金银核壳纳米结构的制备及其局域表面等离子体共振传感研究
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摘要
贵金属纳米粒子拥有较强的局域表面等离子体共振(LSPR)特性,且其LSPR特性与贵金属纳米粒子的组成、形貌和尺寸密切相关。贵金属纳米粒子的LSPR吸收峰对周围介质折射率的变化非常敏感,利用此特点可以制备LSPR生物传感器。LSPR传感器具有便宜、多功能性、高灵敏度等优点。
本论文研究了一种直接在ITO导电玻璃上电沉积Au@Ag(核@壳)纳米粒子的方法。首先通过调节沉积电位、镀液浓度及沉积圈数制备了约80nm直径的Au@Ag纳米粒子,并用紫外-可见光度法、扫描电镜、循环伏安法对其进行了表征。研究了Au@Ag纳米粒子周围介质折射率对其表面等离子体共振吸收的影响,实验得出灵敏度为127nm/RIU,比原来的金纳米粒子的灵敏度提高了76%。
另一方面,通过控制沉积电位,硝酸银及氯金酸的浓度,沉积圈数制备了小粒径(60nm)和大粒径(100nm)的Ag@Au纳米粒子,并用紫外-可见光度法、扫描电镜、循环伏安法、X射线能谱分析对其进行了表征。研究了两种粒径Ag@Au纳米粒子周围介质折射率对其表面等离子体共振吸收的影响,60nm Ag@Au纳米粒子的灵敏度为143nm/RIU,100nm的Ag@Au纳米粒子的灵敏度为220nm/RIU,且Ag@Au纳米粒子传感膜的灵敏度与原来的银纳米粒子传感膜的灵敏度相比,增加了近80%。此外还研究了长链巯基及蛋白质分子在Ag@Au纳米粒子表面的吸附行为,及利用Streptavidin-Biotin的特异性结合来验证Ag@Au的LSPR传感特性。
第三,本论文采用循环伏安法在ITO玻璃上制备了簇状银纳米粒子。并用紫外-可见光度法、扫描电镜对其进行了表征。研究了周围介质折射率对其局域表面等离子体共振吸收的影响,灵敏度可达148nm/RIU。在簇状银纳米上再沉积一层薄的金壳后,其LSPR响应灵敏度达到了316nm/RIU,提高了1.1倍。实验证明,纳米粒子的LSPR性质与其形貌密切相关,可控簇状Ag@Au纳米粒子比球状Ag@Au纳米粒子具有更高的灵敏度。
Noble metal nanoparticles exhibit rich localized surface plasmon resonance properties, which is highly dependent on the composition, shape and size of metal nanoparticles. The dependence of their LSPR wavelengths on the surrounding refractive index is highly sensitive, which is extremely useful to prepare LSPR sensors. This kind of LSPR sensors is cheap, versatile, and yet sensitive.
In this paper, we develop a simple and reproducible method to directly deposit Au core-Ag shell nanoparticles on ITO surface without any organic binder. Au@Ag nanoparticles at an average diameter of 80 nm were prepared by controlling deposition potential, deposition circles and the concentration of HAuCl4 and AgNO3. The Au@Ag nanoparticles on ITO substrate were characterized by means of UV-vis spectroscopy, scanning electron microscopy (SEM) and cyclic voltammetry (CV).The Au@Ag/ITO glasses were applied to development of refractive index sensors for variety of organic solvents. The sensitivity of 80 nm Au@Ag nanoparticles was 127 nm/RIU, which was about 76% higher than that of original gold nanoparticles.
On the other hand, we deposited two different sizes of Ag@Au nanoparticles(60 and 100nm) onto ITO surface by regulating deposition potential, deposition circles and concentration of HAuCl4 and AgNO3. The Ag@Au nanoparticles on ITO substrate were characterized by means of UV-vis spectroscopy, SEM, CV and energy dispersive X-ray spectroscopy (EDS). Two different sizes of Ag@Au nanoparticles on ITO glass were used to investigate the response of different organic solvents. The sensitivities of Ag@Au nanoparticles at an average diameter of 60 and 100nm were 143 and 220nm/RIU, respectively. They were almost 80% higher than that of original silver nanoparticles. Then the analytical performances of sensor chips for monitoring both thiol and protein adsorption were examined. We chose the biotin-streptavidin system to validate the LSPR properties.
Thirdly, we electrochemical deposited silver nanoclusters onto ITO glass surface. The silver nanoclusters on ITO substrate were characterized by means of UV-vis spectroscopy and SEM. We also investigated the optical properties of silver nanoclusters, such as the response of refractive index of various organic solvents, and a sensitivity of 148nm/RIU is obtained. After we deposited one layer of gold onto the silver nanoclusters, the sensitivity reached to 316nm/RIU. By systematically comparing the sensor activities of Ag nanoclusters and Ag@Au nanoclusters, we found that Ag@Au nanoclusters have higher sensitivity.
