CN116482207A - 一种MXene@AuNPs修饰电极的分子印迹电化学传感器及其制备方法和检测方法 - Google Patents
一种MXene@AuNPs修饰电极的分子印迹电化学传感器及其制备方法和检测方法 Download PDFInfo
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Abstract
本发明研究了一种基于MXene@AuNPs复合材料的分子印迹电化学传感器的制备方法和检测方法。本发明以同型半胱氨酸(Hcy)作为研究对象,通过结合纳米复合材料、简便的印迹方法以及新的检测方法,成功构建了新型Hcy分子印迹电化学传感器。首先用超声法合成的MXene@AuNPs复合材料修饰电极以提升导电性和比表面积;然后以Hcy为模板分子,盐酸多巴胺为功能单体,在修饰有MXene@AuNPs的电极表面采用电聚合法一步形成分子印迹膜;最后洗脱模板得到能特异性识别Hcy的分子印迹电化学传感器。在一定浓度范围内,该传感器的电化学响应值与Hcy浓度的对数具有良好的线性关系。所制备的分子印迹电化学传感器灵敏度高、选择性好、稳定性高,已成功应用于实际样品中Hcy的检测。
Description
技术领域
本发明属于电化学传感领域,特别涉及一种MXene@AuNPs复合材料修饰电极的分子印迹电化学传感器的制备方法和检测方法
背景技术
同型半胱氨酸(Hcy),是由人体内的蛋氨酸转化而来的一种高活性的含巯基的氨基酸。在抽血检查的常规项目中,除了常见的血压、血脂和血糖之外,血液中的Hcy水平也是人体重要的健康指标之一。在理想状态下,Hcy的含量是很低的,而且可以被酶催化转化为对大脑和身体有益的谷胱甘肽和S-腺苷蛋氨酸。但当受到遗传因素、营养状况、不良的生活方式、年龄增长、疾病和药物等风险因素影响时,Hcy的转化过程会受到阻碍,致使其在血液中累积而产生毒性,增加人体患病的风险。Hcy水平升高与冠心病、脑卒中、抑郁症、某些癌症以及妊娠期高血压等50多种疾病的患病都具有相关性。因此,在质量监测、药物研究和医学诊断等领域检测Hcy的含量至关重要。目前,常用的测定Hcy的方法有气相色谱-质谱法、高效液相色谱法、毛细管电泳法、荧光偏振免疫分析法及循环酶法。但在这些方法中存在着一些局限性,例如操作繁琐,耗时长,仪器成本高以及样本预处理复杂。由于电化学方法具有良好的选择性、较高的灵敏度、连续可靠性以及便携性,已有报道采用电化学方法来检测Hcy的含量。
纳米金(AuNPs)是指氯金酸在还原剂作用下制备成的不同粒径的金颗粒,AuNPs具有高电子密度、介电特性和催化作用,能与多种生物大分子结合且不影响其生物活性。在电化学传感中,AuNPs被修饰在各种电极材料上,显示出优秀的导电性、稳定性和表面吸附特性,以及良好的表面反应活性。MXene多层纳米片是一种新兴的二维无机化合物材料,通常由几个原子层厚度的过渡金属碳化物、氮化物或碳氮化物构成。由于MXene具有较大的活性区域、良好的金属导电性以及优秀的储能性能,使其作为一种很有前途的电极材料在电化学传感领域备受关注。但其固有的二维结构具有重堆积性,这极大地限制了MXene的电化学特性,同时阻碍了目标分子接近活性区域。因此,对MXene材料的功能化修饰和性质改良是目前研究人员关注的重点。
在大多数电化学或电化学相关的应用研究中,常采用酶、细胞、抗体和核酸适配体等生物活性物质作为生物敏感元件,并将其固定在电极上用于特异性识别目标物。其中,分子印迹聚合物(MIP)具有很强的选择能力,可以专一性识别目标物,常与电化学技术联合用于环境保护、核酸分析、疾病临床诊断、食品药品监督等领域。与传统的生物敏感元件相比,MIP具有优良的稳定性和环境适应性以及专一的选择性和较长的使用寿命,对不同环境均表现出较强的抵抗力。常见的MIP的合成方法有本体聚合,分散聚合,悬浮聚合,沉淀聚合和表面印迹等,传统的合成方法存在合成尺寸难控制、制备过程复杂、分散体系昂贵以及模板分子难洗脱等缺点。电聚合表面印迹法可以通过电化学氧化或还原过程直接将MIP电聚合在导电基底上,该方法操作简便快捷,合成的表面分子印迹聚合物便于洗脱,具有较强的稳定性,可以准确高效地识别目标物,且能长期保存、反复利用,同时还可以实现对生物大分子的分子印迹。
