CN117129464A - 一种表面增强拉曼光谱检测传感器及其制备方法和应用 - Google Patents
一种表面增强拉曼光谱检测传感器及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于光学传感技术领域,具体为一种表面增强拉曼光谱检测传感器及其制备方法和应用。本发明的传感器制备方法包括:在玻碳纤维纸基底上用硼氢化钠和抗坏血酸还原硝酸银,使银纳米颗粒沉积在玻碳纤维纸表面,形成SERS纸基底;使用还原剂TCEP将巯基修饰的重金属离子的核酸适配体DNA进行还原,形成修饰后的纸基SERS传感器,该SERS纸基底对相应的重金属离子具有识别和传感功能,可用于检测牛奶中的重金属离子含量,包括建立重金属离子浓度标准曲线;将牛奶样品置于重金属离子标准品溶液中,用拉曼光谱仪检测拉曼信号;根据标准曲线计算得到重金属离子含量。本发明具有快速、高效、灵敏度高、成本低、操作简单等优点。
Description
技术领域
本发明属于光学传感技术领域,具体涉及表面增强拉曼光谱检测传感器及其制备方法和应用。
背景技术
拉曼效应,指光波在被散射后频率发生变化的现象,1928年由印度物理学家C.V.Raman发现。拉曼光谱能够提供丰富的分子结构信息,且无需对检测样品进行处理,应用十分广泛。1974-1977年,Van Duyne等人发现了表面增强拉曼现象,通过在粗糙的金属表面吸附分子可以将拉曼信号增强106倍左右,这种技术成为表面增强拉曼光谱(SERS)。SERS的主要特点有:1.是一种超灵敏检测技术,可以实现痕量物质检测;2.不仅可以应用于实验室研究,而且在现实生活中的应用也十分广泛,且操作比较简单,是一种多功能的分析技术;3.SERS检测与其他分析技术或平台联用,可以形成色谱分离拉曼检测、毛细管电泳拉曼检测、微流控芯片(纸芯片)拉曼平台。因此,表面增强拉曼光谱以其优异的发光性质,引起了材料科学、化学生物学、生命科学研究者的广泛关注,并用于材料的结构和形貌表征、化学和生物传感器、食品与环境分析、单分子检测、化学反应动力学等领域。
“纸”作为我们生活、工作以及学习中必不可少的工具,给我们带来了很大的便捷。纸基底具有易于加工,吸水性较好,多孔,物理生化惰性、优良的机械强度、携带方便、成本低廉等优点,在临床诊断、食品安全检测、环境卫生监控等方面都具有广阔的应用前景,是未来便携式现场分析装置发展的重要方向,对生物分析和疾病诊断领域中急需的原位表征、临床床边诊断、现场检测等的实现具有重要意义。
重金属通常指自身密度大于4.5g/cm3的金属,其离子往往具备强氧化性等理化性质、能与人体功能蛋白活性部位特异性结合,导致人体的部分正常生理功能无法实现,对人类和多种生物都有毒害作用。其中铅(Pb)、汞(Hg)、镉(Cd)是三种重要的对人体有害的重金属。随着环境污染的加剧,饲养和养殖用水、饲料中有害重金属含量不断增加。随着重金属含量的不断增加,通过重金属的生物迁移,也会影响到农产品中重金属的含量,其中牛奶和水产品中重金属的含量也越来越受到重视。在《食品安全国家标准-食品中污染物限量》(GB[6]2-2017)中规定,生乳、巴氏杀菌乳、灭菌乳、调制乳、发酵乳中的Pb、Hg、Cr的限量分别为0.05mg/kg、0.01mg/kg、0.3mg/kg。因此,重金属离子的检测一直是分析化学领域的重要工作。
发明人的研究发现,利用硼氢化钠和抗坏血酸的还原性,硝酸银可以被逐步还原为均匀的纳米颗粒沉积在玻碳纤维纸上。而这种沉积了银纳米颗粒的玻碳纤维纸提供了高灵敏度和稳定性的拉曼效应增强效果,同时也是一种廉价便捷的表面增强拉曼检测基底。在沉积了银纳米颗粒的玻碳纤维纸上面修饰上特异性识别重金属离子的核酸适配体,能够定量检测不同种类的重金属离子。
