CN115372437B - 一种检测对乙酰氨基酚药物的分子印迹电化学传感器及其检测方法 - Google Patents
一种检测对乙酰氨基酚药物的分子印迹电化学传感器及其检测方法 Download PDFInfo
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Abstract
本发明公开一种检测对乙酰氨基酚分子印迹电化学传感器及其检测方法。该电化学传感器以氮空位氮化碳和银/多壁碳纳米管为复合增敏材料,分子印迹膜MIP为特异检测识别组件,二者共同修饰电极为工作电极,用包括参比电极、对电极在内的三电极体系,与电化学工作站构成检测对乙酰氨基酚的电化学传感器。利用差分脉冲伏安法在该传感器上可高灵敏度、特异选择性检测对乙酰氨基酚药物。本发明提供的传感器,针对对乙酰氨基酚的分析和检测具备简便、廉价、高效、高灵敏度、高选择性和高稳定性的优点。
Description
技术领域
本发明涉及对乙酰氨基酚药物检测技术领域,具体涉及一种高灵敏度、特异选择性检测对乙酰氨基酚的分子印迹电化学传感器及其检测方法,属于药物安全检测技术领域。
背景技术
对乙酰氨基酚被称为扑热息痛或泰诺,是最广泛的退热和镇痛药物。它通常被用作非处方止痛药以缓解疼痛,如背痛,关节炎疼痛,偏头痛和神经痛头痛以及术后疼痛。还可用于退热、止咳等症状。单剂量对乙酰氨基酚对多种急性疼痛症状均有镇痛作用,且无副作用。但过量对乙酰氨基酚(4.0克/天)可引起严重的急性肝损伤,不可逆转的肝坏死和肾功能衰竭,严重时危及生命。据报道血清200 μg/mL持续4 h或6.25 μg/mL持续24 h均可引起肝毒性。在美国和欧洲,过量对乙酰氨基酚引起的急性肝功能衰竭的持续增长和严重程度引起了医学界和权威人士的关注。对乙酰氨基酚的定量检测不仅对临床应用有重要意义,而且对其制剂的质量控制也有重要意义。
目前,国内外有关生物介质、食用性肉质以及药物制剂中的对乙酰氨基酚的测定方法大都采用液相色谱法、气象色谱法、质谱法、分光光度法等方法进行定性、定量分析检测。但这些技术存在仪器昂贵、体积庞大、样品预处理过程复杂、测试周期长、测试费用高等缺点。因此,研发快速、准确、灵敏的对乙酰氨基酚的检测设备和方法具有重要意义。
发明内容
针对上述现有技术存在的问题,本发明的目的是提供一种检测对乙酰氨基酚的分子印迹电化学传感器。
该电化学传感器以氮空位氮化碳(NV-g-C3N4)和银/多壁碳纳米管(Ag@MWCNTs)为复合增敏材料,分子印迹膜(MIP)为特异检测识别组件,二者共同修饰电极为工作电极,用包括参比电极、对电极在内的三电极体系,与电化学工作站构成检测对乙酰氨基酚的电化学传感器。图1为本发明的传感器装置示意图。
一、制备Ag@MWCNTs/NV-g-C3N4复合增敏材料
(1)制备银负载多壁碳纳米管Ag@MWCNTs
将酸化多壁碳纳米管加入到乙二醇中超声混合,然后加入AgNO3溶液,在55~65℃油浴中搅拌1~2 h使得硝酸银在酸化多壁碳纳米管上原位还原;将反应完成后的溶液冷却至室温,过滤、洗涤、干燥得到银负载多壁碳纳米管Ag@MWCNTs;酸化多壁碳纳米管与AgNO3的质量比为10:1~20:1。
(2)制备氮空位石墨化氮化碳NV-g-C3N4
将三聚氰胺于500~600℃高温退火2~4 h,得到石墨化氮化碳g-C3N4;为了提高g-C3N4的电导率、增加活性位点,在氩气保护下600~700℃退火3~5 h,得到具有氮空位的石墨化氮化碳NV-g-C3N4。
(3)制备Ag@MWCNTs/NV-g-C3N4复合增敏材料
