金纳米棒状微粒的胶囊模型及吸收光谱

提出了金纳米棒状微粒的胶囊模型,用Waterman发展的T矩阵方法计算了金纳米棒状微粒的吸收光谱.计算谱和实验谱基本符合,520 nm左右处的吸收峰对应于金纳米棒的横向表面等离体子共振（横模）,长波长处的吸收峰对应于金纳米棒的纵向表面等离体子共振（纵模）.随着金纳米棒纵横比的增加,纵模吸收峰表现出显著的红移,横模吸收峰则微弱地蓝移.此外,计算结果表明,金纳米棒状微粒外部介质的介电常数必须随着金纳米棒纵横比的增大非线性地减小.     

金纳米粒子的电化学合成及光谱表征

采用电化学方法合成各种形状的金纳米粒子,生成的金纳米粒子形貌与施加电流有关,通过匀速递增电流电解的方法,可制备得到哑铃形,球形以及棒状金纳米粒子,采用恒电流电解方法主要获得球形及哑铃形纳米粒子。利用透射电镜、紫外-可见光谱及拉曼光谱对金纳米粒子进行相关表征。紫外-可见光谱研究发现金纳米棒出现位于近红外区间的吸收峰(985 nm),由此推测棒的长径比约为6。以结晶紫为探针分子,研究了金纳米粒子的表面增强拉曼光谱(SERS)效应,并分析得出其平躺的吸附模式。根据形貌表征的结果推断了纳米粒子的生长机理。     

金膜表面等离激元诱导邻巯基苯甲酸脱羧反应的表面增强拉曼光谱研究

贵金属纳米结构表面等离激元共振（SPR）因其广泛的用途而备受关注,它不仅可以催化某些特殊的表面反应,同时还能产生表面增强拉曼散射效应（SERS）,极大增强分子的表面拉曼信号,因此两者结合后可在纳米结构表面采用SERS光谱跟踪SPR催化反应。目前此类研究主要集中在氮氮（N═N）偶联,因此亟待拓展SPR反应种类及提高催化活性和效率。采用SERS光谱研究邻巯基苯甲酸（OMBA）分子在金纳米粒子单层膜（Au MLF）表面的脱羧行为。通过气液界面组装法制备“热点”分布均匀的金纳米粒子单层膜,以此作为基底,探讨了溶液pH值、激光功率及激光照射时长对该基底表面脱羧反应的影响。研究结果表明,吸附在Au MLF表面的OMBA分子在表面等离激元驱动下碱性和中性介质中发生脱羧基反应,生成苯硫酚（TP）,且碱性中反应活性大于中性溶液。在酸性介质中几乎不发生脱羧反应。较强的激光功率,脱羧反应的活性越高;产物SERS强度的增加与激光照射时间成线性关系,时间延长可提高脱羧反应的产率。这为拓展SPR驱动的光催化反应及深入理解其反应机理提供了实验依据。     

金纳米粒子的图案化组装及表面增强拉曼光谱研究

利用聚苯乙烯纳米粒子有序组装结构为模板,进行了金纳米粒子的图案化组装。金纳米粒子在聚苯乙烯纳米粒子底部自组装聚集,形成规则的“面包圈”结构。表面增强拉曼光谱表明,相对于随机分布的金纳米粒子而言,金纳米粒子组装结构具有聚焦电磁场作用,从而使吸附的对巯基苯甲酸的拉曼散射得以进一步增强。     

苯硫酚吸附在新型Ag-Au合金纳米粒子上的表面增强拉曼光谱研究

以柠檬酸钠同时还原制备的Ag-Au合金纳米粒子为种子,用盐酸羟胺进一步使其生长得到粒径为40～60 nm的新型Ag-Au合金纳米粒子,采用UV-Vis光谱和TEM对纳米种子和再生长后的纳米粒子分别进行表征。两种粒子的UV-Vis光谱均只观察到一个等离子体共振峰,其频率随金的摩尔分数(x_Au)增加而红移,且TEM图像表明这两种粒子的颜色均一,因此判断这两种粒子均为合金结构。以苯硫酚为探针分子,研究了该新型合金纳米粒子的表面增强拉曼光谱(SERS),结果表明吸附了苯硫酚的合金纳米粒子的紫外最大吸收峰红移,并在近红外区出现聚集体的吸收峰。在632.8 nm波长激发下,由于表面等离子体共振效应Au上的SERS信号最强,而合金纳米粒子上的SERS信号随x_Au增大而增强。     