使用该方法制备的基底配合BWTEK公司的便携式拉曼光谱仪,可以快速地检测标准样品的重金属离子,而且重金属离子的含量和拉曼光谱特征峰的强度有很好的线性关系。使用本发明对牛奶中的重金属离子进行检测,具有快速高效,灵敏度高,成本低,操作简单的特点。
发明内容
本发明的目的在于提出一种便携、廉价且具有高灵敏度和稳定性的表面增强拉曼光谱检测传感器及其制备方法和应用。
本发明提出的表面增强拉曼光谱检测传感器的制备方法,具体步骤为:
(一)表面增强拉曼光谱检测玻碳纤维纸基底的制备;
以玻碳纤维纸为底板,采用“二次还原法”,室温下,在玻碳纤维纸上分步用硼氢化钠和抗坏血酸还原硝酸银,使银纳米颗粒沉积在玻碳纤维纸表面,形成表面增强拉曼光谱检测纸基底,简称为SERS纸基底;
具体操作流程为:调节水平摇床的震荡速度,室温下,在两块六孔板中分别加入1~5mL0.05M硼氢化钠溶液、1~5mL水、1~5mL 0.05M硝酸银溶液,以及1~5mL 0.05M抗坏血酸溶液、1~5mL水、1~5mL 0.05M硝酸银溶液;将玻碳纤维纸分别浸入各孔中,反应30-60秒,循环8-12次,玻碳纤维纸由白色变为暗灰色,即表明在玻碳纤维纸上沉积上了银纳米颗粒,得到表面增强拉曼光谱检测玻碳纤维纸基底,简称为SERS纸基底;
上述得到的表面增强拉曼光谱检测基底与未修饰的玻碳纤维纸相比,表面颜色变为灰黑色,银纳米颗粒的直径在60nm左右,分布均一(通过扫描电镜图可知);
(二)表面增强拉曼光谱检测玻碳纤维纸基底的修饰;
使用还原剂TCEP(三一(2一甲酰乙基)膦盐酸盐)将巯基修饰的重金属离子的核酸适配体DNA进行还原,将前述SERS纸基底浸泡在还原后的巯基修饰的核酸适配体DNA溶液中反应一段时间,形成修饰后的SERS纸基底,该SERS纸基底对相应的重金属离子具有识别和传感功能,记为纸基SERS传感基底。
具体操作流程为:
(1)将上述得到的SERS纸基底与4-巯基吡啶溶液作用5-15min,得到明显增强的4-巯基吡啶信号,重复5次相同实验,至彼此之间的信号差距小于10%;
(2)将5-50μL的5-100μmol/L的巯基修饰的核酸适配体溶液与0.1-10μL的0.1-10mol/L的TCEP混合,室温下还原15-120min,得到还原态的巯基修饰的核酸适配体溶液;
(3)将4-巯基吡啶信号增强的SERS纸基底浸泡在还原后的巯基修饰的核酸适配体溶液中,静置2-24h,得到修饰后的表面增强拉曼检测传感器,简称为纸基SERS传感器。
本发明制备的纸基SERS传感器,可用于检测牛奶样品中重金属的含量,具体步骤为:
(1)建立标重金属离子浓度标准曲线
配置10-6-10-3M的重金属离子溶液,将纸基SERS传感器浸入溶液中10-20min,取出该纸基SERS传感器,置入定制的塑料模具中心,用便携式拉曼光谱仪检测纸基SERS传感器的拉曼信号,根据1500-1600cm-1处的拉曼信号强度与溶液中重金属离子浓度建立标准曲线;
(2)检测牛奶样品的重金属离子含量
将牛奶样品置于10-3mol/L、10-4mol/L、10-5mol/L、10-6mol/L的重金属离子标准品溶液中;加入1~10mL三氯乙酸和10~60mM EDTA,并在涡旋振荡器上振荡2~20分钟;将混合溶液以5000~20000g离心10~40分钟;收集上清液并通过0.22μm膜过滤;将纸基SERS传感器浸入上述所得的上清液中,10~40分钟,取出该纸基SERS传感器,在拉曼光谱仪上检测拉曼信号,通过1500-1600cm-1处的拉曼信号强度的拉曼信号强度,代入标准曲线计算,即得到样品中残留的重金属离子含量。
