CN113899795A - 基于分子印迹的电化学传感器、制备方法以及磺胺二甲嘧啶的检测方法 - Google Patents
基于分子印迹的电化学传感器、制备方法以及磺胺二甲嘧啶的检测方法 Download PDFInfo
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Abstract
本发明提供一种基于分子印迹的电化学传感器,包括玻碳电极和导电载体,导电载体涂覆在玻碳电极的表面,导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物。本申请将复合碳纳米管和石墨烯材料用于分子印迹电化学传感器的构建中,提高传感器检测灵敏度;结合分子印迹技术,有效解决传统电化学传感器选择性差、抗干扰能力差的难题;利用新型分子印迹电化学传感器,实现复杂水产养殖水环境中磺胺二甲嘧啶的快速、灵敏检测。本发明还涉及一种电化学传感器的制备方法以及磺胺二甲嘧啶的检测方法。
Description
技术领域
本发明属于电化学传感器技术领域,更具体而言,涉及一种基于分子印迹的电化学传感器、制备方法以及磺胺二甲嘧啶的检测方法。
背景技术
随着经济水平提高,沿海地区渔业养殖发展迅猛,中国作为世界第一的水产养殖国家,每年的养殖产量达世界总产量的70%。由于环境污染日益加剧,细菌性疾病在水产养殖,尤其是密集型的养殖系统中发病率极高,对我国水产养殖业的发展造成了较为严重的影响。抗生素作为预防细菌感染和寄生虫病的药物,在水产饲料及水产养殖中广泛应用。抗生素可以有效抑制或者杀灭致病微生物,在控制水产病害过程中发挥着积极作用。但是近年来抗生素的不合理使用导致水产品中药物残留,而残留的抗生素可能引起一系列潜在危害,例如对非靶生物的毒害作用、诱导产生耐药性菌株、污染海洋环境、威胁人类健康等。水产养殖中投入的抗生素仅有20%-30%被鱼类等水产生物吸收,大部分抗生素以原药的形式排入环境,残留在养殖区和废水排放水域,或随悬浮物沉降蓄积于底部沉积物中。此外,抗生素残留的水产品被人摄入后会使部分人产生过敏反应,虽然一般不表现出急性毒性作用,但是会导致耐药菌株的产生,使体内菌群失调。抗生素残留在多种环境因子作用下会发生转移转化或者在动植物体中蓄积,通过食物链的富集作用,使抗生素残留逐渐加深,达到一定浓度时会对人体产生致畸、致癌和致突变作用。
磺胺二甲嘧啶(Sulfadimidine,SM2)是一类人工合成的磺胺类抗菌药,具有抗菌谱广、性质稳定、使用简便、价格低廉等特点,被广泛用于水产养殖中。为保护人类的健康安全,磺胺类抗生素中的磺胺噻唑和磺胺咪已经被禁止用于鱼病防治及作为饲料药物添加剂。国际食品法典委员会(CAC)和我国等许多国家规定,食品中磺胺类抗生素总量及单个磺胺的最大残留量为0.1mg/kg。相比于淡水环境,高盐度的养殖海水基质复杂,其中共存的各种物质(如有机物、无机重金属等)都会影响检测的灵敏度和准确性。因此,为保障水产养殖过程安全,开发快速准确、灵敏度高、选择性好的分析方法检测养殖海水中磺胺二甲嘧啶的残留至关重要。
发明内容
为了解决上述问题,本发明人进行了广泛的研究,通过采用电聚合法构建基于分子印迹的电化学传感器,并将该电化学传感器用于检测水产养殖环境中的磺胺二甲嘧啶。
本公开实施例提供了一种基于分子印迹的电化学传感器,包括玻碳电极和导电载体,导电载体涂覆在玻碳电极的表面,导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物。
碳纳米管和石墨烯是具有优异电学、力学和热学性质的一维和二维新型碳纳米材料,具有较强的机械性能和电子传导能力。选择多壁碳纳米管和石墨烯量子点作为复合材料,其中,石墨烯量子点同时具有亲水的含氧基团和亲油的基面碳环结构,相比石墨烯或氧化石墨烯等材料,更适合作为双亲性表面活性剂提高碳纳米管分散性和导电率。当将多壁碳纳米管和石墨烯量子点组装成三维碳纳米管-石墨烯量子点复合材料,能够发挥它们的协同效应,表现出优异的性能。