本论文研究了一种直接在ITO导电玻璃上电沉积Au@Ag(核@壳)纳米粒子的方法。首先通过调节沉积电位、镀液浓度及沉积圈数制备了约80nm直径的Au@Ag纳米粒子,并用紫外-可见光度法、扫描电镜、循环伏安法对其进行了表征。研究了Au@Ag纳米粒子周围介质折射率对其表面等离子体共振吸收的影响,实验得出灵敏度为127nm/RIU,比原来的金纳米粒子的灵敏度提高了76%。
另一方面,通过控制沉积电位,硝酸银及氯金酸的浓度,沉积圈数制备了小粒径(60nm)和大粒径(100nm)的Ag@Au纳米粒子,并用紫外-可见光度法、扫描电镜、循环伏安法、X射线能谱分析对其进行了表征。研究了两种粒径Ag@Au纳米粒子周围介质折射率对其表面等离子体共振吸收的影响,60nm Ag@Au纳米粒子的灵敏度为143nm/RIU,100nm的Ag@Au纳米粒子的灵敏度为220nm/RIU,且Ag@Au纳米粒子传感膜的灵敏度与原来的银纳米粒子传感膜的灵敏度相比,增加了近80%。此外还研究了长链巯基及蛋白质分子在Ag@Au纳米粒子表面的吸附行为,及利用Streptavidin-Biotin的特异性结合来验证Ag@Au的LSPR传感特性。
第三,本论文采用循环伏安法在ITO玻璃上制备了簇状银纳米粒子。并用紫外-可见光度法、扫描电镜对其进行了表征。研究了周围介质折射率对其局域表面等离子体共振吸收的影响,灵敏度可达148nm/RIU。在簇状银纳米上再沉积一层薄的金壳后,其LSPR响应灵敏度达到了316nm/RIU,提高了1.1倍。实验证明,纳米粒子的LSPR性质与其形貌密切相关,可控簇状Ag@Au纳米粒子比球状Ag@Au纳米粒子具有更高的灵敏度。
Noble metal nanoparticles exhibit rich localized surface plasmon resonance properties, which is highly dependent on the composition, shape and size of metal nanoparticles. The dependence of their LSPR wavelengths on the surrounding refractive index is highly sensitive, which is extremely useful to prepare LSPR sensors. This kind of LSPR sensors is cheap, versatile, and yet sensitive.
In this paper, we develop a simple and reproducible method to directly deposit Au core-Ag shell nanoparticles on ITO surface without any organic binder. Au@Ag nanoparticles at an average diameter of 80 nm were prepared by controlling deposition potential, deposition circles and the concentration of HAuCl4 and AgNO3. The Au@Ag nanoparticles on ITO substrate were characterized by means of UV-vis spectroscopy, scanning electron microscopy (SEM) and cyclic voltammetry (CV).The Au@Ag/ITO glasses were applied to development of refractive index sensors for variety of organic solvents. The sensitivity of 80 nm Au@Ag nanoparticles was 127 nm/RIU, which was about 76% higher than that of original gold nanoparticles.
On the other hand, we deposited two different sizes of Ag@Au nanoparticles(60 and 100nm) onto ITO surface by regulating deposition potential, deposition circles and concentration of HAuCl4 and AgNO3. The Ag@Au nanoparticles on ITO substrate were characterized by means of UV-vis spectroscopy, SEM, CV and energy dispersive X-ray spectroscopy (EDS). Two different sizes of Ag@Au nanoparticles on ITO glass were used to investigate the response of different organic solvents. The sensitivities of Ag@Au nanoparticles at an average diameter of 60 and 100nm were 143 and 220nm/RIU, respectively. They were almost 80% higher than that of original silver nanoparticles. Then the analytical performances of sensor chips for monitoring both thiol and protein adsorption were examined. We chose the biotin-streptavidin system to validate the LSPR properties.
Thirdly, we electrochemical deposited silver nanoclusters onto ITO glass surface. The silver nanoclusters on ITO substrate were characterized by means of UV-vis spectroscopy and SEM. We also investigated the optical properties of silver nanoclusters, such as the response of refractive index of various organic solvents, and a sensitivity of 148nm/RIU is obtained. After we deposited one layer of gold onto the silver nanoclusters, the sensitivity reached to 316nm/RIU. By systematically comparing the sensor activities of Ag nanoclusters and Ag@Au nanoclusters, we found that Ag@Au nanoclusters have higher sensitivity.
引文
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