与现有方法相比,本发明的纸基SERS传感器制备方法简便,廉价无污染;用于检测标准品重金属离子,特征峰强度与浓度线性关系好,灵敏度高;用于检测牛奶样品中重金属离子,快速高效,便携且易现场检测。
(1)合成方法简便,廉价,无污染:表面增强拉曼检测基底的制备采用“两步还原法”,不需要复杂的仪器,不需要高温、强酸强碱等苛刻条件,反应条件比较温和,操作简单,玻碳纤维纸价格便宜,对环境十分友好。
(2)特征峰强度与浓度线性关系好:纸基SERS传感器检测重金属离子所得的特征峰强度与浓度线性关系(R2)在10-3-10-6M浓度之间为0.92。
(3)快速高效:利用该纸基SERS传感器检测牛奶样品中的重金属离子可在1h之内完成。
(4)便携且易现场检测:利用纸基SERS传感器以及便携式拉曼光谱仪检测牛奶样品中的重金属离子可以解决检测场地问题,可以做到现场检测。
附图说明
图1为表面增强拉曼检测基底制备及检测流程示意图。
图2为SERS纸芯片修饰银纳米颗粒的SEM图,小图为局部放大图。合成的银纳米颗粒平均直径为60nm。
图3为未经修饰的纸芯片(左)与经过纳米银颗粒修饰的纸芯片(右)置于载玻片的照片。
图4为10-3mol/L、10-4mol/L、10-5mol/L、10-6mol/L的铅离子溶液为样本检测得到的拉曼光谱。
图5为铅离子浓度与1505.42cm-1处拉曼峰强度的线性关系图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的技术方案进行清楚地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
制备纸基SERS传感器
调节水平摇床的震荡速度为120往复/分钟,室温下在两块六孔板中分别加入3mL0.05M硼氢化钠溶液、3mL水、3mL 0.05M硝酸银溶液和3mL 0.05M抗坏血酸溶液、3mL水、3mL0.05M硝酸银溶液,将玻碳纤维纸分别浸入各孔30s,循环8次,玻碳纤维纸由白色变为暗灰色,即在纸上沉淀了银纳米颗粒,SEM图如图2所示。
将10μL的15μmol/L的巯基修饰的核酸适配体溶液与1μL的1mol/L的TCEP混合,室温下还原30min,得到还原态的巯基修饰的核酸适配体溶液。其中核酸适配体的具体序列为:5′-ROX-CAACGGTTGGTGTGGTTGG-SH-3′。
将4-巯基吡啶信号增强的SERS纸基底浸泡在还原后的巯基修饰的核酸适配体溶液中,静置24h,得到纸基SERS传感器,如图3所示。
实施例2
检测牛奶样品中的Pb2+
配置10-6-10-3M的Pb2+标准品溶液,将制备好的SERS纸基底浸入溶液中20min,取出该基底,置入订制的塑料模具中心,用便携式拉曼光谱仪检测1500-1600cm-1处的拉曼信号强度,如图4所示。根据拉曼信号强度与溶液中Pb2+标准品的浓度建立标准曲线,如图5所示。
检测Pb2+所得的拉曼信号与10-6-10-3mol/L浓度之间呈线性关系,线性方程为拉曼强度(a.u.)=-359.32lg CPb(II)+2586.3。
将购买的牛奶置于10-6的Pb2+标准溶液中,加入10mL三氯乙酸和60mM EDTA,并在涡旋振荡器上振荡20分钟;将混合溶液以20000g离心40分钟。收集上清液并通过0.22μm膜过滤。将制备好的SERS纸基底浸入溶液中20min,取出该基底,置入订制的塑料模具中心,用便携式拉曼光谱仪检测1500-1600cm-1处的拉曼信号强度。带入标准曲线计算,即可得到用加标回收法测得的牛奶样品中残留的Pb2+含量。