采用多壁碳纳米管和石墨烯量子点的超声混合物作为导电载体,并涂覆在玻碳电极的表面,能够制备出具有较高灵敏度的电化学传感器,能够有效解决传统电化学传感器选择性差、抗干扰能力差的难题,实现复杂水产养殖水环境中磺胺二甲嘧啶的快速、灵敏检测。
分子印迹聚合物(Molecularly imprinted polymers,MIPs)是一种人工合成的高分子有机化合物,其能够模拟“抗原-抗体”原理特异性识别靶分析物。此外,MIPs还具有较高的机械强度、耐酸碱、可重复利用性强等特点。
通过循环伏安法(CV)、差分脉冲伏安法(DPV)和交流阻抗谱法(EIS)评价分子印迹电化学传感器的电化学性能。
如图1所示,当在玻碳电极表面负载包括多壁碳纳米管和石墨烯量子点的超声混合物的导电载体后,修饰后的玻碳电极峰电流响应显著增大,表明修饰后的玻碳电极电化学性能显著提高。
在一些实施例中,多壁碳纳米管和石墨烯量子点复合材料质量比为1:0.2、或者1:0.5、或者1:1、或者1:1.5、或者1:2。
可选地,超声混合物为质量比为1:1的多壁碳纳米管与石墨烯量子点在N,N-二甲基甲酰胺溶液中超声混合20min。当多壁碳纳米管和石墨烯量子点质量比为1:1,浓度为1.0g/L时,分散液无挂壁和团聚现象,多壁碳纳米管和石墨烯量子点可以稳定复合分散,且滴涂后,修饰电极表现出较好的峰电流。
本公开实施例还提供了一种用于制备如上述的电化学传感器的方法,以磺胺二甲嘧啶作为模板分子,以吡咯作为功能单体,在含有LiClO4的乙腈溶液中采用循环伏安扫描法,在涂覆有多壁碳纳米管和石墨烯量子点超声混合物的玻碳电极表面修饰分子印迹膜,再利用化学洗脱方法,将修饰电极表面的模板分子洗脱,所得修饰电极即为分子印迹电化学传感器。
采用本公开实施例提供的制备电化学传感器的方法,可以通过改变电聚合参数来控制聚合物成核及形成的速率,通过扫描圈数控制分子印迹修饰膜的厚度,选择适当的支持电解质控制分子印迹修饰膜的形态,电聚合形成的分子印迹修饰膜中的模板分子更容易洗脱。而现有的分子印迹电化学传感器制备方法涂覆的聚合物不均匀,导电性差,并且表面吸附的模板分子不以洗脱。
在一些实施例中,玻碳电极涂覆5μL-15μL浓度为1g/mL的碳纳米管和石墨烯量子点超声混合物,玻碳电极作为工作电极,还包括参比电极和对电极,参比电极为Ag/AgCl电极,对电极为铂丝电极。
当多壁碳纳米管和石墨烯量子点复合纳米材料滴涂量为5-15uL时,修饰电极的电化学响应表现出较优良的导电性。在该体积范围内,可保证复合碳纳米材料将玻碳电极表面完全覆盖。
可选地,玻碳电极涂覆15μL浓度为1g/mL的多壁碳纳米管和石墨烯量子点超声混合物。
结合图1所示,随着复合碳纳米材料涂覆量的增加,可以有效提高修饰电极电流响应和灵敏度等电化学性能。本申请中,复合碳纳米材料是指多壁碳纳米管和石墨烯量子点的超声混合物。
在一些实施例中,乙腈溶液含有1mmol/L磺胺二甲嘧啶、10mmol/L吡咯和0.1mmol/L LiClO4。LiClO4作为支持电解质有助于电子迁移,乙腈作为溶剂为分子印迹有机膜的形成提供了稳定的聚合环境,并作为致孔剂参与反应使形成的分子印迹聚合膜疏松多孔,磺胺二甲嘧啶和吡咯分别作为模板和单体通过电聚合形成分子印迹聚合膜。
在一些实施例中,循环伏安扫描测试的电压扫描范围设定为0V~1.8V,扫描速率为50mV/min。
本公开实施例还提供了一种磺胺类抗生素的检测方法,采用上述的电化学传感器对水产养殖水环境中的磺胺二甲嘧啶进行检测。
在一些实施例中,包括如下步骤:
(1)将分子印迹电化学传感器置于0.1mol/L的KCl溶液(含5mmol/L[Fe(CN)6]3-/4-),利用差分脉冲伏安法测定初始峰电流;
(2)将分子印迹电化学传感器置于不同标准浓度的二甲嘧啶的电解液中富集一定时间,取出后再次置于0.1mol/L的KCl溶液(含5mmol/L[Fe(CN)6]3-/4-),利用差分脉冲伏安法测定对应浓度下的峰电流;
(3)建立峰电流差值与磺胺二甲嘧啶标准溶液浓度对数的线性关系曲线;
