CN109856101A - 一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法 - Google Patents

一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法 Download PDF

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CN109856101A
CN109856101A CN201910236390.5A CN201910236390A CN109856101A CN 109856101 A CN109856101 A CN 109856101A CN 201910236390 A CN201910236390 A CN 201910236390A CN 109856101 A CN109856101 A CN 109856101A
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金辉
桂日军
孙玉娇
姜晓文
孙泽君
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Qingdao University
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Abstract

本发明属于纳米杂化物和比率传感的制备技术领域，具体涉及一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法。制备电活性物质A或B内包覆SiO2纳米球，与碳点(CDs)或金纳米簇(AuNCs)连接制备偶联物，将偶联物与DNA适体连接。向两种DNA‑偶联物分散液中加入离子或生物分子，拟合比率荧光峰强度(ICDs/IAuNCs)与离子或生物分子浓度间的线性关系，实现比率荧光传感。基于DNA终端巯基将A‑SiO2@CDs‑DNA连接在金电极表面，加入B‑SiO2@AuNCs‑DNA、离子或生物分子，拟合离子或生物分子浓度与比率电流峰强度(IB/IA)间的线性关系，实现比率电化学传感。与现有技术相比，本发明的杂化物可用于生物样品中特定离子和生物分子的荧光和电化学同时比率传感。

Description

一种可同时用作比率荧光和比率电化学传感的纳米杂化物的 制备方法
技术领域：
本发明属于纳米杂化物和比率传感的制备技术领域，具体涉及一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其制备的纳米杂化物可用于生物样品中特定离子和生物分子的双信号比率传感。
背景技术：
胶体半导体纳米晶或量子点具有诸多显著优于传统有机染料、荧光蛋白及其它荧光纳米材料的发光性质，发射光谱尺寸可调、半峰宽窄、激发光谱宽、量子产率高、光稳定性好等，在化学、材料学、生物学及医学等领域展现出巨大的应用前景。半导体量子点中通常含有毒重金属元素如Cd,Hg,Pb等，制约了在生物、医学及环境领域的广泛应用。近年来，低毒量子点已成为纳米材料领域的研究热点，尤其是碳量子点相关研究被大量报道。由于低毒性和生物相容性，碳量子点广泛应用于化学/生物传感和成像。在荧光分析中，相比基于单一荧光改变来定量被测物的方法，基于双荧光比率的方法具有更高的定量精确性，可有效消除背景/自体荧光干扰。碳量子点与另一种荧光体组成传感体系，被测物引起传感体系中的比率荧光改变，构建基于碳量子点的比率荧光分析方法。
电化学分析法可执行高灵敏的电化学信号检测，主要源于在液-固界面对高富集电信号传感的特征。当被测物加入电解液中会快速在电极表面发生相互作用，引起电信号改变用于被测物分析。单一电化学信号检测方法易受背景、试剂、系统和环境条件等因素的影响，从而导致测定结果的波动。采用双信号比值处理获得信号的强度比率即比率电化学分析方法，具备自校准功能，有效消除了自体和背景信号的干扰，提高了检测结果的准确性和可靠性。
