CN116519769A - 基于Pd/P-g-C3N4同时检测多巴胺和抗精神病药物及其制备方法 - Google Patents
基于Pd/P-g-C3N4同时检测多巴胺和抗精神病药物及其制备方法 Download PDFInfo
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Abstract
本发明提供一种基于Pd/P‑g‑C3N4同时检测抗精神病药物和多巴胺物质及其制备方法。通过元素掺杂(P元素和金属元素Pd)对g‑C3N4进行改性，制备二维纳米材料钯/磷共掺杂氮化碳片(记作Pd/P‑g‑C3N4)。将其修饰于玻碳电极表面作为工作电极，饱和甘汞电极作为参比电极，铂丝电极作为对电极，与电化学工作站相连接构建电化学传感器。采用DPV检测法用于同时分析多巴胺和抗精神病药物(氯丙嗪和氯氮平)。本发明所制备的传感器抗干扰能力强，灵敏度高，稳定性高，成本低，制备工艺简便。
Description
技术领域
本发明属于纳米材料、电化学分析和生物传感器的交叉学科技术领域，具体涉及Pd/P-g-C3N4制备方法及应用于同时检测多巴胺和抗精神病药物。
背景技术
近几十年来，精神障碍疾病已成为人类面临的重大健康问题之一。据国家精神障碍信息管理系统数据显示，截至2018年底，我国的严重精神障碍患者数已高达599万例。因此，对精神疾病的治疗引起人们的广泛重视。氯丙嗪(CPZ，报道的第一种有效的典型抗精神病药物)和氯氮平(CLZ，非典型抗精神病药物的黄金标准)作为目前临床最常用的治疗精神分裂药物，用于控制各种精神障碍、抑郁、偏执、焦虑和紧张。但由于两种药物的治疗窗较窄，过量和持续使用会导致一系列严重副反应疾病的出现，如锥体外系症状、粒细胞减少症、内分泌障碍、迟发性运动障碍、肝肿大以及癌症等严重疾病。因此对药物的体内浓度监测是必要的。目前对于CPZ或CLZ常用的分析技术有气相色谱法、荧光光谱法、液相色谱-质谱联用法、高效液相色谱法、毛细管电泳法。但上述技术成本较高，操作复杂且耗时长，在实际应用中受到一定的限制。此外，CPZ和CLZ作为多巴胺受体阻断剂，服用后会引起体内多巴胺(DA)的含量变化，如果同时监测药物与DA的含量可以更准确地把握患者情况。基于此，本发明开发一种同时检测CPZ、CLZ和DA的分析方法是具有重要意义的。
电化学传感技术具有成本低、前处理简单、响应速度快、高灵敏性和选择性等优点，在药物和生物分子检测领域受到广泛关注。众所周知，石墨相氮化碳(g-C3N4)作为一种典型的类石墨层状材料，平面由高度有序的三-s-三嗪(C6N7)单元与叔氨基相连，有利于与目标化合物的相互作用，在传感器应用方面具有巨大潜力。本发明在g-C3N4的基础上，选择了非金属元素磷(P)掺杂合成块状磷掺杂氮化碳(P-g-C3N4)，通过质子化将其剥离成P-g-C3N4纳米片。再将金属Pd沉积在P-g-C3N4纳米片表面，最终制备出质子化的二维钯/磷氮化碳纳米片(记作Pd/P-g-C3N4)。并将其修饰于玻碳电极(GCE)表面作为电化学传感器的检测探针，实现多巴胺(DA)和抗精神病药物(CPZ和CLZ)三种物质的共同检测并其应用于实际样品，为临床药物监测提供新的解决方案。
发明内容
针对现有技术的不足，本发明提供一种钯/磷共掺杂氮化碳(Pd/P-g-C3N4)修饰的玻碳电极。
本发明提供的钯/磷共掺杂氮化碳(Pd/P-g-C3N4)修饰的玻碳电极用于多巴胺、氯丙嗪和氯氮平的检测。
本发明提供一种用于多巴胺、氯丙嗪和氯氮平的检测电化学传感器，包括钯/磷共掺杂氮化碳(Pd/P-g-C3N4)修饰的玻碳电极、参比电极，对电极和电化学工作站。