在电聚合表面印迹法制备MIP的过程中,合成MIP所采用的功能单体的种类,聚合溶液的比例和浓度,以及电聚合过程的电位、聚合速率和聚合圈数等条件决定了所合成的MIP的结构和表面特征。目前,采用电聚合表面印迹法以制备分子印迹电化学传感器用于检测Hcy含量的研究还未经报道,所制备的分子印迹电化学传感器在电化学测试过程中的可行性和稳定性也尚未明确。
发明内容
本发明的目的是制备一种以MXene@AuNPs复合材料修饰电极,并在修饰电极表面电聚合分子印迹聚合物的分子印迹电化学传感器,并用于同型半胱氨酸的快速检测。
本发明的目的主要通过以下技术手段实现:
本发明中一种MXene@AuNPs复合材料修饰电极的分子印迹电化学传感器的结构:
1)氯金酸(HAuCl4)在还原剂柠檬酸三钠的作用下发生聚合,制备成一定大小的纳米金(AuNPs);
2)将AuNPs加入至MXene材料中,在超声条件下均匀分散制成MXene@AuNPs复合材料;
3)工作电极选用玻碳电极(GCE),首先在电极表面滴涂MXene@AuNPs复合材料,记为MXene@AuNPs/GCE;
4)在MXene@AuNPs/GCE表面以同型半胱氨酸(Hcy)为模板分子,盐酸多巴胺(DA)为功能单体进行电聚合,得到分子印迹聚合物修饰的电极;
5)最后通过洗脱液将模板分子Hcy去除,形成MIP/MXene@AuNPs/GCE。
本发明中MXene@AuNPs复合材料修饰电极具体步骤如下:
1)将0.04%氯金酸(HAuCl4)加热搅拌至沸腾(160℃),迅速向其中加入1.00%柠檬酸三钠溶液,溶液颜色由淡黄色变为紫红色,待溶液颜色无变化后停止加热,将其转移至室温避光搅拌即可制成纳米金(AuNPs),装入棕色瓶避光4℃保存备用;
2)称取一定量的MXene材料,将其均匀分散在N,N-二甲基甲酰胺(DMF)溶液中,形成MXene分散液;
3)将制备好的AuNPs加入至MXene分散液中,超声混合2小时,均匀分散制成MXene@AuNPs复合材料分散液;
4)取一定量的MXene@AuNPs分散液滴加到玻碳电极(GCE)表面,室温晾干命名为MXene@AuNPs/GCE。
本发明中制备同型半胱氨酸分子印迹电化学传感器具体步骤如下:
5)称取一定量的盐酸多巴胺(DA)和同型半胱氨酸(Hcy)分别作为功能单体和模板分子,在磷酸盐缓冲溶液(pH=7.9)中进行电聚合反应;
6)将制备的分子印迹聚合物修饰的电极用超纯水冲洗,并浸入到洗脱液中浸泡以除去模板分子Hcy,命名为MIP/MXene@AuNPs/GCE;
7)作为对照组,制备非印迹聚合物(NIP)修饰的电极,在制备过程中除了在电聚合反应时不添加模板分子Hcy,其他过程均与MIP/MXene@AuNPs/GCE的制备过程保持一致,命名为NIP/MXene@AuNPs/GCE。
基于MXene@AuNPs复合材料修饰电极的分子印迹电化学传感器对同型半胱氨酸的特异性识别和检测:
8)将修饰电极浸入到含[K3Fe(CN)6]的KCl溶液中,随后对各个修饰电极进行电化学伏安法(CV)扫描和交流阻抗法(EIS)测量,扫描后便可得到相应的CV图和EIS图;
9)将制备的分子印迹电化学传感器浸入一系列浓度的同型半胱氨酸标准溶液中进行吸附,利用差分脉冲伏安法(DPV)进行测量,以溶度的对数与DPV响应值作图;
10)选用色氨酸(Trp)和半胱氨酸(Cys)作为同型半胱氨酸的干扰物来评价MIP/MXene@AuNPs/GCE的选择性。
进一步的,所述步骤1)中加入1.00%柠檬酸三钠溶液的量为5.60mL。