Claims (6)
1.一种表面增强拉曼光谱检测传感器的制备方法,其特征在于,具体步骤为:
(一)表面增强拉曼光谱检测玻碳纤维纸基底的制备;
以玻碳纤维纸为底板,采用“二次还原法”,室温下,在玻碳纤维纸上分步用硼氢化钠和抗坏血酸还原硝酸银,使银纳米颗粒沉积在玻碳纤维纸表面,形成表面增强拉曼光谱检测纸基底,简称为SERS纸基底;
(二)表面增强拉曼光谱检测玻碳纤维纸基底的修饰;
使用还原剂TCEP将巯基修饰的重金属离子的核酸适配体DNA进行还原,将前述SERS纸基底浸泡在还原后的巯基修饰的核酸适配体DNA溶液中反应一段时间,形成修饰后的SERS纸基底,该SERS纸基底对相应的重金属离子具有识别和传感功能,记为纸基SERS传感器。
2.根据权利要求1所述的制备方法,其特征在于,步骤(一)的具体操作流程为:
调节水平摇床的震荡速度,室温下,在两块六孔板中分别加入1~5mL 0.05M硼氢化钠溶液、1~5mL水、1~5mL 0.05M硝酸银溶液,以及1~5mL 0.05M抗坏血酸溶液、1~5mL水、1~5mL0.05M硝酸银溶液;将玻碳纤维纸分别浸入各孔中,反应30-60秒,循环8-12次,玻碳纤维纸由白色变为暗灰色,即表明在玻碳纤维纸上沉积上了银纳米颗粒,得到表面增强拉曼光谱检测玻碳纤维纸基底。
3.根据权利要求2所述的制备方法,其特征在于,步骤(二)的具体操作流程为:
(1)将上述得到的SERS纸基底与4-巯基吡啶溶液作用5-15min,得到明显增强的4-巯基吡啶信号,重复5次相同实验,至彼此之间的信号差距小于10%;
(2)将5-50μL的5-100μmol/L的巯基修饰的核酸适配体溶液与0.1-10μL的0.1-10mol/L的TCEP混合,室温下还原15-120min,得到还原态的巯基修饰的核酸适配体溶液;
(3)将4-巯基吡啶信号增强的SERS纸基底浸泡在还原后的巯基修饰的核酸适配体溶液中,静置2-24h,得到修饰后的表面增强拉曼检测传感器,简称为纸基SERS传感器。
4.由权利要求1-3之一所述制备方法得到的表面增强拉曼光谱检测传感器。
5.如权利要求4所述的表面增强拉曼光谱检测传感器在检测牛奶样品中重金属的含量中的应用,具体步骤为:
(1)建立标重金属离子浓度标准曲线
配置10-6-10-3M的重金属离子溶液,将纸基SERS传感器浸入溶液中10-20min,取出该纸基SERS传感器,置入定制的塑料模具中心,用便携式拉曼光谱仪检测纸基SERS传感器的拉曼信号,根据1500-1600cm-1处的拉曼信号强度与溶液中重金属离子浓度建立标准曲线;
(2)检测牛奶样品的重金属离子含量
将牛奶样品置于10-3mol/L、10-4mol/L、10-5mol/L、10-6mol/L的重金属离子标准品溶液中;加入1~10mL三氯乙酸和10~60mM EDTA,并在涡旋振荡器上振荡2~20分钟;将混合溶液以5000~20000g离心10~40分钟;收集上清液并通过0.22μm膜过滤;将纸基SERS传感器浸入上述所得的上清液中,10~40分钟,取出该纸基SERS传感器,在拉曼光谱仪上检测拉曼信号,通过1500-1600cm-1处的拉曼信号强度的拉曼信号强度,代入标准曲线计算,即得到样品中残留的重金属离子含量。
6.根据权利要求5所述的应用,其特征在于,重金属离子Pb2+的浓度标准曲线为直线,其方程为:拉曼强度(a.u.)=-359.32lg CPb(II)+2586.3,浓度为10-6-10-3mol/L浓度。
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