本发明提供所述钯/磷共掺杂氮化碳(Pd/P-g-C3N4)修饰的玻碳电极的制备方法，包括以下步骤：
1)P-g-C3N4的制备：取三聚氰胺和磷酸氢二铵，加水搅拌均匀得到白色悬浊液，置于100℃水浴中使其水分挥发得到三聚氰胺磷酸氢二铵的白色固体混合物，取混合物至马弗炉中煅烧，得到磷掺杂的氮化碳P-g-C3N4粗品。将P-g-C3N4粗品加入硝酸中，加热回流，冷却至室温，用超纯水洗涤至中性，干燥过夜，纯化得到P-g-C3N4。
2)Pd/P-g-C3N4的制备：取P-g-C3N4加入蒸馏水中超声，加入醋酸钯溶液得到混悬液，滴加氢氧化钠溶液将混悬液调为碱性，搅拌，加入过量的硼氢化钠溶液，冷却至室温，用超纯水洗涤至中性，干燥过夜，得到磷/钯掺杂的氮化碳Pd/P-g-C3N4。
3)工作电极的预处理：取适量不同粒径大小的Al2O3抛光粉末打磨电极，再超声进行洗涤，氮气吹扫干待用。
4)修饰电极：取Pd/P-g-C3N4悬浮液滴涂到玻碳电极的圆盘镜面，然后置于室温下自然晾干，使其形成稳定的膜。将电极插入硫酸溶液中，采用循环伏安法(CV)进行电极活性。
优选地，所述步骤1)中P-g-C3N4的制备方法如下：取三聚氰胺，加入磷酸氢二铵，加水搅拌均匀得到白色悬浊液，置于100℃水浴中使其水分挥发得到三聚氰胺磷酸氢二铵固体混合物，取混合物5g移至小坩埚在马弗炉中以550℃保持4h，得到P-g-C3N4粗品。将1gP-g-C3N4粗品粉末加入100mL5mol/L的硝酸中，在温度为120℃下加热回流12h，冷却至室温，用超纯水洗涤至中性，于60℃烘箱中干燥过夜，纯化得到P-g-C3N4。
优选地，所述步骤2)中Pd/P-g-C3N4的制备方法如下：取100mgP-g-C3N4加入到10mL蒸馏水中超声15min，分别加入浓度为4.26mM的醋酸钯溶液得到黄色混悬液，滴加0.1M氢氧化钠将混悬液调为pH为10，在50℃下搅拌6h，加入过量的0.1M的硼氢化钠溶液，冷却至室温，用超纯水洗涤至中性，于60℃烘箱中干燥过夜，得到Pd/P-g-C3N4。
优选地，所述Pd/P-g-C3N4中磷掺杂的质量份数为3～20％；钯掺杂的质量份数为1～5％；优选地，所述Pd/P-g-C3N4中磷掺杂的质量份数为10％；钯掺杂的质量份数为4％。
优选地，所述步骤3)中Al2O3抛光粉的粒径选自1μm、0.3μm和0.05μm，
优选地，所述步骤3)中的预处理方法为：将电极垂直在抛光绒布上画“8”字依次打磨5min至电极成光滑镜面，再依次用去离子水、丙酮、乙醇各超声洗涤5min以确保电极表面完全干净，氮气吹干待用。
优选地，所述步骤4)中修饰电极的方法为：取10mg的Pd/P-g-C3N4分散到5mL的超纯水中，超声处理15min后搅拌6h，得到浓度为2mg/mL的悬浮液，准确量取6.0μL复合材料滴涂到玻碳电极的圆盘镜面，然后置于室温下自然晾干，使其形成稳定的膜。
本发明提供了所述钯/磷共掺杂氮化碳(Pd/P-g-C3N4)修饰的玻碳电极用于多巴胺、氯丙嗪和氯氮平的检测方法，包括以下步骤：
S1采用DPV法进行测定标准曲线：加入不同浓度的多巴胺、氯丙嗪和氯氮平的混合溶液，使各物质与Pd/P-g-C3N4特异性结合，在修饰电极表面发生氧化还原反应，通过在电解质溶液中电子传输，引起电信号的改变，一定浓度范围内浓度与电信号呈现线性关系，得到多巴胺、氯丙嗪和氯氮平的标准曲线。
S2采用DPV法对未知浓度的多巴胺、氯丙嗪和氯氮平混合溶液进行测定电信号，利用多巴胺、氯丙嗪和氯氮平的标准曲线进行定量。
优选地，所述步骤S1中电解质溶液为pH为7的KH2PO4-Na2HPO4溶液。