进一步的,所述步骤3)中制备的MXene@AuNPs复合材料分散液(水:DMF=1:1)的浓度为2.50mg/mL。
进一步的,所述步骤4)中MXene@AuNPs分散液的滴加量为10μL。
进一步的,所述步骤5)中电聚合反应的条件为在含有1.67mmol/L盐酸多巴胺和5.00mmol/L同型半胱氨酸的0.01mol/L磷酸盐缓冲溶液(pH=7.9)中进行电聚合反应,以0.05V/s的扫描速率,在-0.5V~+0.5V的电位范围内进行循环伏安法电聚合10个循环。
进一步的,所述步骤6)中洗脱液为乙醇溶液,浸泡时间为12分钟。
进一步的,所述步骤9)中同型半胱氨酸标准溶液的浓度为10-13,10-12,10-11,10-10,10-9,10-8,10-7,10-6,10-5mol/L;吸附时间为6分钟。
本发明的有益效果:该方法合成的MXene@AuNPs复合材料能有效改善MXene材料的重堆积性,具有良好的导电性和稳定性。所制备的分子印迹电化学传感器对同型半胱氨酸具较强的专一性识别能力,在一定浓度范围内同型半胱氨酸浓度的对数与DPV响应值呈良好线性关系,能够快速、准确地检测同型半胱氨酸的含量。
本发明中,通过超声混合而成的MXene@AuNPs复合材料不仅导电性好,而且稳定性高。与其他已报道的合成方法相比,这种方法具有操作便捷、合成成本低和时间短的优势。本发明中,通过电聚合表面印迹法在修饰电极表面直接电聚合制备分子印迹聚合物,作为特异性识别结构。与传统的分子印迹聚合物制备方法相比,这种电聚合表面印迹法具有操作简单、节省时间、印迹过程可调控等优势。该分子印迹电化学传感器灵敏度高、选择性好,已成功应用于实际样品中同型半胱氨酸含量的检测。
附图说明
图1不同修饰电极在含有K3Fe(CN)6的KCl溶液中的循环伏安(CV)图
图2分子印迹电化学传感器(MIP/MXene@AuNPs/GCE)吸附同型半胱氨酸的差分脉冲伏安法(DPV)图
图3分子印迹电化学传感器(MIP/MXene@AuNPs/GCE)洗脱模板和吸附目标物时间图
图4分子印迹电化学传感器(MIP/MXene@AuNPs/GCE)DPV响应值与同型半胱氨酸浓度对数的线性关系图
具体实施方式
实施例1
1.一种MXene@AuNPs复合材料修饰电极的分子印迹电化学传感器,包括工作电极,其特征在于,在所述工作电极外依次修饰了MXene@AuNPs复合材料和聚多巴胺分子印迹层,所述聚多巴胺分子印迹层具有目标氨基酸的印迹空穴。
2.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述工作电极为玻碳电极,所述MXene@AuNPs复合材料为电极修饰材料,是一种掺杂金属纳米颗粒的二维材料,具有导电性好和稳定性高等优势。MXene@AuNPs复合材料由AuNPs和MXene超声复合而成,还原法制备的AuNPs稳定性很高,层状结构的MXene具有较大的比表面积和优良的导电性,使得所制备的MXene@AuNPs复合材料具有较多的活性位点,表现出较好的电化学活性。通过超声法简单、快速合成MXene@AuNPs复合材料并用于修饰电极制备分子印迹电化学传感器的报道至今还没有。
3.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述聚多巴胺分子印迹层,提供目标氨基酸的印迹孔穴。多巴胺作为功能单体与模板氨基酸在通电条件下发生电聚合,功能单体在电极表面聚合的同时,将模板氨基酸嵌入其中,从而将特异性识别位点引入分子印迹聚合物中。聚多巴胺分子印迹聚合物的厚度可以通过电聚合扫描圈数决定,印迹聚合物的导电情况以及电聚合过程中发生氧化还原反应可以通过循环伏安图直观地反应出来。
4.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述聚多巴胺分子印迹层为多巴胺与目标氨基酸的交联层,在电聚合多巴胺分子印迹层后除去目标氨基酸形成印迹孔穴。
