CN107153089A - 一种树枝状纳米复合物多柔比星电化学传感器的制备方法 - Google Patents
一种树枝状纳米复合物多柔比星电化学传感器的制备方法 Download PDFInfo
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Abstract
本发明属于纳米材料与生化传感的交叉技术领域，涉及一种基于银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物多柔比星电化学传感器的制备方法：采用Hummers法制备氧化石墨烯，以柠檬酸溶剂热碳化法制备碳点；在氧化石墨烯、碳点与氢氧化二氨合银的混合电解液中，采用电沉积法和共还原反应在玻碳电极界面制备银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物，通过电化学工作站测量，拟合多柔比星在电解液中浓度与其氧化电流峰强度间的线性关系，构建基于该复合物的多柔比星电化学传感器；该传感器工艺简单，制备成本低，产品灵敏度高，可作为一种新颖的电化学传感器用于多柔比星的高效检测。
Description
技术领域：
本发明属于纳米材料与生化传感的交叉技术领域，具体涉及一种基于银纳米颗粒/碳点/还原氧化石墨烯三组分的树枝状纳米复合物多柔比星电化学传感器的制备方法，其制备的传感器可用于多柔比星的高效检测。
背景技术：
多柔比星俗称阿霉素，是一种重要的蒽环类抗生素，被广泛应用于多种类型肿瘤的治疗，如恶性淋巴瘤、乳腺癌、支气管肺癌、卵巢癌、软组织肉瘤、成骨肉瘤等。高剂量的多柔比星对人体的副作用主要表现为对骨髓造血功能的损害以及对心脏的损伤。多柔比星的浓度水平可充当一种有效的信号指示，用于人体健康因子、相关肿瘤疾病的诊断及治疗的监控。鉴于多柔比星的以上特征，开发一种简单有效的检测多柔比星的方法对于肿瘤疾病的诊断和治疗具有重要意义。
常规用于多柔比星定性和定量检测的方法包括高效液相色谱法、毛细管电泳法、紫外-可见吸收光谱法、荧光光谱法、电化学法等。这些用于多柔比星检测的仪器分析方法普遍存在某些缺陷，如复杂的前处理、耗时的操作和较低的灵敏性。相比之下，电化学分析法尤其是电化学生物传感器具备显著的优势，源于多柔比星分子中苯醌和氢醌结构所引起的优异电化学活性。电化学生物传感器的明显优点主要包括操作简单、低成本和高灵敏性。在先前的报道中，不同纳米材料改性的电极已被用于电化学传感多柔比星，如β-环糊精-石墨烯杂化物纳米片改性玻碳电极(Electrochemical sensor for ultrasensitivedetermination of doxorubicin and methotrexate based onβ-cyclodextrin-graphenehybrid nanosheets,Electroanalysis,2011,23,2400)，磁性Fe3O4-氧化石墨烯-亚硫酸复合物膜改性的电极(Room temperature in situ chemical synthesis of Fe3O4/graphene,Ceram.Int.,2012,38,6411)，石墨烯量子点改性电极(Sensing of doxorubicinhydrochloride using graphene quantum dot modified glassy carbon electrode,J.Mol.Liq.,2016,221,354)，氧化型多壁碳纳米管改性的电极(Electrochemicallyoxidized multiwalled carbon nanotube/glassy carbon electrode as a probe forsimultaneous determination of dopamine and doxorubicin in biological samples,Anal.Bioanal.Chem.,2016,408,2577)等用于多柔比星电化学传感研究。