优选地，所述步骤S1中所述的DPV测试参数如下：电势扫描为-0.2-1.0V；振幅为0.05V；脉冲0.06s；脉冲周期0.5s；灵敏度为1.0×10-5。
优选地，所述步骤S1中多巴胺在0.05-2.50μM和2.50-250.00μM浓度范围内呈现良好线性，检测限为10nM；氯氮平在0.02-10.00μM和10.00μM-100.00μM浓度范围内呈现良好线性，检测限为5nM；氯丙嗪在0.02-10.00μM和10.00μM-100.00μM浓度范围内呈现良好线性，检测限为5nM。各物质的加标回收率在95.9-102.0％之间。
本发明的有益效果：本发明以石墨相氮化碳纳米材料为基础，通过元素掺杂(P元素和金属元素Pd)对其进行改性，提高电子传输能力。将制备的二维纳米材料钯/磷共掺杂氮化碳(记作Pd/P-g-C3N4)修饰于玻碳电极表面，采用传统三电极体系构建电化学传感器，在最佳实验检测条件下，涵盖的亚治疗性、治疗性和毒性浓度范围内实现对多巴胺以及抗精神病药物(氯氮平和氯丙嗪)的痕量检测，并呈现良好的线性关系。与现有检测技术相比，该传感器具有制备工艺简单、成本低、灵敏度高和较好选择性，在药物监测方面具有良好的应用前景。
附图说明
图1为Pd/P-g-C3N4修饰的电极制备工艺图
图2为采用高分辨率透射电镜(HR-TEM)观察制备的Pd/P-g-C3N4的形貌
图3为Pd/P-g-C3N4复合材料修饰电极在(a)不同类型0.1M磷酸盐缓冲溶液(pH7.0)、(b)涂覆不同浓度的Pd/P-g-C3N4以及(c)不同pH下检测混标的CV图
图4为Pd/P-g-C3N4传感器在检测不同浓度的混标溶液的DPV图(a)；多巴胺浓度与其氧化峰电流值的线性关系图(b)；氯氮平浓度与其氧化峰电流值的线性关系图(c)；氯丙嗪浓度与其氧化峰电流强度的线性关系图(d)。
具体实施方式
下面的实施例可以使本专业的本领域技术人员更全面地理解本发明，但并不因此将本发明限制在所述的实施例范围之中。
实施例1
(1)Pd/P-g-C3N4的制备
取三聚氰胺6.000g，分别加入磷酸氢二铵(0.7675、1.2792、2.5584和5.1168g)，加水搅拌均匀得到白色悬浊液，置于100℃水浴中使其水分挥发得到三聚氰胺磷酸氢二铵的白色固体混合物，取混合物5g移至小坩埚在马弗炉中以(5℃/min)550℃保持4h，得到不同掺杂比的X％P-g-C3N4。将1gX％P-g-C3N4粉末加入100mL5mol/L的硝酸中，在温度为120℃下加热回流12h。冷却至室温，用超纯水洗涤至中性，于60℃烘箱中干燥过夜。最终得到3％、5％、10％、15％、20％的P-g-C3N4。
分别取100mgX％P-g-C3N4加入到10mL蒸馏水中超声15min，分别加入(5mL、10mL、15mL、20mL、25mL)浓度为4.26mM的醋酸钯溶液得到黄色混悬液，滴加0.1M氢氧化钠将混悬液调为碱性(pH＝10)，在50℃下搅拌6h，加入过量的0.1M的硼氢化钠溶液，冷却至室温，用超纯水洗涤至中性，于60℃烘箱中干燥过夜，得到的灰色固体为不同掺杂比的X％Pd/P-g-C3N4。如图2所示，在不同放大倍数下清晰地显示Pd/P-g-C3N4呈纳米片状结构，纳米片表面负载了均一的Pd纳米颗粒。
(2)工作电极的预处理
取适量不同粒径大小的Al2O3抛光粉末打磨电极，再超声进行洗涤，氮气吹扫干待用。
(3)修饰电极
取Pd/P-g-C3N4悬浮液滴涂到玻碳电极的圆盘镜面，然后置于室温下自然晾干，使其形成稳定的膜。将电极插入硫酸溶液中，采用循环伏安法(CV)进行电极活性。
(4)条件优化