采用湿式机械超声混合法制备Ag@MWCNTs/NV-g-C3N4复合物。将Ag@MWCNTs和NV-g-C3N4按质量比1:1加入到乙醇溶液中,超声0.5~1h,离心、洗涤、干燥得到Ag@MWCNTs/NV-g-C3N4复合增敏材料。
图2A的XRD谱图中可以看到MWCNTs、Ag纳米颗粒和NV-g-C3N4的衍射峰;图2B和2C是场发射透射电子显微镜图(TEM),图中可以观察到丝线状MWCNTs和点状Ag纳米颗粒,图2D(TEM)和2E(SEM)中可以看到MWCNTs和片状NV-g-C3N4。
二、制备MIP/Ag@MWCNTs/NV-g-C3N4/GCE
(1)制备Ag@MWCNTs/NV-g-C3N4/GCE
将Ag@MWCNTs/NV-g-C3N4复合增敏材料加入到DMF溶液中超声混合,得到黑色Ag@MWCNTs/NV-g-C3N4悬浮液,将其滴涂在玻碳电极表面,自然晾干,得到Ag@MWCNTs/NV-g-C3N4/GCE复合增敏材料修饰电极;Ag@MWCNTs/NV-g-C3N4悬浮液的浓度为1.0~2.0 mg/mL。
(2)制备MIP/Ag@MWCNTs/NV-g-C3N4/GCE
利用电聚合技术,以对乙酰氨基酚为模板分子,以吡咯为聚合单体,在溶液介质中在复合增敏材料修饰的玻碳电极表面电聚合制备分子印迹膜,经电化学洗脱后得到分子印迹/复合增敏材料修饰的传感电极;具体制备如下:
将Ag@MWCNTs/NV-g-C3N4/GCE修饰电极浸泡在含有吡咯、对乙酰氨基酚和高氯酸锂的磷酸盐缓冲液中,以铂片电极为对电极,Ag/AgCl为参比电极,Ag@MWCNTs/NV-g-C3N4/GCE为工作电极,利用循环伏安法在-0.8 ~ 1.8 V的电压范围内,以50 mV/s的扫描速度扫描5~7圈,在Ag@MWCNTs/NV-g-C3N4/GCE表面制备含有模板分子的聚吡咯膜(洗脱前MIP/Ag@MWCNTs/NV-g-C3N4/GCE),SEM图如图3A。
将洗脱前的MIP/Ag@MWCNTs/NV-g-C3N4/GCE浸入0.1 mol/L NaOH溶液中,利用循环伏安法在-0.6 ~ 1.2 V电压范围内,以50 mV/s的扫描速度扫描10~20圈,得到工作电极MIP/Ag@MWCNTs/NV-g-C3N4/GCE,SEM图如图3B。
(3)修饰电极的性能
所有电化学测试均在电化学工作站(CHI660E)上进行,使用常规的三电极体系。将铂片电极(面积1 cm2)用作对电极,将Ag/AgCl浸入饱和KCl溶液中作为参比电极,工作电极为MIP/Ag@MWCNTs/NV-g-C3N4/GCE,将NaH2PO4和Na2HPO4·12H2O溶解在超纯水中制备0.1mol/L磷酸盐缓冲液(PBS)。为了消除每次电化学测量之前溶液介质中溶解氧的干扰,用高纯氮气通入溶液介质中30 min。在50 mV/s的扫速下,5 mmol/L铁氰化钾含有0.1 mol/LKCl溶液中进行循坏伏安法(CV)测试,考察修饰电极的导电性能。频率10 kHz至0.1 Hz的范围内,在5 mmol/L铁氰化钾含有0.1 mol/L KCl溶液中进行电化学阻抗谱(EIS)测量,并根据获得的奈奎斯特图确定电阻。
图4A和4B为复合增敏材料、GCE和修饰电极的CV曲线和阻抗图。从CV曲线可以看出,复合增敏材料的导电性最好,未洗脱的MIP+复合增敏材料的导电性最差,洗脱后MIP+复合增敏材料的电导性优于裸电极,仅比复合增敏材料修饰电极的导电性稍弱。阻抗图与CV图结果基本一致,复合增敏材料修饰电极的电阻最小,其次是洗脱后的MIP+复合增敏材料膜修饰电极,电阻最大的是未洗脱MIP+复合增敏材料膜修饰电极。
三、电化学检测对乙酰氨基酚