张明等制备了可电聚合的有机荧光传感材料用于金属离子的荧光或电化学检测(中国发明专利，公开号CN102899032A)；Zhang等制备了氮掺杂碳量子点用于荧光和电化学传感三硝基甲苯(L.Zhang,Y.Han,J.Zhu,Y.Zhai,S.Dong.Simple and sensitivefluorescent and electrochemical trinitrotoluene sensors based on aqueouscarbon dots.Anal.Chem.2015,87:2033)；Zhang等构筑了聚乙烯醇与石墨烯量子点的纳米纤维膜用于荧光和电化学传感H2O2和葡萄糖(P.Zhang,X.Zhao,Y.Ji,Z.Ouyang,X.Wen,J.Li,Z.Su,G.Wei.Electrospinning graphene quantum dots into a nanofibrousmembrane for dual-purpose fluorescent and electrochemicalbiosensors.J.Mater.Chem.B 2015,3:2487)。尽管先前的工作涉及了同一探针材料分别用于荧光和电化学检测目标物，但未涉及双信号比率检测方法。截至目前，尚未有基于同一纳米杂化物探针体系，同时用于比率荧光和比率电化学传感的国内外文献和专利的报道。基于此，本发明设计了新型的纳米杂化物探针，该探针可用于生物样品中特定离子和生物分子的双信号比率荧光和比率电化学同时传感。
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、灵敏度高的可同时用作比率荧光和比率电化学传感的纳米杂化物。
为实现上述目的，本发明涉及的一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法包括以下步骤：
1.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，该方法具体包括以下步骤：
(1)电活性物质溶于无水乙醇，加入(3-氨丙基)三乙氧基硅烷(APTS)搅拌均匀，放置避光处保存。加入氨水与乙醇并搅拌均匀，再加入正硅酸乙酯(TEOS)继续搅拌，然后加入TEOS进行反应。产物经高速离心、乙醇洗涤、真空干燥等处理制得电活性物质内包封的SiO2纳米球，将其分散在APTS与醋酸的混合液中，室温搅拌反应，采用类似方法提纯得到表面-NH2化的SiO2纳米球。
(2)柠檬酸和硫脲分散在二甲基甲酰胺中，转入含聚四氟乙烯内衬的微型高压反应釜中，在特定温度下搅拌反应，产物冷却至室温，经高速离心、乙醇和水洗涤、真空干燥等操作制得表面-COOH化的碳点(CDs)。
(3)将巯基十一酸分散在NaOH溶液中，快速搅拌下加入HAuCl4水溶液，用NaOH溶液调节混合液澄清，滴加NaBH4溶液，在室温下搅拌反应，产物进行透析、旋蒸、离心、洗涤和干燥等处理制得表面-COOH化的金纳米簇(AuNCs)。
(4)将偶联剂N-羟基硫代琥珀酸亚胺(NHS)和1-乙基-(3-二甲基氨基丙基)碳二亚胺(EDC)盐酸盐分散在磷酸盐水缓冲液中，加入表面-NH2化且电活性物质内包封的SiO2纳米球，搅拌均匀，放置避光处超声，磁力搅拌下将表面-COOH化CDs或AuNCs水分散液加入混合液中，搅拌反应，产物经离心、洗涤、干燥等后处理分别制得SiO2@CDs和SiO2@AuNCs两种偶联物。
(5)向Tris-HCl和NaOH水溶液中加入偶联剂NHS和EDC盐酸盐，加入SiO2@CDs或SiO2@AuNCs，连续搅拌反应，添加特异性单链DNA适体，在室温下搅拌反应，产物经透析、旋蒸、离心、洗涤、干燥等后处理制得纳米杂化物即SiO2@CDs-DNA或SiO2@AuNCs-DNA。
(6)在纳米杂化物的水分散液中加入特定离子或生物分子，测定混合液的荧光发射光谱，构建离子或生物分子浓度与比率荧光峰强度ICDs/IAuNCs之间的线性关系，实现对特定离子或生物分子的比率荧光传感。
(7)将分散在Tris-HCl中纳米杂化物转入装有金电极的电解槽中，金电极表面与DNA终端巯基通过Au-S键结合，将纳米杂化物连接在金电极表面，加入特定离子或生物分子，采用电化学工作站测定方波伏安曲线，构建离子或生物分子浓度与比率电流峰强度I电活性物质B/I电活性物质A之间的线性关系，实现对特定离子或生物分子的比率电化学传感。
步骤(1)中所述的电活性物质是指二茂铁(Fc)、亚甲基蓝(MB)、硫堇(TH)等电化学氧化还原探针分子，SiO2纳米球的平均尺寸为50～200nm；
步骤(2)中所述的反应温度为100～200℃，反应时间为3～10h；