为了使三种物质被同时检测且所呈现较好的峰形，对检测条件进行优化是必要的。考察存在混标的情况下，采用CV法考察了不同支持电解质(磷酸氢二钠-柠檬酸、磷酸二氢钾-氢氧化钠、磷酸氢二钠-磷酸二氢钾)，修饰电极的涂覆浓度(1-5mg/mL)以及检测pH(3-7)条件。
(5)物质检测
实验采用DPV法进行测定，加入不同浓度的多巴胺、氯丙嗪和氯氮平的混合溶液，使各物质与Pd/P-g-C3N4特异性结合，在修饰电极表面发生氧化还原反应，通过在电解质溶液中电子传输，引起电信号的改变，在一定浓度范围内呈现线性关系，并应用于生物样品中多物质的同时痕量检测。
步骤(1)中所述的Pd/P-g-C3N4中P的掺杂质量为10％；Pd的掺杂质量为4％。
步骤(2)中所述的Al2O3抛光粉末(1μm、0.3μm、0.05μm)于抛光绒布上，滴加适量水调成糊状，将电极垂直在抛光绒布上画“8”字依次打磨5min至电极成光滑镜面，再依次用去离子水、丙酮、乙醇各超声洗涤5min以确保电极表面完全干净，氮气吹扫干待用。
步骤(3)中所述的取10mg的Pd/P-g-C3N4分散到5mL的超纯水中，超声处理15min后搅拌6h，得到浓度为2mg/mL的悬浮液，移液枪准确量取6.0μL复合材料滴涂到玻碳电极的圆盘镜面，然后置于室温下自然晾干，使其形成稳定的膜。活化的CV测试参数：电势扫描为-0.6-1.2V；扫描速度0.05V/s；扫描圈数为50圈；灵敏度为1.0×10-5。
如图3所示，混标在Pd/P-g-C3N4的涂覆浓度为2mg/mL下修饰电极，选用pH为7的KH2PO4-Na2HPO4作为支持电解质时检测物质的峰形最好，氧化峰电流响应最大。步骤(4)中在Pd/P-g-C3N4的涂覆浓度为2mg/mL下修饰电极，选用pH为7的KH2PO4-Na2HPO4作为支持电解质为最佳实验条件，以此条件进行后续实验。
如图4所示，步骤(5)中所述的DPV测试参数如下：电势扫描为-0.2-1.0V；振幅为0.05V；脉冲0.06s；脉冲周期0.5s；灵敏度为1.0×10-5。多巴胺在0.05-2.50μM和2.50-250.00μM浓度范围内呈现良好线性，检测限为10nM；氯氮平在0.02-10.00μM和10.00μM-100.00μM浓度范围内呈现良好线性，检测限为5nM；氯丙嗪在0.02-10.00μM和10.00μM-100.00μM浓度范围内呈现良好线性，检测限为5nM。各物质的加标回收率在95.9-102.0％之间。
Claims (10)
1.一种钯/磷共掺杂氮化碳Pd/P-g-C3N4修饰的玻碳电极。
2.权利要求1所述的Pd/P-g-C3N4修饰的玻碳电极用于多巴胺、氯丙嗪和氯氮平的检测。
3.一种用于多巴胺、氯丙嗪和氯氮平的检测电化学传感器，包括权利要求1所述的Pd/P-g-C3N4修饰的玻碳电极、参比电极，对电极和电化学工作站。
4.权利要求1所述的Pd/P-g-C3N4修饰的玻碳电极的制备方法，包括以下步骤：
1)P-g-C3N4的制备：取三聚氰胺和磷酸氢二铵，加水搅拌均匀得到白色悬浊液，置于100℃水浴中使其水分挥发得到三聚氰胺磷酸氢二铵的固体混合物，取混合物至马弗炉中煅烧，得到磷掺杂的氮化碳P-g-C3N4粗品；将P-g-C3N4粗品加入硝酸中，加热回流，冷却至室温，用超纯水洗涤至中性，干燥过夜，纯化得到P-g-C3N4；
2)Pd/P-g-C3N4的制备：取P-g-C3N4加入蒸馏水中超声，加入醋酸钯溶液得到混悬液，滴加氢氧化钠溶液将混悬液调为碱性，搅拌，加入过量的硼氢化钠溶液，冷却至室温，用超纯水洗涤至中性，干燥过夜，得到磷/钯掺杂的氮化碳Pd/P-g-C3N4；
3)工作电极的预处理：取适量不同粒径大小的Al2O3抛光粉末打磨电极，再超声进行洗涤，氮气吹扫干待用；