(4)将分子印迹电化学传感器置于浓度待测的磺胺二甲嘧啶溶液中富集,取出后置于0.1mol/L的KCl溶液(含5mmol/L[Fe(CN)6]3-/4-),利用差分脉冲伏安法测定对应峰电流;
(5)利用峰电流差值和对应的线性关系曲线计算待测样品中磺胺二甲嘧啶的浓度。
在一些实施例中,电解液为PBS缓冲溶液和/或ABS缓冲溶液,PBS缓冲溶液的pH范围为6.0~8.0,ABS缓冲溶液的pH范围为4.0~6.0。这样,能能够模拟海水基质环境,选择最佳的pH可以确保磺胺二甲嘧啶以分子形式存在,使分子印迹电化学传感器更快的吸附磺胺二甲嘧啶。
在一些实施例中,富集时间为1min~10min。这样,能够确保分子印迹电化学传感器与磺胺二甲嘧啶达到吸附平衡。
在一些实施例中,洗脱溶剂为甲醇/乙酸、乙醇/NaOH、0.5mol/L的H2SO4中的一种或多种。这样是为了将分子印迹电化学传感器表面吸附的磺胺二甲嘧啶全部洗脱,实现分子印迹电化学传感器的再生,以重复利用。
在一些实施例中,洗脱时间为1min~10min。这样,能够确保在最短的时间实现有效洗脱,提高整体检测效率
在一些实施例中,洗脱液为甲醇/乙酸、乙醇/NaOH、0.5mol/L的H2SO4中的一种或多种。
本公开实施例提供的基于分子印迹的电化学传感器、制备方法以及磺胺二甲嘧啶的检测方法,可以实现以下技术效果:将复合碳纳米管和石墨烯量子点材料用于分子印迹电化学传感器的构建中,提高传感器检测灵敏度;结合分子印迹技术,有效解决传统电化学传感器选择性差、抗干扰能力差的难题;利用新型分子印迹电化学传感器,实现复杂水产养殖水环境中磺胺二甲嘧啶的快速、灵敏检测。
以上的总体描述和下文中的描述仅是示例性和解释性的,不用于限制本申请。
附图说明
图1是涂覆不同体积1g/L的复合碳纳米材料的玻碳电极的循环伏安曲线。
具体实施方式
实施例1
一种基于分子印迹的电化学传感器,包括玻碳电极和导电载体,导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物,多壁碳纳米管和石墨烯量子点的质量比为1:1。制备方法包括:以磺胺二甲嘧啶作为模板分子,以吡咯作为功能单体,在含有LiClO4的乙腈溶液中采用循环伏安扫描法,在涂覆有多壁碳纳米管和石墨烯量子点超声混合物的玻碳电极表面修饰分子印迹膜,再利用化学洗脱方法,将修饰电极表面的模板分子洗脱,得到分子印迹电化学传感器。玻碳电极涂覆15μL浓度为1mg/mL的碳纳米管和石墨烯量子点超声混合物,所述玻碳电极作为工作电极,参比电极为Ag/AgCl电极,对电极为铂丝电极。乙腈溶液含有1mmol/L磺胺二甲嘧啶、10mmol/L吡咯和0.1mmol/L LiClO4。循环伏安扫描测试的电压扫描范围设定为0V~1.8V,扫描速率为50mV/min。
对比例1
导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物,多壁碳纳米管和石墨烯量子点的质量比为1:0.2,其余方案内容同实施例1。
对比例2
导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物,多壁碳纳米管和石墨烯量子点的质量比为1:0.5,其余方案内容同实施例1。
对比例3
导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物,多壁碳纳米管和石墨烯量子点的质量比为1:1.5,其余方案内容同实施例1。
对比例4
导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物,多壁碳纳米管和石墨烯量子点的质量比为1:2,其余方案内容同实施例1。
实施例2
玻碳电极涂覆5μL浓度为1mg/mL的碳纳米管和石墨烯量子点超声混合物,其余方案内容同实施例1。
实施例3
玻碳电极涂覆8μL浓度为1mg/mL的碳纳米管和石墨烯量子点超声混合物,其余方案内容同实施例1。
实施例4