(1)工作曲线的绘制
在pH为7.4的PBS中,加入对乙酰氨基酚,使其浓度为分别为0.007、0.01、0.03、0.05、0.1、0.3、0.5、1、3、5、10、30、50、100 μmol/L作为乙酰氨基酚标准溶液。每种浓度溶液测试前,将高纯氮气通入测试溶液中并保持30 min以除去溶解氧的干扰。铂片电极(面积1cm2)作对电极,Ag/AgCl作参比电极,MIP/Ag@MWCNTs/NV-g-C3N4/GCE为工作电极,将工作电极浸入用0.1 mol/LPBS配置的不同浓度的对乙酰氨基酚标准溶液中孵育90 s,在0.1 ~0.7 V电位窗口范围内,以50 mV/s的扫速进行差分脉冲伏安检测(DPV),所得DPV曲线如图5A所示。记录每种浓度对应的最大电流值Ip,分别以对乙酰氨基酚标准溶液浓度为横坐标,电流值Ip为纵坐标,绘制标准工作曲线,得到检测对乙酰氨基酚的线性方程,如图5B所示。图5A和5B分别显示了不同浓度对乙酰氨基酚标准溶液的差分脉冲伏安曲线和线性标准工作曲线。对乙酰氨基酚浓度在0.007 ~ 5 μmol/L范围内,电流值与对乙酰氨基酚浓度的线性关系为Ip=1.8360C+3.13,R2=0.9915;对乙酰氨基酚浓度在5 ~ 100 μmol/L范围内,电流值与对乙酰氨基酚浓度的线性关系为Ip=0.0909C+11.3209,R2=0.9941;其中C为对乙酰氨基酚浓度,单位μmol/L;Ip为电流值,单位μA。本发明的传感器检测对乙酰氨基酚的线性工作范围为0.007 ~ 5 μmol/L和5 ~ 100 μmol/L,最低检测线为2.33 nmol/L (S/N = 3)。
(2)检测对乙酰氨基酚的浓度
用磷酸盐缓冲溶液将待测液的pH调节至7.4,将电化学传感器中的工作电极、参比电极和对电极构成三电极体系,利用差分脉冲伏安法在0.1 ~ 0.7 V电位窗口范围内对对乙酰氨基酚待测液进行检测,读取检测电流值Ip,将该电流值带入线性方程中,通过计算得到该待测液中的对乙酰氨基酚的浓度。
(3)修饰电极的稳定性
将制备的修饰电极存于冰箱一定时间后检测相同浓度的对乙酰氨基酚,比较储存前后检测结果,考察传感器的稳定性。用制备的MIP/Ag@MWCNTs/NV-g-C3N4/GCE电极检测对乙酰氨基酚的PBS溶液(pH =7.4,浓度为0.01 mmol/L);将制备的相同的电极存储在4℃冰箱中,分别15天、30天后再次检测对乙酰氨基酚溶液,比较电流信号强弱变化如图6所示,15天后电流强度仍为原始强度的90.3%,30天后电流强度仍为原始强度的84.8%,表明所发明的修饰电极的稳定性良好。
(4)修饰电极的再现性
平行制备5根修饰电极,对相同浓度的对乙酰氨基酚进行检测,比较检测结果的相对标准偏差,评价传感器的重现性。用平行制备的5根MIP/Ag@MWCNTs/NV-g-C3N4/GCE电极检测对乙酰氨基酚溶液(pH=7.4,浓度为0.01 mmol/L),记录的电流值如图7所示,电流变化相对标准偏差为0.975%,说明本发明所制备的电极具有良好的再现性。
(5)修饰电极的选择性和抗干扰性
用本发明的传感器同时检测对乙酰氨基酚和常见共存物尿酸、多巴胺、葡萄糖,比较检测结果,以评价传感器的选择性。将制备的MIP/Ag@MWCNTs/NV-g-C3N4/GCE电极分别检测对乙酰氨基酚的PBS溶液(AP)(pH=7.4,浓度为0.01 mmol/L)、抗坏血酸(AA)、多巴胺(DA)和葡萄糖(GL),得到DPV曲线如图8A所示,柱状图如图8B所示;电极对对乙酰氨基酚具有良好的选择性,对其他物质的选择性较低。