海胆状金纳米粒子表面形貌对表面增强喇曼散射特性的影响

采用改进的一步还原法合成了多种海胆状金纳米粒子,并对它们的表面增强喇曼散射特性与其表面形貌的关系进行了实验研究.实验表明,合成的海胆状金纳米粒子的直径及表面的尖刺大小可以通过改变加入到氯金酸溶液中的硝酸银的量来调节.当加入到氯金酸溶液中的硝酸银为1μL时,合成的海胆状金纳米粒子的直径最小而尖刺最长.同时测量的紫外-可见-近红外吸收光谱表明,海胆状金纳米粒子的局域表面等离子体共振带会随着加入到氯金酸溶液中的硝酸银量的增加而变宽.此外,通过喇曼标记分子对巯基苯甲酸(4MBA)的喇曼光谱测量发现,较小直径和较长尖刺的海胆状金纳米粒子具有更强的表面增强喇曼散射活性.     

不同粒径、超均匀球形金纳米粒子合成及其表面增强拉曼散射效应研究

以氯金酸为原料,抗坏血酸为还原剂,柠檬酸钠为保护剂,用化学还原(种子生长)法制备了不同粒径、超均匀的球形金纳米粒子溶胶,并通过紫外可见吸收光谱(UV-Vis)和扫描电子显微镜(SEM)进行表征。结果表明,随着金纳米粒子粒径的增大,其UV-Vis光谱中的吸收峰发生红移并出现四极峰。为进一步研究金纳米粒子表面增强拉曼散射(SERS)效应的作用机理并优化其灵敏度,我们以罗丹明6G(R6G)为探针分子,对不同粒径的金纳米粒子进行SERS表征,发现R6G的SERS信号随着金纳米粒子的增大先增强后减弱。当金纳米粒子的平均粒径达到120 nm时,产生最强SERS信号增强,增强因子约为1.1×107。三维时域有限差分法(3D-FDTD)理论模拟纳米粒子阵列电磁场分布结果与实验数据的趋势一致。     

纳米金表面修饰与表面等离子体共振传感器的相互作用研究

为了分析纳米金表面修饰对表面等离子体共振(SPR)的放大作用,以及其对传感器本身的影响,首先,基于色散介质的吸收理论,通过建立波长型SPR生物传感器四层膜结构的数学模型,理论分析了传感器表面所吸附纳米金对传感器的影响:纳米金的表面修饰,改变了表面等离子体传感器中棱镜表面各介质层内电磁场的能量分布,削弱了金属膜在共振吸收中的作用,从而使SPR曲线的半波宽度增加,最小反射系数增大,金膜的最优膜厚度也随之改变.其次,通过不同厚度的金膜外吸附纳米金的对比试验,验证了此理论.金膜厚45nm、表面修饰10nm纳米金颗 关键词： 表面等离子体共振 生物传感器 纳米金 金属膜     

金纳米环双体尺寸和耦合效应对表面等离子体共振特性的影响

采用离散偶极子近似方法系统地研究了金纳米环双体的消光光谱及其电场分布. 计算结果表明, 金纳米环双体在耦合作用下的共振消光峰对应着不同振动模式, 改变金纳米环双体的排列方式、 间距和尺寸大小, 其表面等离子体共振消光峰发生红移或蓝移. 因此可以通过对金纳米环双体结构参数和排列方式的设定, 调节其表面等离子体共振消光峰的位置. 电场分布表明, 水平排列的金纳米环双体较单个金纳米环产生更强的局部表面增强电场. 适当的小间距, 较大的内外半径的金纳米环水平阵列更适合做表面增强拉曼散射的衬底, 在生物分子检测等领域具有潜在的应用.     

表面增强拉曼光谱快速检测尿液中的尿酸

表面增强拉曼光谱是一种表面灵敏度极高的“指纹”光谱技术,检测限可达单分子级别。它可以实现痕量物质的特异性识别及快速、无损检测,广泛应用于生命科学、电化学、环境安全等领域以及人们的日常生活中。通过种子生长法成功地实现了形貌均匀、尺寸可调的球形金纳米粒子的制备,并以此作为增强基底进一步探索其粒径对尿酸拉曼谱峰强度的影响。结果表明,金纳米粒子的尺寸显著影响其拉曼增强能力。在研究范围内,随着金纳米粒子尺寸的增加,其拉曼增强能力逐渐增加。在激光波长为638 nm时,150 nm的金纳米粒子具有最优的拉曼增强能力。这使得它们可适用于尿酸溶液的快速高灵敏度分析,检测限可达0.01 mmol·L-1。进一步的研究还表明,该方法可用于痕量尿酸的定量检测。在0.01～0.5 mmol·L-1范围内,尿酸的浓度与其特征拉曼峰640 cm-1处的峰强度之间呈线性关系,线性相关系数达0.98。将该方法用于真实样品(正常人体尿液)的快速检测,发现该方法不受尿液中其他成分的干扰,可以实现人体尿液中尿酸含量的快速测定。研究结果表明,以金纳米粒子作为基底的表面增强拉曼光谱方法可方便、快速地对尿液中尿酸的含量进行分析,极大地拓展了表面增强拉曼光谱在临床上的应用与研究。     