5.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述目标氨基酸为同型半胱氨酸。
实施例2
本发明中MXene@AuNPs复合材料修饰电极具体步骤如下:
1)将0.04%氯金酸(HAuCl4)加热搅拌至沸腾(160℃),迅速向其中加入5.60mL1.00%柠檬酸三钠溶液,溶液颜色由淡黄色变为紫红色,待溶液颜色无变化后停止加热,将其转移至室温避光搅拌即可制成纳米金(AuNPs),装入棕色瓶避光4℃保存备用;
2)称取一定量的MXene材料,将其均匀分散在N,N-二甲基甲酰胺(DMF)溶液中,形成MXene分散液;
3)将制备好的AuNPs加入至MXene分散液中,超声混合2小时,均匀分散制成2.50mg/mL MXene@AuNPs复合材料分散液(水:DMF=1:1);
4)量取10μL MXene@AuNPs分散液滴加到玻碳电极(GCE)表面,室温晾干命名为MXene@AuNPs/GCE。
本发明中制备同型半胱氨酸分子印迹电化学传感器具体步骤如下:
5)电聚合反应的条件为在含有1.67mmol/L盐酸多巴胺和5.00mmol/L同型半胱氨酸的0.01mol/L磷酸盐缓冲溶液(pH=7.9)中进行电聚合反应:扫描速率为0.05V/s,在-0.5V~+0.5V的电位范围内进行循环伏安法电聚合10个循环;
6)将制备的分子印迹聚合物修饰的电极用超纯水冲洗,并放入乙醇溶液中浸泡12分钟以除去模板分子Hcy,命名为MIP/MXene@AuNPs/GCE;
7)作为对照组,制备非印迹聚合物(NIP)修饰的电极,在制备过程中除了在电聚合反应时不添加模板分子Hcy,其他过程均与MIP/MXene@AuNPs/GCE的制备过程保持一致,命名为NIP/MXene@AuNPs/GCE。
实施例3
基于实例2所制备的分子印迹电化学传感器对同型半胱氨酸的特异性识别和检测:
1)将修饰电极浸入到含[K3Fe(CN)6]的KCl溶液中,随后对各个修饰电极进行电化学伏安法(CV)扫描和交流阻抗法(EIS)测量,扫描后便可得到相应的CV图和EIS图;
2)将制备的分子印迹电化学传感器浸入含有10-13,10-12,10-11,10-10,10-9,10-8,10-7,10-6,10-5mol/L的同型半胱氨酸标准溶液中进行吸附,利用差分脉冲伏安法(DPV)进行测量,以溶度的对数与DPV响应值作图;
3)选用色氨酸(Trp)和半胱氨酸(Cys)作为同型半胱氨酸的干扰物来评价MIP/MXene@AuNPs/GCE的选择性。
如附图4所示,峰电流值与Hcy浓度的对数在10-13~10-5mol/L范围内呈现良好的线性关系,线性回归方程为△I/(I-I0)=0.07583Lg CHcy(fM)+0.13215(R2=0.994),经计算最低检出限(LOD)为11.81fM。与其他已报道的电化学法检测Hcy的结果相比,本研究具有更宽的线性范围和更低的检出限,用于实际检测的灵敏度更高。
实施例4
除了“步骤5)中盐酸多巴胺:同型半胱氨酸的摩尔比为3:1”之外,其它各步骤及操作与实施例2的均相同。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种MXene@AuNPs复合材料修饰电极的分子印迹电化学传感器,包括工作电极,其特征在于,在所述工作电极外依次修饰了MXene@AuNPs复合材料和聚多巴胺分子印迹层,所述聚多巴胺分子印迹层具有目标氨基酸的印迹空穴。