在一定浓度对乙酰氨基酚的PBS中加入一些无机盐离子:钠、钾、铜和镁离子(Na+、K+、Cu2+、Mg2+),对溶液中的对乙酰氨基酚进行检测,考察这些无机盐离子对检测结果的干扰性。在pH=7.4的PBS溶液中加入对乙酰氨基酚,其浓度为0.01 mmol/L,再向溶液中加入浓度50倍于对乙酰氨基酚浓度的钠、钾、铜和镁离子(Na+、K+、Cu2+、Mg2+),用发明的电极检测其中的对乙酰氨基酚,其电流响应柱状图如图9所示。这些无机盐离子对对乙酰氨基酚的检测几乎没有影响。
综上所述,本发明利用大比表面积、高催化活性的Ag@MWCNTs/NV-g-C3N4复合增敏材料制备修饰电极,使电化学传感具有超高的检测灵敏度,检测限为纳摩尔级,达到甚至低于现有的传统检测手段的检测限;分子印迹技术使传感器具有针对对乙酰氨基酚的靶向特异选择性,不受其他共存物质、生物基质等的干扰;同时,复合增敏材料及分子印迹聚合物均具有较高的稳定性,因此所制备的传感器具有优良的稳定性和再现性。本发明的电化学传感器能够实现快速、高灵敏度、特异选择性检测对乙酰氨基酚,其样品前处理及分析检测操作简单、分析时间短、设备便携,适用于生物基质、药品制剂等中的对乙酰氨基酚的快速灵敏检测。
附图说明
图1是本发明制备的传感器装置示意图;
图2是本发明制备的Ag@MWCNTs/NV-g-C3N4材料的XRD、TEM及SEM图片;
图3是本发明制备的MIP/Ag@MWCNTs/NV-g-C3N4/GCE洗脱前(A)和洗脱后(B)的SEM图;
图4是本发明制备的复合增敏修饰材料及MIP+复合增敏材料修饰的电极的CV曲线(A)和阻抗图(B);
图5是本发明制备的传感器检测不同浓度对乙酰氨基酚标准溶液的DPV曲线(A)和线性标准工作曲线(B);
图6是本发明制备的传感器的稳定性测试;
图7是本发明制备的传感器的再现性测试;
图8是本发明制备的传感器的选择性测试;
图9是本发明制备的传感器的抗干扰性测试;
图10是本发明制备的传感器检测血清(A)和尿液(B)中的对乙酰氨基酚DPV曲线。
具体实施方式
下面结合具体实施案例对检测对乙酰氨基酚药物的分子印迹电化学传感器的制备及检测性能作进一步说明。
实施例1MIP/Ag@MWCNTs/NV-g-C3N4/GCE电极的制备
(1)制备Ag@MWCNTs/NV-g-C3N4
1 gMWCNTs添加到90 mL 65 wt.%硝酸溶液中,120℃油浴5 h。用乙醇和去离子水清洗和过滤直到pH为6,滤液在60℃真空干燥24 h,得到酸化MWCNTs。将100 mg酸化MWCNTs加入到100 mL乙二醇中超声0.5 h,然后加入500 μL 0.1 mol/L的AgNO3溶液,在60℃油浴中搅拌1 h。将溶液冷却至室温后,过滤、洗涤、干燥得到Ag@MWCNTs。
将三聚氰胺在大气气氛下550℃高温退火3 h,得到g-C3N4。将g-C3N4在650℃氩气保护下退火4 h,得到NV-g-C3N4。
将1 g Ag@MWCNTs和1g NV-g-C3N4加入到50 mL乙醇溶液中,超声混合0.5 h,离心、洗涤、干燥得到Ag@MWCNTs/NV-g-C3N4粉末。用XRD分析发现所制材料的成分为Ag、MWCNTs和NV-g-C3N4,如图2A所示,TEM和SEM可以观察到纳米颗粒状Ag,丝线状MWCNTs和片状NV-g-C3N4,如图2B-E所示。
(2)制备MIP/Ag@MWCNTs/NV-g-C3N4/GCE修饰电极
