CN103454261A - 一种利用拉曼光谱定量测定纳米微粒的方法 - Google Patents
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Abstract
本发明公开了一种利用拉曼光谱定量测定纳米微粒的方法。首先在水相中制备Ag2S胶体溶液，并在常温和冰冻条件下保存待用；其次，将Ag2S胶体溶液稀释到合适浓度并分别加入含有银胶、NaCl、罗丹明6G的基底中，配成不同浓度的溶液；最后将配置好的溶液以未加Ag2S样品的溶液为空白样，应用DXRsmart拉曼光谱仪，进行采样，收集样品峰，观察1508cm-1处的样品特征峰随浓度不同的变化。计算收集到样品峰强度与空白样品相对应的峰强度，然后用相对峰强度对浓度作图。本发明方法简便，灵敏度高，丰富了纳米颗粒的测定方法。
Description
技术领域
本发明涉及一种利用拉曼光谱测定纳米微粒含量的方法。
背景技术
无机半导体纳米晶体，通常被称为胶体量子点。量子点以其具有不同于宏观材料的独特物理化学性能，引起了国内外研究者广泛的兴趣。目前，随着量子点不断地深入研究，基于量子点荧光增强或淬灭的原理应用于重金属阳离子、有机小分子和药物分子的检测等屡见报道。与利用金属阳离子对量子点的荧光猝灭来测定阳离子浓度的不同，本发明是基于表面增强拉曼散射（SERS）的活性表面荧光增强或淬灭的机制：荧光物质罗丹明6G（Rh6G）分子吸附在银胶表面并在波长1508cm-1处产生一个较强的SERS散射峰，当加入Ag2S量子点时，体系中SERS峰相对强度发生减弱，并随着Ag2S加入量的增加在一定范围内成线性减小的趋势，根据这一现象从而建立了一种拉曼光谱技术测量Ag2S量子点浓度的新方法。
发明内容
本发明的目的是提供一种利用拉曼光谱技术定量测定纳米粒子浓度的方法。
具体步骤为：
（1）在水相体系中，用0.016-0.25g L-半胱氨酸修饰0.10-0.80mmolAgNO3，并用NaOH调节pH=9-12，再加入0.05-0.20mmolNa2S，最终获得棕红色的Ag2S胶体量子点，将Ag2S胶体量子点常温或冰冻保存。
（2）取步骤（1）所得Ag2S胶体量子点用二次蒸馏水稀释后得到0.3090×103ppb浓度的Ag2S胶体量子点溶液；以500uL浓度为19.9×103ppb银胶、100uL浓度为1mol/L的NaCl溶液和100uL浓度为5.23×10-5mol/L的罗丹明6G（Rh6G）溶液为基底，取一组容量瓶，用移液枪分别准确量取基底溶液于容量管中，再分别加入0-170uL稀释后的Ag2S胶体量子点溶液，定容到2mL，从而配成0-26.27ppb不同浓度的溶液。
（3）将步骤（2）配置好的溶液以未加Ag2S胶体量子点的溶液为空白样，应用DXR smart拉曼光谱仪，进行采样，收集样品峰，观察1508cm-1处的样品特征峰随浓度不同的变化；计算收集到样品峰强度与空白样品相对应的峰强度，然后用相对峰强度对浓度作图。
（4）在常温下或冰冻保存下，分别在2.01-5.10ppb 及1.64-10.91ppb范围内，表面增强拉曼散射（SERS）峰相对强度与Ag2S胶体溶液的浓度均呈线性关系，其中，常温下的相关系数为-0.9510，检测限为2.01ppb，而冰冻保存的相关系数为-0.9926，检测限为1.64ppb。
本发明方法简便，灵敏度高，丰富了纳米颗粒的测定方法。
附图说明
图1为本发明Ag2S胶体量子点合成装置示意图。
图2为本发明Ag2S胶体量子点的紫外可见吸收光谱图（a）和荧光光谱图（b）。
图3为本发明Ag2S胶体量子点常温和冰冻处理后的荧光光谱图。
图4为本发明含不同浓度Ag2S胶体量子点的基底溶液体系的拉曼光谱图；图中：a -0ppb；b -2.41ppb ；c -3.96ppb ；d -5.50ppb 。
图5为本发明实施例1中SERS峰相对强度与Ag2S胶体量子点浓度的线性关系图。
具体实施方法
实施例1：
（1）将0.1g的L-半胱氨酸（L-Cysteine，L-Cys）粒状固体置于圆底烧瓶中，加入100mL去离子水，常温下搅拌溶解，加入0.25mmol的AgNO3，并用NaOH调节pH=11，再加入0.10mmolNa2S，最终获得棕红色的Ag2S胶体量子点，放置冰箱中保存待用。
（2）取步骤（1）所得溶液用二次蒸馏水稀释后得到浓度为0.3090×103ppb的Ag2S胶体量子点溶液；以500uL浓度为19.9×103ppb银胶、100uL浓度为1mol/L的NaCl溶液和100uL浓度为5.23×10-5mol/L的Rh6G溶液为基底，取12个容量瓶，用移液枪分别准确量取基底溶液于容量管中，再分别加入浓度为0.3090×103ppb的Ag2S胶体量子点溶液0 uL、5.6 uL、10.6 uL、15.6 uL、20.6 uL、25.6 uL、30.6 uL、35.6 uL、50.6 uL、60.6 uL、70.6uL和80.6 uL定容到2mL，从而配成浓度为0-12.45ppb的Ag2S胶体量子点溶液体系。