在这些报道的多柔比星电化学传感研究中，普遍使用了单一的碳纳米材料作为底物去修饰电极界面，为进一步提高多柔比星电化学传感的检测效率，有必要引入两种或多种电活性物质作为底物，如贵金属银纳米颗粒、碳点和还原氧化石墨烯，获得不同种类电活性物质的协同效应，以提高电极界面的电导率，增加表面积和活性位点，加快电子迁移速率，实现对多柔比星高灵敏电化学信号检测。截至目前，尚未有银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物的制备方法，及其应用于多柔比星电化学高灵敏检测相关的国内外文献和专利等资料报道。
发明内容：
本发明的目的在于克服上述现有技术存在的缺陷，设计一种方法简单、成本低和高灵敏性的基于银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物多柔比星电化学传感器的制备方法。
为了实现上述目的，本发明涉及的基于银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物多柔比星电化学传感器的制备工艺包括以下步骤：
(1)采用Hummers方法制备氧化石墨烯：将1.0克石墨加入250毫升圆底三口瓶中，滴加25毫升浓硫酸碳化石墨，缓慢搅拌反应24小时，之后加入1.5克高锰酸钾，将三口瓶转移至冰浴中冷却，继续搅拌反应30分钟，然后升温至60℃，搅拌反应45分钟，其间每间隔15分钟加入3毫升二次蒸馏水，反应完毕后，加入180毫升二次蒸馏水用以终止反应，产物冷却至室温，将溶液过滤，沉淀物经过洗涤干燥，得到氧化石墨烯；
(2)将柠檬酸和碳酸氢铵进行溶剂热碳化制备碳点：将1.0克柠檬酸和2.0克碳酸氢铵溶于10毫升二甲基亚砜中，将混合液转移至反应釜中，在160℃下搅拌反应6小时，将反应溶液冷却至室温后，加入20毫升质量浓度为50毫克/毫升的氢氧化钠水溶液，搅拌反应1分钟，在16000转/分钟的转速下用离心机离心10分钟，所得沉淀物溶于二次蒸馏水，再次离心分离去除残留盐和碱，最后冷冻干燥得到碳点；
(3)将步骤(1)制备的氧化石墨烯与步骤(2)制备的碳点充分混合，配制成质量浓度为1.0～2.0毫克/毫升的均质碳点/氧化石墨烯水分散液，其中碳点与氧化石墨烯的质量比为1:5～5:1；
(4)在物质的量浓度为50毫摩/升的硝酸银水溶液中加入氨水制备得到40毫摩/升的氢氧化二氨合银水溶液，将溶液与步骤(3)制备的碳点/氧化石墨烯水分散液混合，制得三者均匀混合的水分散液，碳点/氧化石墨烯与氢氧化二氨合银质量浓度比为1:10～10:1；
(5)将步骤(4)制备的碳点/氧化石墨烯与氢氧化二氨合银水分散液加入盛有物质的量浓度为1毫摩/升的磷酸盐水缓冲溶液的电解池中，电解池中插入玻碳电极，采用循环伏安法在玻碳电极界面通过一步电沉积方法将氧化石墨烯和氢氧化二氨合银共还原成还原氧化石墨烯和银纳米颗粒，循环伏安法扫描速率为0～50毫伏/秒，扫描电压0～2.0伏，循环次数0～20圈，在玻碳电极界面制备出银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物；
(6)将步骤(5)制得的银纳米颗粒/碳点/还原氧化石墨烯/玻碳电极电化学传感体系作为传感器，采用差示脉冲伏安法测定传感体系的电化学曲线，拟合氧化电流峰强度Ip(微安)与多柔比星浓度([DOX],0～250×10-8摩/升)之间的线性关系：Ip(微安)＝2.197+8.293[DOX]，即获得基于银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物的多柔比星电化学传感器。
本发明与现有技术相比，采用一步电沉积法发生共还原反应在玻碳电极界面制备银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物，基于多柔比星在该复合物修饰的玻碳电极界面高敏感的电化学信号响应，可构建出高灵敏的多柔比星电化学传感器；其制备工艺简单，制备成本低，产品灵敏度高，能够发展成为一种新颖的电化学生物传感器，适用于生物样品中多柔比星的高效检测。
附图说明：
图1为本发明涉及的纳米复合物电化学传感器制备与多柔比星检测原理示意图。
图2为本发明涉及的纳米复合物的扫描电子显微镜和透射电子显微镜照片。
图3为本发明涉及的银纳米颗粒/碳点/还原氧化石墨烯-玻碳电极传感体系对多柔比星的电化学信号响应，以及传感体系氧化电流峰强度与多柔比星浓度之间的线性关系图。
具体实施方式：
下面结合附图并通过具体实施例对本发明进行详细说明。
实施例1：