基底电极选用直径3 mm(几何面积7.065 mm2)的玻碳电极。在使用前,用直径为1、0.3和0.05 μm的氧化铝粉末在麂皮上抛光,然后用乙醇和水的混合物(1:1体积比)冲洗,然后用氮气干燥。将5mgAg@MWCNTs/NV-g-C3N4粉末加入到5 mLDMF(1.0 mg/mL)中超声0.5 h,得到黑色悬浮液。取5 μL上述悬浮液滴在GCE表面,自然晾干,得到复合增敏材料修饰电极。CV测试曲线见图4A。EIS测试曲线见图4B。
将NaH2PO4和Na2HPO4·12H2O溶解在超纯水中制备0.1 mol/L磷酸盐缓冲液(PBS),使pH为7。将复合增敏材料修饰电极浸泡在含有0.025 mol/L吡咯、0.01 mol/L对乙酰氨基酚和0.1 mol/L高氯酸锂的PBS中。在电化学工作站上,铂片电极(面积1 cm2)作对电极,Ag/AgCl作参比电极,Ag@MWCNTs/NV-g-C3N4/GCE为工作电极,在-0.8 ~ 1.8 V的电压范围内,以50 mV/s的扫描速度进行CV扫描5圈,在Ag@MWCNTs/NV-g-C3N4/GCE上获得印迹模板分子的聚吡咯膜(洗脱前MIP/Ag@MWCNTs/NV-g-C3N4/GCE)。在0.1 mol/L NaOH溶液中,在-0.6 ~ 1.2V电压范围内,以50 mV/s的扫描速度CV扫描10圈,得到MIP/Ag@MWCNTs/NV-g-C3N4/GCE。CV测试曲线见图4A。EIS测试曲线见图4B。
实施例2血清中对乙酰氨基酚的检测
取100 mL血清,加入0.0529 mg对乙酰氨基酚,配置成对乙酰氨基酚浓度为3.5 μmol/L的血清样本,取其中的10 mL进行DPV检测,DPV曲线如图10A所示。所得曲线的电流值Ip为9.3872μA,带入线性方程Ip = 1.83603C + 3.13,计算得到的浓度C为3.408μmol/L,经计算,样本的回收率为97.4 %,回收率结果令人满意。
实施例3血清中对乙酰氨基酚的检测
取100 mL血清,加入0.0680mg对乙酰氨基酚,配置成对乙酰氨基酚浓度为4.5 μmol/L的尿液样本,取其中的10 mL进行DPV检测,DPV曲线如图10A所示。所得曲线的电流值Ip为11.1994μA,带入线性方程Ip = 1.83603C + 3.13,计算得到的浓度C为4.395μmol/L,经计算,样本的回收率为97.7 %,回收率结果令人满意。
实施例4尿液中对乙酰氨基酚的检测
取100 mL尿液,加入0.0529 mg对乙酰氨基酚,配置成对乙酰氨基酚浓度为3.5 μmol/L的尿液样本,取其中的10 mL进行DPV检测,DPV检测曲线如图10B所示。所得曲线的电流值Ip为9.3193 μA,带入线性方程Ip = 1.83603C + 3.13,计算得到的浓度C为3.371 μmol/L。经计算,样本的回收率为96.3 %,回收率结果令人满意。
实施例5 尿液中对乙酰氨基酚的检测
取100 mL尿液,加入0.0680 mg对乙酰氨基酚,配置成对乙酰氨基酚浓度为4.5 μmol/L的尿液样本,取其中的10 mL进行DPV检测,DPV检测曲线如图10B所示。所得曲线的电流值Ip为11.3591 μA,带入线性方程Ip = 1.83603C + 3.13,计算得到的浓度C为4.482 μmol/L,经计算,样本的回收率为99.6 %,回收率结果令人满意。
Claims (7)
1.一种检测对乙酰氨基酚药物的分子印迹型电化学传感器,其特征在于:所述电化学传感器以氮空位氮化碳和银负载多壁碳纳米管为复合增敏材料,分子印迹膜MIP为特异检测识别组件,二者共同修饰电极为工作电极;所述工作电极的制备包括以下步骤:
(1)Ag@MWCNTs/NV-g-C3N4复合增敏材料的制备