步骤(3)中所述的搅拌反应时间为12～48h；
步骤(4)中所述的偶联剂NHS和EDC盐酸盐的质量比为1:1～1:3，搅拌反应时间为6～12h；
步骤(5)中所述的搅拌反应时间为6～18h；
步骤(6)和(7)中所述的特定离子是指Ag+,Hg2+,Pb2+等，生物分子是指凝血酶、脂多糖、癌胚抗原、甲胎蛋白等肿瘤生物标志物，特定离子或生物分子的摩尔浓度为1nM～1mM；
本发明制备了两种电活性物质A和B分别内包覆的表面-NH2化的SiO2纳米球，采用“羧-胺”反应将它们分别与表面-COOH化的碳点CDs或金纳米簇AuNCs连接，制备偶联物A-SiO2@CDs和B-SiO2@AuNCs，采用“羧-胺”反应将两种偶联物分别与终端为-NH2的特定单链DNA适体连接制备DNA-偶联物。向两种DNA-偶联物的混合水分散液中加入特定离子或生物分子，由于DNA碱基与特定离子相互作用形成复合物或四连体等结构，生物分子与其适体DNA链特异性结合形成卷曲纠缠的复合物，导致两种DNA-偶联物发生自组装，进而引起从CDs到AuNCs的荧光共振能量转移(FRET)，构建比率荧光峰强度ICDs/IAuNCs与特定离子或生物分子浓度之间的线性关系，实现比率荧光传感。基于DNA终端-SH和Au-S键合，将A-SiO2@CDs-DNA连接在金电极表面，在含有B-SiO2@AuNCs-DNA的电解液中加入特定的离子或生物分子，两种DNA-偶联物在金电极表面发生自组装，采用电化学工作站测定方波伏安曲线，可构建特定离子或生物分子浓度与比率电流峰强度IB/IA之间的线性关系，实现比率电化学传感。
附图说明：
图1.纳米杂化物同时比率荧光和比率电化学传感的示意图；
图2.纳米杂化物用作离子和生物分子比率荧光传感的制备及原理示意图；
图3.纳米杂化物用作离子和生物分子比率电化学传感的制备及原理示意图；
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：
本发明涉及的一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其制备过程与检测原理如图1～3所示，具体制备步骤如下：
将Fc或MB溶于无水乙醇，加入APTS搅拌均匀，避光处保存。加入氨水与乙醇搅拌均匀，加入TEOS搅拌反应，再加入TEOS继续反应。产物经离心、洗涤、干燥等处理制得Fc或MB内包封的SiO2纳米球～80nm。产物分散在APTS与醋酸的混合液中，室温搅拌反应，采用类似方法提纯制得表面-NH2化SiO2纳米球。
柠檬酸和硫脲分散在二甲基甲酰胺中，转入含聚四氟乙烯内衬的微型高压反应釜中，在160℃下搅拌反应6h，产物冷却至室温，经离心、乙醇和水洗涤、干燥等处理制得表面-COOH化CDs。
将巯基十一酸分散在NaOH溶液中，快速搅拌下加入HAuCl4水溶液，用NaOH调节混合液澄清，滴加NaBH4溶液，室温搅拌反应24h，产物经透析、旋蒸、离心、洗涤和干燥等处理制得表面-COOH化AuNCs。
将NHS和EDC盐酸盐以质量比1:1分散在磷酸盐水缓冲液中，加入表面-NH2化且Fc或MB内包封的SiO2纳米球，搅拌均匀，避光超声，磁力搅拌，将表面-COOH化CDs或AuNCs加入混合液中，搅拌反应8h，产物经离心、洗涤、干燥等后处理分别制得Fc-SiO2@CDs和MB-SiO2@AuNCs两种偶联物。
向Tris-HCl和NaOH水溶液中加入偶联剂NHS和EDC盐酸盐，加入Fc-SiO2@CDs或MB-SiO2@AuNCs，连续搅拌，添加特异性单链DNA适体，在室温下搅拌反应12h，产物经透析、旋蒸、离心、洗涤、干燥等后处理制得纳米杂化物即Fc-SiO2@CDs-DNA或MB-SiO2@AuNCs-DNA。
向纳米杂化物的水分散液中加入Ag+或凝血酶，测定混合液的荧光发射光谱，构建Ag+或凝血酶浓度与比率荧光峰强度ICDs/IAuNCs之间的线性关系，实现对Ag+或凝血酶的比率荧光传感。将分散在Tris-HCl中的纳米杂化物转入装有金电极的电解槽中，金电极表面与DNA终端巯基通过Au-S键结合，将纳米杂化物连接在金电极表面，加入Ag+或凝血酶，采用电化学工作站测定方波伏安曲线，构建Ag+或凝血酶浓度与比率电流峰强度IMB/IFc之间的线性关系，实现对Ag+或凝血酶的比率电化学传感，Ag+或凝血酶的浓度范围为5nM～0.1mM。