本实施例基于银纳米颗粒/碳点/还原氧化石墨烯复合物的电化学传感器制备与多柔比星检测示意图参见图1所示，首先采用Hummers方法制备氧化石墨烯：将1.0克石墨加入250毫升三口瓶中，滴加25毫升浓硫酸碳化石墨，缓慢搅拌反应24小时；加入1.5克高锰酸钾，转移三口瓶至冰浴装置中冷却，继续搅拌反应30分钟；升温至60℃，反应45分钟；其间每间隔15分钟加入3毫升二次蒸馏水，然后加入180毫升二次蒸馏水用以终止反应，冷却产物至室温，将溶液过滤，沉淀物经过洗涤干燥，制得氧化石墨烯。将柠檬酸和碳酸氢铵进行溶剂热碳化制备碳点：将1.0克柠檬酸和2.0克尿素溶于10毫升二甲基亚砜中，将此混合液转移至反应釜中，在160℃下反应6小时，冷却反应溶液至室温，加入20毫升质量浓度为50毫克/毫升的氢氧化钠水溶液，搅拌反应1分钟，在16000转/分钟转速下用离心机离心10分钟，所得沉淀物溶于二次蒸馏水，再次离心分离去除残留盐和碱，最后冷冻干燥得到碳点。将新制备的氧化石墨烯与碳点充分混合，分别将二者配制成相同质量浓度1.0毫克/毫升的水分散液，以体积比3:1充分混合，在室温下搅拌30分钟，配制成均质混合液；再在50毫摩/升的硝酸银水溶液中加入质量分数为1％的氨水溶液，充分搅拌至澄清透明制得氢氧化二氨合银水溶液，氢氧化二氨合银浓度调节为40毫摩/升；然后选取一根玻碳电极，将其打磨至镜面，然后插入1毫摩/升,pH 7.0经除氧的磷酸盐缓冲液中，检测其电化学信号直至达到稳定；将上述的碳点/氧化石墨烯水分散液与氢氧化二氨合银水溶液以体积比1:1混合作为电解液，再插入打磨后的玻碳电极，采用循环伏安法对玻碳电极界面进行电沉积处理，其中扫描速率为20毫伏/秒，扫描电压0～1.0伏，循环次数5圈，制得银纳米颗粒/碳点/还原氧化石墨烯-玻碳电极传感体系，银纳米颗粒/碳点/还原氧化石墨烯复合物的结构如图2所示，展现出清晰的三组分树枝状纳米复合物结构；反应结束后，加入10纳摩/升～2.5微摩/升多柔比星至电解液中，采用差示脉冲伏安法测定传感体系的电化学曲线，拟合氧化电流峰强度与多柔比星浓度之间的线性关系，构建多柔比星电化学传感器(参见图3)；该传感器制备工艺简单，成本低，具备高灵敏性和高选择性，对多柔比星浓度的检测范围是1纳摩/升～5微摩/升，检测极限为3纳摩/升。
实施例2：
本实施例采用Hummers方法制备氧化石墨烯，将柠檬酸和碳酸氢铵进行溶剂热碳化制备碳点(具体方法同实施例1)，分别将二者配制成相同质量浓度2.0毫克/毫升的水分散液，然后以体积比1:1充分混合，在室温下搅拌30分钟，配制成均质混合液；再在50毫摩/升的硝酸银水溶液中加入质量分数为1％的氨水溶液，充分搅拌至澄清透明制得氢氧化二氨合银水溶液，氢氧化二氨合银浓度调节为40毫摩/升；选取一根玻碳电极，将其打磨至镜面，然后插入1毫摩/升,pH 7.0经除氧的磷酸盐缓冲液中，检测其电化学信号直至达到稳定；然后将上述的碳点-氧化石墨烯水分散液与氢氧化二氨合银水溶液以体积比3:1混合作为电解液，再插入打磨后的玻碳电极，采用循环伏安法对玻碳电极界面进行电沉积处理，其中扫描速率为30毫伏/秒，扫描电压0～1.5伏，循环次数10圈，制得银纳米颗粒/碳点/还原氧化石墨烯-玻碳电极传感体系；反应结束后，加入1纳摩/升～5微摩/升多柔比星至电解液中，采用差示脉冲伏安法测定传感体系的电化学曲线，拟合氧化电流峰强度与多柔比星浓度之间的线性关系，构建多柔比星电化学传感器；该传感器制备工艺简单，成本低，具备高灵敏性和高选择性，对多柔比星浓度的检测范围是1纳摩/升～5微摩/升，检测极限为0.3纳摩/升。
实施例3：
本实施例采用Hummers方法制备氧化石墨烯，将柠檬酸和碳酸氢铵进行溶剂热碳化制备碳点(具体方法同实施例1)，分别将二者配制成相同质量浓度1.5毫克/毫升的水分散液，然后以体积比1:3充分混合，在室温下搅拌30分钟，配制成均质混合液；再在50毫摩/升的硝酸银水溶液中加入质量分数为1％的氨水溶液，充分搅拌至澄清透明制得氢氧化二氨合银水溶液，氢氧化二氨合银浓度调节为40毫摩/升；然后选取一根玻碳电极，将其打磨至镜面，然后插入1毫摩/升,pH 7.0经除氧的磷酸盐缓冲液中，检测其电化学信号直至达到稳定；将上述的碳点-氧化石墨烯水分散液与氢氧化二氨合银水溶液以体积比1:3混合作为电解液，再插入打磨后的玻碳电极，采用循环伏安法对玻碳电极界面进行电沉积处理，其中扫描速率为40毫伏/秒，扫描电压0.5～2.0伏，循环次数15圈，制得银纳米颗粒/碳点/还原氧化石墨烯-玻碳电极传感体系；反应结束后，加入10纳摩/升～10微摩/升多柔比星至电解液中，采用差示脉冲伏安法测定传感体系的电化学曲线，拟合氧化电流峰强度与多柔比星浓度之间的线性关系，构建多柔比星电化学传感器；该传感器制备工艺简单，成本低，具备高灵敏性和高选择性，对多柔比星浓度的检测范围是10纳摩/升～10微摩/升，检测极限为4纳摩/升。
