新型SERS基底的制备及其性能研究
摘要
自从1974年表面增强拉曼散射现象(SERS)发现以来,由于其克服了普通拉曼光谱所固有的信号弱、易受干扰等缺点,而且具有检测灵敏度高,能够直接给出分子结构信息等特点,从而得到了人们广泛的关注。目前,SERS技术在理论和实验方面都取得了极大的发展,但由于传统SERS基底(按相态分为“固态基底”,“悬浮态基底”)所存在的一些不可克服的缺点,从而限制了SERS技术在实际中的应用。因此,发展一种新的基底制备体系,并获得稳定、全面、高效、重现性好的SERS信号,已成为SERS研究领域所面临的一个现实的挑战。主要内容如下：
1.参考大量的文献,选取不同的合成方法,控制特定的反应条件,引入不同的表面活性剂,制备了多种具有不同表面化学性质、不同形貌和尺寸的纳米Au、Ag粒子,并利用紫外-可见光吸收光谱、透射电镜、扫描电镜等分析手段对纳米粒子的结构进行了表征。
2.引入处理过的氧化石墨烯(GO)为“悬浮态”的承载平台,考查其对所得纳米粒子的负载能力,并得到了能在水中稳定悬浮的团聚体/GO复合基底。通过改变团聚条件,可以实现对团聚体尺寸、负载密度等因素的控制。
3.选取球形银、立方银、无包覆剂银等不同类型纳米粒子作为SERS活性基底,以四巯基吡啶(4-Mpy)为探针分子,考查上述不同种类复合型基底的SERS特征。选取1600cm-1附近的振动,对比计算得出它们的SERS增强因子约为105左右,并讨论了其增强机制。
4.将低浓度的牛血清蛋白(BSA)吸附到无包覆剂银所得的清洁基底上,得到了较好的SERS信号,而且在4℃下信号能够长时间稳定存在。利用这种基底对生物大分子的分析检测具有很大的发展前景。
Since the first discovery of surface-enhanced Raman scattering (SERS) on electrochemically roughened Ag electrode in 1974, it has been attracting our great attention for its enormous potential application. Previously Raman Scattering (RS) is limited by its inherent weakness, since only a small amount of light is inelastic scattered. In contrast, SERS is provided with greatly increased signal by orders of magnitude in the presence of nano-structured surfaces. At presnt, we have made great progress in SERS detection of many probe molecules with common substrate ("solid substrates" and "liquid substrates"), but there is still some imperfection, which limits practical use. It becomes urgent to develop a bran-new substrate system to gain stable, comprehensive, efficient, high-sensitive, repeatable SERS signal. The main conclusions are listed as follows.
1. Firstly, we looked up abundant articles and made use of these methods. By controlling reaction factor and surfactant added, we synthesized various Au and Ag nanoparticles with different surface property, size and shape. UV-Vis absorption spectrophotometry and transmission eleetron microscopy (TEM) are mainly used to check the stability, size and shape of the colloidal sol.
2. We introduced treated Graphene Oxide sheets (GO) with special size as suspended micro-platform to study the loading capacity to different nanoparticles. Then such aggregates/GO multiple substrates could suspend well in liquid phase. Moreover, it's feasible to regulate the size of aggregates and loading density by varying aggregating factor.
3. Three kinds of different silver colloidal sol are prepared to aggregate on such platform to obtain substrates. And 4-Mpy was selected as probe molecule to test SERS spectra on these substrates. In SERS spectra, some change in intensity and shift in frequency can be observed compared to normal Raman spectrum due to interaction between molecules and SERS substrates. The representative band at approximate 1600 cm-1(C=C stretching) is selected to calculate the enhancement factor values, and they are around 105.
4. We also tested enhancement capacity to Bovine Serum Albumin (BSA) by such substrates. Upon simple mixture of BSA and substrates, apparent SERS signals were immediately obtained. Above all, the mixture could keep stable at 4℃for long, and SERS signals barely changed. It showed the potential of this aggregate system as a convenient and powerful SERS-active substrate for biological detection.
1.参考大量的文献,选取不同的合成方法,控制特定的反应条件,引入不同的表面活性剂,制备了多种具有不同表面化学性质、不同形貌和尺寸的纳米Au、Ag粒子,并利用紫外-可见光吸收光谱、透射电镜、扫描电镜等分析手段对纳米粒子的结构进行了表征。
2.引入处理过的氧化石墨烯(GO)为“悬浮态”的承载平台,考查其对所得纳米粒子的负载能力,并得到了能在水中稳定悬浮的团聚体/GO复合基底。通过改变团聚条件,可以实现对团聚体尺寸、负载密度等因素的控制。
3.选取球形银、立方银、无包覆剂银等不同类型纳米粒子作为SERS活性基底,以四巯基吡啶(4-Mpy)为探针分子,考查上述不同种类复合型基底的SERS特征。选取1600cm-1附近的振动,对比计算得出它们的SERS增强因子约为105左右,并讨论了其增强机制。
4.将低浓度的牛血清蛋白(BSA)吸附到无包覆剂银所得的清洁基底上,得到了较好的SERS信号,而且在4℃下信号能够长时间稳定存在。利用这种基底对生物大分子的分析检测具有很大的发展前景。
Since the first discovery of surface-enhanced Raman scattering (SERS) on electrochemically roughened Ag electrode in 1974, it has been attracting our great attention for its enormous potential application. Previously Raman Scattering (RS) is limited by its inherent weakness, since only a small amount of light is inelastic scattered. In contrast, SERS is provided with greatly increased signal by orders of magnitude in the presence of nano-structured surfaces. At presnt, we have made great progress in SERS detection of many probe molecules with common substrate ("solid substrates" and "liquid substrates"), but there is still some imperfection, which limits practical use. It becomes urgent to develop a bran-new substrate system to gain stable, comprehensive, efficient, high-sensitive, repeatable SERS signal. The main conclusions are listed as follows.
1. Firstly, we looked up abundant articles and made use of these methods. By controlling reaction factor and surfactant added, we synthesized various Au and Ag nanoparticles with different surface property, size and shape. UV-Vis absorption spectrophotometry and transmission eleetron microscopy (TEM) are mainly used to check the stability, size and shape of the colloidal sol.
2. We introduced treated Graphene Oxide sheets (GO) with special size as suspended micro-platform to study the loading capacity to different nanoparticles. Then such aggregates/GO multiple substrates could suspend well in liquid phase. Moreover, it's feasible to regulate the size of aggregates and loading density by varying aggregating factor.
3. Three kinds of different silver colloidal sol are prepared to aggregate on such platform to obtain substrates. And 4-Mpy was selected as probe molecule to test SERS spectra on these substrates. In SERS spectra, some change in intensity and shift in frequency can be observed compared to normal Raman spectrum due to interaction between molecules and SERS substrates. The representative band at approximate 1600 cm-1(C=C stretching) is selected to calculate the enhancement factor values, and they are around 105.
4. We also tested enhancement capacity to Bovine Serum Albumin (BSA) by such substrates. Upon simple mixture of BSA and substrates, apparent SERS signals were immediately obtained. Above all, the mixture could keep stable at 4℃for long, and SERS signals barely changed. It showed the potential of this aggregate system as a convenient and powerful SERS-active substrate for biological detection.
引文
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[9]Hyunhyub Ko, Srikanth Singamaneni, Vladimir V. Tsukruk. Nanostructured Surfaces and Assemblies as SERS Media [J]. small,2008,4 (10):1576-1599.
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