（3）将步骤（2）配置的浓度为0-12.45ppb的溶液并以未加Ag2S胶体量子点的溶液为空白样，应用DXR smart拉曼光谱仪，进行采样，收集样品峰，观察1508cm-1处的样品特征峰随浓度不同的变化。计算收集到样品的峰强度与空白样品相对应的峰强度，然后用相对峰强度对浓度作图。
（4）以不同浓度的Ag2S的拉曼谱图的相对峰高对浓度作图，发现在浓度为1.64-10.91ppb范围内，Ag2S胶体量子点的谱图的相对峰高对浓度均呈线性关系，相关系数R为-0.9926，最低检测限为1.64ppb。
实施例2：
（1）同实施例1中制备Ag2S胶体量子点，常温下保存待用。
（2）取步骤（1）所得溶液用二次蒸馏水稀释后得到浓度为0.3090×103ppb的Ag2S胶体量子点溶液；以500uL浓度为19.9×103ppb银胶、100uL浓度为1mol/L的NaCl溶液和100uL浓度为5.23×10-5mol/L的Rh6G溶液为基底，取10个容量瓶，用移液枪分别准确量取基底溶液于容量管中，再分别加入浓度为0.3090×103ppb的Ag2S胶体量子点溶液0uL、1uL、2uL、3uL 、8uL、13uL、18uL、23uL、28uL、33uL，定容到2mL，从而配成浓度为0-5.10ppb的Ag2S胶体量子点溶液体系。
（3）同实施例1步骤（3）。
（4）以溶液体系中不同浓度的Ag2S胶体量子点的拉曼谱图的相对峰高对浓度作图，发现在浓度为2.01-5.10ppb范围内，Ag2S的谱图的相对峰高对浓度均呈线性关系，相关系数R为-0.9510，最低检测限为2.01ppb。
Claims (2)
1.一种利用拉曼光谱定量测定纳米微粒的方法，其特征在于具体步骤为：
（1）在水相体系中，用0.016-0.25g L-半胱氨酸修饰0.10-0.80mmolAgNO3，并用NaOH调节pH=9-12，再加入0.05-0.20mmolNa2S，最终获得棕红色的Ag2S胶体量子点，将Ag2S胶体量子点常温或冰冻保存；
（2）取步骤（1）所得Ag2S胶体量子点用二次蒸馏水稀释后得到0.3090×103ppb浓度的Ag2S胶体量子点溶液；以500uL浓度为19.9×103ppb的银胶、100uL浓度为1mol/L的NaCl溶液和100uL浓度为5.23×10-5mol/L的罗丹明6G即Rh6G溶液为基底，取一组容量瓶，用移液枪分别准确量取基底溶液于容量管中，再分别加入0-170uL稀释后的Ag2S胶体量子点溶液，定容到2mL，从而配成0-26.27ppb不同浓度的Ag2S胶体量子点溶液；
（3）将步骤（2）配置好的溶液以未加Ag2S胶体量子点的溶液为空白样，应用DXR smart拉曼光谱仪，进行采样，收集样品峰，观察1508cm-1处的样品特征峰随浓度不同的变化；计算收集到样品峰强度与空白样品相对应的峰强度，然后用相对峰强度对浓度作图。
2.根据权利要求1所述的方法，其特征在于（4）在常温下或冰冻保存下，分别在2.01-5.10ppb 及1.64-10.91ppb范围内，表面增强拉曼散射即SERS峰相对强度与Ag2S胶体溶液的浓度均呈线性关系，其中，常温下的相关系数为-0.9510，检测限为2.01ppb，而冰冻保存的相关系数为-0.9926，检测限为1.64ppb。
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Application publication date: 20131218 Assignee: GUANGXI KE SUI ENVIRONMENTAL TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980045094 Denomination of invention: A Method for Quantitative Determination of Nanoparticles Using Raman Spectroscopy Granted publication date: 20150923 License type: Common License Record date: 20231101 Application publication date: 20131218 Assignee: Guilin Qianzhuo Environmental Testing Technology Service Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980045092 Denomination of invention: A Method for Quantitative Determination of Nanoparticles Using Raman Spectroscopy Granted publication date: 20150923 License type: Common License Record date: 20231101 |
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