Claims (1)
1.一种树枝状纳米复合物多柔比星电化学传感器的制备方法，其特征在于具体工艺包括以下步骤：
(1)采用Hummers方法制备氧化石墨烯：将1.0克石墨加入250毫升圆底三口瓶中，滴加25毫升浓硫酸碳化石墨，缓慢搅拌反应24小时，之后加入1.5克高锰酸钾，将三口瓶转移至冰浴中冷却，继续搅拌反应30分钟，然后升温至60℃，搅拌反应45分钟，其间每间隔15分钟加入3毫升二次蒸馏水，反应完毕后，加入180毫升二次蒸馏水用以终止反应，产物冷却至室温，将溶液过滤，沉淀物经过洗涤干燥，得到氧化石墨烯；
(2)将柠檬酸和碳酸氢铵进行溶剂热碳化制备碳点：将1.0克柠檬酸和2.0克碳酸氢铵溶于10毫升二甲基亚砜中，将混合液转移至反应釜中，在160℃下搅拌反应6小时，将反应溶液冷却至室温后，加入20毫升质量浓度为50毫克/毫升的氢氧化钠水溶液，搅拌反应1分钟，在16000转/分钟的转速下用离心机离心10分钟，所得沉淀物溶于二次蒸馏水，再次离心分离去除残留盐和碱，最后冷冻干燥得到碳点；
(3)将步骤(1)制备的氧化石墨烯与步骤(2)制备的碳点充分混合，配制成质量浓度为1.0～2.0毫克/毫升的均质碳点/氧化石墨烯水分散液，其中碳点与氧化石墨烯的质量比为1:5～5:1；
(4)在物质的量浓度为50毫摩/升的硝酸银水溶液中加入氨水制备得到40毫摩/升的氢氧化二氨合银水溶液，将溶液与步骤(3)制备的碳点/氧化石墨烯水分散液混合，制得三者均匀混合的水分散液，碳点/氧化石墨烯与氢氧化二氨合银质量浓度比为1:10～10:1；
(5)将步骤(4)制备的碳点/氧化石墨烯与氢氧化二氨合银水分散液加入盛有物质的量浓度为1毫摩/升的磷酸盐水缓冲溶液的电解池中，电解池中插入玻碳电极，采用循环伏安法在玻碳电极界面通过一步电沉积方法将氧化石墨烯和氢氧化二氨合银共还原成还原氧化石墨烯和银纳米颗粒，循环伏安法扫描速率为0～50毫伏/秒，扫描电压0～2.0伏，循环次数0～20圈，在玻碳电极界面制备出银纳米颗粒/碳点/还原氧化石墨烯三组分树枝状纳米复合物；
(6)将步骤(5)制得的银纳米颗粒/碳点/还原氧化石墨烯/玻碳电极电化学传感体系作为传感器，采用差示脉冲伏安法测定传感体系的电化学曲线，拟合氧化电流峰强度Ip(微安)与多柔比星浓度([DOX],0～250×10-8摩/升)之间的线性关系：Ip(微安)＝2.197+8.293[DOX]，即获得一种树枝状纳米复合物的多柔比星电化学传感器。
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| CN110568037A (zh) * | 2019-09-02 | 2019-12-13 | 江南大学 | 用于啶虫脒和吡虫啉联合毒性评价的电化学细胞传感器的构建方法及其应用 |
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| CN114538409A (zh) * | 2022-01-28 | 2022-05-27 | 湖南邦普循环科技有限公司 | 氮掺杂碳点-还原氧化石墨烯复合材料的制备方法和应用 |
| WO2023142668A1 (zh) * | 2022-01-28 | 2023-08-03 | 湖南邦普循环科技有限公司 | 氮掺杂碳点-还原氧化石墨烯复合材料的制备方法和应用 |
| CN116588917A (zh) * | 2023-06-30 | 2023-08-15 | 苏州擎动动力科技有限公司 | 一种载体及其制备方法和应用 |
| CN116588917B (zh) * | 2023-06-30 | 2024-05-14 | 苏州擎动动力科技有限公司 | 一种载体及其制备方法和应用 |
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