4)修饰电极：取Pd/P-g-C3N4悬浮液滴涂到玻碳电极的圆盘镜面，然后置于室温下自然晾干，使其形成稳定的膜；将电极插入硫酸溶液中，采用循环伏安法CV进行电极活性测定。
5.根据权利要求4所述的制备方法，其特征在于，所述步骤1)中P-g-C3N4的制备方法如下：取三聚氰胺，加入磷酸氢二铵，加水搅拌均匀得到白色悬浊液，置于100℃水浴中使其水分挥发得到三聚氰胺磷酸氢二铵均匀的白色固体混合物，取混合物5g移至小坩埚在马弗炉中以550℃保持4h，得到P-g-C3N4粗品；将1gP-g-C3N4粗品粉末加入100mL5mol/L的硝酸中，在温度为120℃下加热回流12h，冷却至室温，用超纯水洗涤至中性，于60℃烘箱中干燥过夜，纯化得到P-g-C3N4。
6.根据权利要求4所述的制备方法，其特征在于，所述步骤2)中Pd/P-g-C3N4的制备方法如下：取100mgP-g-C3N4加入到10mL蒸馏水中超声15min，分别加入浓度为4.26mM的醋酸钯溶液得到黄色混悬液，滴加0.1M氢氧化钠将混悬液调为pH为10，在50℃下搅拌6h，加入过量的0.1M的硼氢化钠溶液，冷却至室温，用超纯水洗涤至中性，于60℃烘箱中干燥过夜，得到Pd/P-g-C3N4。
7.根据权利要求4所述的制备方法，其特征在于，所述Pd/P-g-C3N4中磷掺杂的质量份数为3～20％；钯掺杂的质量份数为1～5％；优选地，所述Pd/P-g-C3N4中磷掺杂的质量份数为10％；钯掺杂的质量份数为4％。
8.根据权利要求4所述的制备方法，其特征在于，所述步骤3)中Al2O3抛光粉的粒径选自1μm、0.3μm和0.05μm，优选地，所述步骤3)中的预处理方法为：将电极垂直在抛光绒布上画“8”字依次打磨5min至电极成光滑镜面，再依次用去离子水、丙酮、乙醇各超声洗涤5min以确保电极表面完全干净，氮气吹干待用。
9.根据权利要求4所述的制备方法，其特征在于，所述步骤4)中修饰电极的方法为：取10mg的Pd/P-g-C3N4分散到5mL的超纯水中，超声处理15min后搅拌6h，得到浓度为2mg/mL的悬浮液，准确量取6.0μL复合材料滴涂到玻碳电极的圆盘镜面，然后置于室温下自然晾干，使其形成稳定的膜。
10.权利要求1所述的Pd/P-g-C3N4修饰的玻碳电极用于多巴胺、氯丙嗪和氯氮平的检测方法，包括以下步骤：
S1采用DPV法进行测定标准曲线：加入不同浓度的多巴胺、氯丙嗪和氯氮平的混合溶液，使各物质与Pd/P-g-C3N4特异性结合，在修饰电极表面发生氧化还原反应，通过在电解质溶液中电子传输，引起电信号的改变，一定浓度范围内浓度与电信号呈现线性关系，得到多巴胺、氯丙嗪和氯氮平的标准曲线；
S2采用DPV法对未知浓度的多巴胺、氯丙嗪和氯氮平溶液进行测定电信号，利用多巴胺、氯丙嗪和氯氮平的标准曲线进行定量；
优选地，所述步骤S1中电解质溶液为pH为7的KH2PO4-Na2HPO4溶液；
优选地，所述步骤S1中所述的DPV测试参数如下：电势扫描为-0.2-1.0V；振幅为0.05V；脉冲0.06s；脉冲周期0.5s；灵敏度为1.0×10-5；
优选地，所述步骤S1中多巴胺在0.05-2.50μM和2.50-250.00μM浓度范围内呈现良好线性，检测限为10nM；氯氮平在0.02-10.00μM和10.00μM-100.00μM浓度范围内呈现良好线性，检测限为5nM；氯丙嗪在0.02-10.00μM和10.00μM-100.00μM浓度范围内呈现良好线性，检测限为5nM；各物质的加标回收率在95.9-102.0％之间。
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