2.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述工作电极为玻碳电极,所述MXene@AuNPs复合材料为电极修饰材料,是一种掺杂金属纳米颗粒的二维材料,具有导电性好和稳定性高等优势。MXene@AuNPs复合材料由AuNPs和MXene超声复合而成,还原法制备的AuNPs稳定性很高,层状结构的MXene具有较大的比表面积和优良的导电性,使得所制备的MXene@AuNPs复合材料具有较多的活性位点,表现出较好的电化学活性。通过超声法简单、快速合成MXene@AuNPs复合材料并用于修饰电极制备分子印迹电化学传感器的报道至今还没有。
3.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述聚多巴胺分子印迹层,提供目标氨基酸的印迹孔穴。多巴胺作为功能单体与模板氨基酸在通电条件下发生电聚合,功能单体在电极表面聚合的同时,将模板氨基酸嵌入其中,从而将特异性识别位点引入分子印迹聚合物中。聚多巴胺分子印迹聚合物的厚度可以通过电聚合扫描圈数决定,印迹聚合物的导电情况以及电聚合过程中发生氧化还原反应可以通过循环伏安图直观地反应出来。
4.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述聚多巴胺分子印迹层为多巴胺与目标氨基酸的交联层,在电聚合多巴胺分子印迹层后除去目标氨基酸形成印迹孔穴。
5.根据权利要求1所述的分子印迹电化学传感器,其特征在于,所述目标氨基酸为同型半胱氨酸。
6.一种权利要求1所述分子印迹电化学传感器的制备方法,其特征在于,包括以下步骤:
1)将0.04%氯金酸(HAuCl4)加热搅拌至沸腾(160℃),迅速向其中加入5.60mL 1.00%柠檬酸三钠溶液,溶液颜色由淡黄色变为紫红色,待溶液颜色无变化后停止加热,将其转移至室温避光搅拌即可制成纳米金(AuNPs),装入棕色瓶避光4℃保存备用;
2)称取一定量的MXene材料,将其均匀分散在N,N-二甲基甲酰胺(DMF)溶液中,形成MXene分散液;
3)将制备好的AuNPs加入至MXene分散液中,超声混合2小时,均匀分散制成MXene@AuNPs复合材料分散液(水:DMF=1:1);
4)量取10μL的MXene@AuNPs分散液滴加到玻碳电极(GCE)表面,室温晾干形成电极修饰层;
5)称取一定量的盐酸多巴胺(DA)和同型半胱氨酸(Hcy)分别作为功能单体和模板分子,在磷酸盐缓冲溶液(pH=7.9)中进行电聚合反应;
6)将制备的分子印迹聚合物修饰的电极用超纯水冲洗,并浸入到乙醇洗脱液中浸泡12分钟以除去模板分子Hcy。
7.根据权利要求6所述的制备方法,其特征在于:在步骤6)后进行步骤7)制备对照组,按照步骤1)—6)的方法制备非印迹聚合物,聚合过程中不加入同型半胱氨酸。
8.根据权利要求6所述的制备方法,其特征在于:步骤5)中电聚合反应的条件为在含有1.67mmol/L盐酸多巴胺和5.00mmol/L同型半胱氨酸的0.01mol/L磷酸盐缓冲溶液(pH=7.9)中进行电聚合反应,以0.05V/s的扫描速率,在-0.5V~+0.5V的电位范围内进行循环伏安法电聚合10个循环。
9.一种采用权利要求1所述分子印迹电化学传感器检测同型半胱氨酸的方法,其特征在于,包括以下步骤:
1)将修饰电极浸入到含[K3Fe(CN)6]的KCl溶液中,随后对各个修饰电极进行电化学伏安法(CV)扫描和交流阻抗法(EIS)测量,扫描后便可得到相应的CV图和EIS图;
2)将制备的分子印迹电化学传感器浸入一系列浓度的同型半胱氨酸标准溶液中进行吸附,利用差分脉冲伏安法(DPV)进行测量,以溶度的对数与DPV响应值作图;
3)选用色氨酸(Trp)和半胱氨酸(Cys)作为同型半胱氨酸的干扰物来评价MIP/MXene@AuNPs/GCE的选择性。
10.根据权利要求9所述的检测方法,其特征在于:步骤2)中同型半胱氨酸标准溶液的浓度为10-13,10-12,10-11,10-10,10-9,10-8,10-7,10-6,10-5mol/L;吸附时间为6分钟。
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