实施例2：
将Fc或MB溶于无水乙醇，加入APTS搅拌均匀，避光处保存。加入氨水与乙醇搅拌均匀，加入TEOS搅拌反应，再加入TEOS继续反应。产物经离心、洗涤、干燥等处理制得Fc或MB内包封的SiO2纳米球～100nm。产物分散在APTS与醋酸的混合液中，室温搅拌反应，采用类似方法提纯制得表面-NH2化SiO2纳米球。
柠檬酸和硫脲分散在二甲基甲酰胺中，转入含聚四氟乙烯内衬的微型高压反应釜中，在180℃下搅拌反应5h，产物冷却至室温，经离心、乙醇和水洗涤、干燥等处理制得表面-COOH化CDs。
将巯基十一酸分散在NaOH溶液中，快速搅拌下加入HAuCl4水溶液，用NaOH调节混合液澄清，滴加NaBH4溶液，室温搅拌反应18h，产物经透析、旋蒸、离心、洗涤和干燥等处理制得表面-COOH化AuNCs。
将NHS和EDC盐酸盐以质量比1:2分散在磷酸盐水缓冲液中，加入表面-NH2化且Fc或MB内包封的SiO2纳米球，搅拌均匀，避光超声，磁力搅拌，将表面-COOH化CDs或AuNCs加入混合液中，搅拌反应10h，产物经离心、洗涤、干燥等后处理分别制得Fc-SiO2@CDs和MB-SiO2@AuNCs两种偶联物。
向Tris-HCl和NaOH水溶液中加入偶联剂NHS和EDC盐酸盐，加入Fc-SiO2@CDs或MB-SiO2@AuNCs，连续搅拌，添加特异性单链DNA适体，在室温下搅拌反应15h，产物经透析、旋蒸、离心、洗涤、干燥等后处理制得纳米杂化物即Fc-SiO2@CDs-DNA或MB-SiO2@AuNCs-DNA。
向纳米杂化物的水分散液中加入Hg2+或脂多糖，测定混合液的荧光发射光谱，构建Hg2+或脂多糖浓度与比率荧光峰强度ICDs/IAuNCs之间的线性关系，实现对Hg2+或脂多糖的比率荧光传感。将分散在Tris-HCl中的纳米杂化物转入装有金电极的电解槽中，金电极表面与DNA终端巯基通过Au-S键结合，将纳米杂化物连接在金电极表面，加入Hg2+或脂多糖，采用电化学工作站测定方波伏安曲线，构建Hg2+或脂多糖浓度与比率电流峰强度IMB/IFc之间的线性关系，实现对Hg2+或脂多糖的比率电化学传感，Hg2+或脂多糖的浓度范围为10nM～0.5mM。
实施例3：
将Fc或MB溶于无水乙醇，加入APTS搅拌均匀，避光处保存。加入氨水与乙醇搅拌均匀，加入TEOS搅拌反应，再加入TEOS继续反应。产物经离心、洗涤、干燥等处理制得Fc或MB内包封的SiO2纳米球～120nm。产物分散在APTS与醋酸的混合液中，室温搅拌反应，采用类似方法提纯制得表面-NH2化SiO2纳米球。
柠檬酸和硫脲分散在二甲基甲酰胺中，转入含聚四氟乙烯内衬的微型高压反应釜中，在200℃下搅拌反应3h，产物冷却至室温，经离心、乙醇和水洗涤、干燥等处理制得表面-COOH化CDs。
将巯基十一酸分散在NaOH溶液中，快速搅拌下加入HAuCl4水溶液，用NaOH调节混合液澄清，滴加NaBH4溶液，室温搅拌反应36h，产物经透析、旋蒸、离心、洗涤和干燥等处理制得表面-COOH化AuNCs。
将NHS和EDC盐酸盐以质量比1:3分散在磷酸盐水缓冲液中，加入表面-NH2化且Fc或MB内包封的SiO2纳米球，搅拌均匀，避光超声，磁力搅拌，将表面-COOH化CDs或AuNCs加入混合液中，搅拌反应12h，产物经离心、洗涤、干燥等后处理分别制得Fc-SiO2@CDs和MB-SiO2@AuNCs两种偶联物。
向Tris-HCl和NaOH水溶液中加入偶联剂NHS和EDC盐酸盐，加入Fc-SiO2@CDs或MB-SiO2@AuNCs，连续搅拌，添加特异性单链DNA适体，在室温下搅拌反应18h，产物经透析、旋蒸、离心、洗涤、干燥等后处理制得纳米杂化物即Fc-SiO2@CDs-DNA或MB-SiO2@AuNCs-DNA。
向纳米杂化物的水分散液中加入Pb2+或癌胚抗原，测定混合液的荧光发射光谱，构建Pb2+或癌胚抗原浓度与比率荧光峰强度ICDs/IAuNCs之间的线性关系，实现对Pb2+或癌胚抗原的比率荧光传感。将分散在Tris-HCl中的纳米杂化物转入装有金电极的电解槽中，金电极表面与DNA终端巯基通过Au-S键结合，将纳米杂化物连接在金电极表面，加入Pb2+或癌胚抗原，采用电化学工作站测定方波伏安曲线，构建Pb2+或癌胚抗原浓度与比率电流峰强度IMB/IFc之间的线性关系，实现对Pb2+或癌胚抗原的比率电化学传感，Pb2+或癌胚抗原的浓度范围为100nM～1mM。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (7)

