所制得的聚合物电极置于异丁醇/乙酸溶液中洗脱50min，然后将洗脱后的电极用蒸馏水冲洗，在室温下晾干备用。
实施例6
工作曲线的绘制
采用方波伏安法进行啶虫脒的浓度测定实验。方波伏安法起止电位为-0.4 V-0.6 V，电位增量0.005 V，方波频率 15Hz，方波幅度0.1V，检测底液为2.0 mM K3[Fe(CN)6]和0.1 MKCl。每次使用后，将电极浸在异丁醇/乙酸溶液中，用磁力搅拌器洗脱30min，去除聚合膜中吸附的模板分子，以便重复使用。根据己知啶虫脒的浓度与方波伏安峰电流的差值绘制标准曲线，检出限为1.7×10-7 mol/L，线性范围为1×10-6 mol/L-2×10-5 mol/L。

Claims (5)

1.一种啶虫脒分子印迹电化学传感器的制备方法，其特征在于这种啶虫脒分子印迹电化学传感器的制备方法是以石墨烯修饰的丝网印刷碳电极作为基底，在亚甲基蓝和啶虫脒的酸性硫酸钠溶液中电聚合形成分子印迹聚合物制得，这种方法制备出的分子印迹电化学传感器对啶虫脒的检出限为1.7×10-7 mol/L，线性范围为1×10-6 mol/L-2×10-5 mol/L；制备方法包括以下步骤：（一）将丝网印刷碳电极依次用丙酮，乙醇和去离子水中分别超声洗涤数分钟，然后将电极于K3Fe(CN)6中扫描，得到可逆的循环伏安峰，证明电极处理好；然后将分散好的石墨烯悬浮液滴加到丝网印刷碳电极上，形成均匀分散层，自然晾干，得到石墨烯修饰的电极；（二）将亚甲基蓝和啶虫脒溶解在酸性硫酸钠溶液中，混合均匀，亚甲基蓝和啶虫脒的摩尔比为1:3-6:3；（三）将前面混合好的溶液作为电解质溶液，把石墨烯修饰的电极置于混合溶液中，采用循环伏安法进行电化学聚合形成分子印迹聚合物，用异丁醇/乙酸溶液洗去啶虫脒模板分子，得到啶虫脒的分子印迹电化学传感器。
2.根据权利要求1所述的啶虫脒分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中电解质溶液为酸性硫酸钠溶液，pH为1-5。
3.根据权利要求1所述的啶虫脒分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中滴加到丝网印刷碳电极上的石墨烯悬浮液的量为2μL-10μL。
4.根据权利要求1所述的啶虫脒分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中电化学聚合方法为循环伏安法，电压范围：0.1V-1.2V，扫描速率: 30mV/s-100mV/s，扫描周期: 20圈-80圈。
5.根据权利要求1所述的啶虫脒分子印迹电化学传感器的制备方法，其特征在于，所述的制备方法中异丁醇/乙酸溶液浓度为1:1-6:1。
CN202010626009.9A 2020-07-02 2020-07-02 一种啶虫脒分子印迹电化学传感器的制备方法 Pending CN111551601A (zh)

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