将酸化多壁碳纳米管加入到乙二醇中超声混合,然后加入AgNO3溶液,在55~65℃油浴中搅拌1~2 h;将反应完成后的溶液冷却至室温,过滤、洗涤、干燥得到银负载多壁碳纳米管Ag@MWCNTs;
将三聚氰胺于500~600℃高温退火2~4 h,得到石墨化氮化碳g-C3N4;然后在氩气保护下600~700℃退火3~5 h,得到具有氮空位的石墨化氮化碳NV-g-C3N4;
将Ag@MWCNTs和NV-g-C3N4加入到乙醇溶液中,超声0.5~1h,离心、洗涤、干燥得到Ag@MWCNTs/NV-g-C3N4复合增敏材料;
(2)MIP/Ag@MWCNTs/NV-g-C3N4/GCE修饰电极的制备
将Ag@MWCNTs/NV-g-C3N4复合增敏材料加入到DMF溶液中超声混合,得到黑色Ag@MWCNTs/NV-g-C3N4悬浮液,将其滴涂在玻碳电极表面,自然晾干,得到Ag@MWCNTs/NV-g-C3N4/GCE复合增敏材料修饰电极;
将Ag@MWCNTs/NV-g-C3N4/GCE修饰电极浸泡在含有吡咯、对乙酰氨基酚和高氯酸锂的磷酸盐缓冲液中,以铂片电极为对电极,Ag/AgCl为参比电极,Ag@MWCNTs/NV-g-C3N4/GCE为工作电极,利用循环伏安法在-0.8 ~ 1.8 V的电压范围内,以50 mV/s的扫描速度扫描5~7圈,然后将电极浸入0.1 mol/LNaOH溶液中,利用循环伏安法在-0.6 ~ 1.2 V电压范围内,以50mV/s的扫描速度扫描10~20圈,得到工作电极MIP/Ag@MWCNTs/NV-g-C3N4/GCE。
2.根据权利要求1所述的检测对乙酰氨基酚药物的分子印迹型电化学传感器,其特征在于:步骤(1)中,酸化多壁碳纳米管与AgNO3的质量比为10:1 ~ 20:1;Ag@MWCNTs和NV-g-C3N4的质量比为1:1。
3.根据权利要求1所述的检测对乙酰氨基酚药物的分子印迹型电化学传感器,其特征在于:步骤(2)中,Ag@MWCNTs/NV-g-C3N4悬浮液的浓度为1.0~2.0 mg/mL。
4.根据权利要求1所述的检测对乙酰氨基酚药物的分子印迹型电化学传感器,其特征在于:步骤(2)中,磷酸盐缓冲液中,模板分子的浓度为0.01 mol/L,吡咯单体的浓度为0.025 ~ 0.050mol/L,高氯酸锂的浓度为0.1 mol/L。
5.根据权利要求1所述的检测对乙酰氨基酚药物的分子印迹型电化学传感器,其特征在于:所述电化学传感器还包括参比电极和对电极;所述参比电极为浸入饱和KCl溶液中的银/氯化银电极;所述对电极为铂片电极,铂片表面积为1cm2。
6.根据权利要求1-5任一项所述的电化学传感器在检测对乙酰氨基酚药物中的应用。
7.根据权利要求6所述的电化学传感器在检测对乙酰氨基酚药物中的应用,其特征在于:用磷酸盐缓冲溶液将待测液的pH调节至7.4,将电化学传感器中的工作电极、参比电极和对电极构成三电极体系,利用差分脉冲伏安法在0.1 ~ 0.7 V电位窗口范围内对对乙酰氨基酚待测液进行检测,测得相应的电流值;根据电流值和乙酰氨基酚浓度的线性关系计算得到对乙酰氨基酚待测液的浓度;电流值和乙酰氨基酚浓度的线性关系如下:
对乙酰氨基酚浓度在0.007 ~ 5 μmol/L范围内,电流值与对乙酰氨基酚浓度的线性关系为Ip=1.8360C+3.13,R2=0.9915;对乙酰氨基酚浓度在5 ~ 100 μmol/L范围内,电流值与对乙酰氨基酚浓度的线性关系为Ip=0.0909C+11.3209,R2=0.9941;
C——对乙酰氨基酚浓度,单位μmol/L;
Ip——电流值,单位μA。
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