1.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，该方法具体包括以下步骤：
(1)电活性物质溶于无水乙醇，加入(3-氨丙基)三乙氧基硅烷(APTS)搅拌均匀，放置避光处保存；加入氨水与乙醇并搅拌均匀，再加入正硅酸乙酯(TEOS)继续搅拌，然后加入TEOS进行反应；产物经高速离心、乙醇洗涤、真空干燥等处理制得电活性物质内包封的SiO2纳米球，将其分散在APTS与醋酸的混合液中，室温搅拌反应，采用类似方法提纯得到表面-NH2化的SiO2纳米球；
(2)柠檬酸和硫脲分散在二甲基甲酰胺中，转入含聚四氟乙烯内衬的微型高压反应釜中，在特定温度下搅拌反应，产物冷却至室温，经高速离心、乙醇和水洗涤、真空干燥等操作制得表面-COOH化的碳点(CDs)；
(3)将巯基十一酸分散在NaOH溶液中，快速搅拌下加入HAuCl4水溶液，用NaOH溶液调节混合液澄清，滴加NaBH4溶液，在室温下搅拌反应，产物进行透析、旋蒸、离心、洗涤和干燥等处理制得表面-COOH化的金纳米簇(AuNCs)；
(4)将偶联剂N-羟基硫代琥珀酸亚胺(NHS)和1-乙基-(3-二甲基氨基丙基)碳二亚胺(EDC)盐酸盐分散在磷酸盐水缓冲液中，加入表面-NH2化且电活性物质内包封的SiO2纳米球，搅拌均匀，放置避光处超声，磁力搅拌下将表面-COOH化CDs或AuNCs水分散液加入混合液中，搅拌反应，产物经离心、洗涤、干燥等后处理分别制得SiO2@CDs和SiO2@AuNCs两种偶联物；
(5)向Tris-HCl和NaOH水溶液中加入偶联剂NHS和EDC盐酸盐，加入SiO2@CDs或SiO2@AuNCs，连续搅拌反应，添加特异性单链DNA适体，在室温下搅拌反应，产物经透析、旋蒸、离心、洗涤、干燥等后处理制得纳米杂化物即SiO2@CDs-DNA或SiO2@AuNCs-DNA；
(6)在纳米杂化物的水分散液中加入特定离子或生物分子，测定混合液的荧光发射光谱，构建离子或生物分子浓度与比率荧光峰强度ICDs/IAuNCs之间的线性关系，实现对特定离子或生物分子的比率荧光传感；
(7)将分散在Tris-HCl中纳米杂化物转入装有金电极的电解槽中，金电极表面与DNA终端巯基通过Au-S键结合，将纳米杂化物连接在金电极表面，加入特定离子或生物分子，采用电化学工作站测定方波伏安曲线，构建离子或生物分子浓度与比率电流峰强度I电活性物质B/I电活性物质A之间的线性关系，实现对特定离子或生物分子的比率电化学传感。
2.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，步骤(1)中所述的电活性物质是指二茂铁(Fc)、亚甲基蓝(MB)、硫堇(TH)等电化学氧化还原探针分子，SiO2纳米球的平均尺寸为50～200nm。
3.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，步骤(2)中所述的反应温度为100～200℃，反应时间为3～10h。
4.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，步骤(3)中所述的搅拌反应时间为12～48h。
5.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，步骤(4)中所述的偶联剂NHS和EDC的质量比为1:1～1:3，搅拌反应时间为6～12h。
6.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，步骤(5)中所述的搅拌反应时间为6～18h。
7.一种可同时用作比率荧光和比率电化学传感的纳米杂化物的制备方法，其特征在于，步骤(6)和(7)中所述的特定离子是指Ag+,Hg2+,Pb2+等，生物分子是指凝血酶、脂多糖、癌胚抗原、甲胎蛋白等肿瘤生物标志物，特定离子或生物分子的摩尔浓度为1nM～1mM。
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