玻碳电极涂覆15μL浓度为1mg/mL的碳纳米管和石墨烯量子点超声混合物,其余方案内容同实施例1。
对比例5
玻碳电极涂覆0μL浓度为1mg/mL的碳纳米管和石墨烯量子点超声混合物,其余方案内容同实施例1。
对比例6
玻碳电极涂覆20μL浓度为1mg/mL的碳纳米管和石墨烯量子点超声混合物,其余方案内容同实施例1。
将实施例1-4和对比例1-6制备的分子印迹电化学传感器进行性能测试,数据如下表所示:
性能参数 | CV电流响应/1×10<sup>-4</sup>A |
实施例1 | 4.911 |
对比例1 | 4.669 |
对比例2 | 3.536 |
对比例3 | 2.693 |
对比例4 | 2.567 |
实施例2 | 4.911 |
实施例3 | 5.990 |
实施例4 | 8.932 |
对比例5 | 1.966 |
对比例6 | 3.735 |
Claims (10)
1.一种基于分子印迹的电化学传感器,其特征在于,包括玻碳电极和导电载体,所述导电载体涂覆在所述玻碳电极的表面,所述导电载体包括多壁碳纳米管和石墨烯量子点的超声混合物。
2.根据权利要求1所述的电化学传感器,其特征在于,所述超声混合物为质量比为1:1的所述多壁碳纳米管与所述石墨烯量子点在N,N-二甲基甲酰胺溶液中超声混合20min。
3.一种用于制备如权利要求1或2所述的电化学传感器的方法,其特征在于,以磺胺二甲嘧啶作为模板分子,以吡咯作为功能单体,在含有LiClO4的乙腈溶液中采用循环伏安扫描法,在涂覆有多壁碳纳米管和石墨烯量子点超声混合物的玻碳电极表面修饰分子印迹膜,再利用化学洗脱方法,将修饰电极表面的模板分子洗脱,所得修饰电极即为分子印迹电化学传感器。
4.根据权利要求3所述的方法,其特征在于,所述玻碳电极涂覆5μL-15μL浓度为1mg/mL的多壁碳纳米管和石墨烯量子点超声混合物,所述玻碳电极作为工作电极,还包括参比电极和对电极,所述参比电极为Ag/AgCl电极,所述对电极为铂丝电极。
5.根据权利要求3所述的方法,其特征在于,所述乙腈溶液含有1mmol/L磺胺二甲嘧啶、10mmol/L吡咯和0.1mmol/L LiClO4。
6.根据权利要求3所述的方法,其特征在于,所述循环伏安扫描测试的电压扫描范围设定为0V~1.8V,扫描速率为50mV/min。
7.一种磺胺类抗生素的检测方法,其特征在于,采用如权利要求1或2所述的电化学传感器对水产养殖水环境中的磺胺二甲嘧啶进行检测。
8.根据权利要求7所述的检测方法,其特征在于,包括如下步骤:
(1)将分子印迹电化学传感器置于0.1mol/L的KCl溶液(含5mmol/L[Fe(CN)6]3-/4-),利用差分脉冲伏安法测定初始峰电流;
(2)将分子印迹电化学传感器置于含不同标准浓度的磺胺二甲嘧啶的电解液中作为标准溶液,富集一定时间后取出,取出后再次置于0.1mol/L的KCl溶液(含5mmol/L[Fe(CN)6]3-/4-),利用差分脉冲伏安法测定对应浓度下的峰电流;
(3)建立峰电流差值与磺胺二甲嘧啶标准溶液浓度对数的线性关系曲线;
(4)将分子印迹电化学传感器置于浓度待测的磺胺二甲嘧啶样品溶液中富集,取出后置于0.1mol/L的KCl溶液(含5mmol/L[Fe(CN)6]3-/4-),利用差分脉冲伏安法测定对应峰电流;
(5)利用峰电流差值和对应的线性关系曲线计算待测样品中磺胺二甲嘧啶的浓度;
(6)将步骤(5)使用后的分子印迹电化学传感器置于洗脱液中,搅拌洗脱1-15min,以洗脱掉传感器表面吸附的磺胺二甲嘧啶,用去离子水清洗后,于4℃保存待下次使用。
9.根据权利要求8所述的检测方法,其特征在于,所述电解液为PBS缓冲溶液和/或ABS缓冲溶液,所述PBS缓冲溶液的pH范围为6.0~8.0,所述ABS缓冲溶液的pH范围为4.0~6.0。
10.根据权利要求8所述的检测方法,其特征在于,富集时间为1min~10min。
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