Shape and size dependence of the surface plasmon resonance of gold nanoparticles studied by Photoacoustic technique

We report on the optical absorption properties of as prepared gold naoparticles of different shapes and sizes measured by photoacoustic (PA) method. The gold nanoparticles of two different shapes (dots, rods) have been prepared using the seed mediated growth method. The shape and the size of these different nanoparticles were determined by STM measurements. PA spectra show the splitting of the surface plasmon resonance (SPR) into two modes (transverse and longitudinal) in case of gold nanorods. The increase in the aspect ratio of the nanorods leads to clear redshifts of the longitudinal SPR. These shifts were used to determine the dielectric constant of the surrounding medium and its variation with the aspect ratios.     

Radius-dependent binding or repelling forces exerted on metal nano-sphere clusters by infrared-induced plasmonic resonance

The force exerted on metal nano-particles is investigated numerically when the particles are in contact to form a cluster and are illuminated by a light of their fundamental plasmonic resonance frequency. For touching spheres, the mode of resonance changes drastically from those of separate spheres, and the resonance typically appears in the infrared wavelength range. For silver and gold two-sphere clusters, i.e. homo-dimers, of various radii, the magnitudes and the directions of the exerted forces are analyzed. It is found that the field enhancement in the gap region between the spheres depends largely on the sphere radius, and the force on the fundamental resonance exhibits binding only for small spheres; the greatest binding force is observed for radii of 40–60 nm; and the force turns to repelling when the radius becomes greater than approximately 100–150 nm as the field in the gap region becomes weaker.     

Using gold colloid nanoparticles to modulate the surface enhanced fluorescence of Rhodamine B

Enhanced fluorescence from Rhodamine B (RB) mixed with gold colloids has been observed under ultraviolet irradiation. Spectroscopic studies show that with the increasing gold colloids content, the fluorescence of RB at about 590 nm increases firstly and then decreases with slight red shift. These features observed in the experiment can be explained by the local electric field enhancement via surface plasmon resonance (SPR) of gold nanoparticles. Fluorescence enhancement is obtained when the emission frequency of RB lies within the bandwidth of local field enhancement from gold nanoparticles. Theoretical calculation results show that the local field band red shifts obviously with increase the thickness of dye shell which capped on gold particle, whereas the fluorescence band of RB is fixed around 590 nm. Therefore, the red shift and non-monotonic change of fluorescence intensity from RB is attributed to the dye shell dependent red shift of local field band of gold particles.     

Bimetallic Silver–Gold Film Waveguide Surface Plasmon Resonance Sensor

Abstract

It is desirable that a surface plasmon resonance (SPR) sensor is highly sensitive to binding interactions within the sensing region, generate evanescent fields with long penetration depths, and utilize a metal film that is very stable even in extreme environmental conditions. In this study, we present the first example of a wavelength-modulated waveguide SPR sensor with a bimetallic silver–gold film for surface plasmon excitation. The underlying silver yields better evanescent field enhancement of the sensing surface, while the overlying gold ensures that the stability of the metallic film is not compromised. It is shown experimentally that in terms of dλ/dn, the bimetallic film waveguide SPR configuration has a sensitivity of 1232 nm/RIU, greater than two times improvement from the 594 nm/RIU achievable with single gold film waveguide SPR sensor. The higher sensitivity, compact nature, and better evanescent field enhancement of this configuration provides the potential to biosensing applications.     

Bimetallic Silver-Gold Film Waveguide Surface Plasmon Resonance Sensor

It is desirable that a surface plasmon resonance (SPR) sensor is highly sensitive to binding interactions within the sensing region, generate evanescent fields with long penetration depths, and utilize a metal film that is very stable even in extreme environmental conditions. In this study, we present the first example of a wavelength-modulated waveguide SPR sensor with a bimetallic silver-gold film for surface plasmon excitation. The underlying silver yields better evanescent field enhancement of the sensing surface, while the overlying gold ensures that the stability of the metallic film is not compromised. It is shown experimentally that in terms of dλ/dn, the bimetallic film waveguide SPR configuration has a sensitivity of 1232 nm/RIU, greater than two times improvement from the 594 nm/RIU achievable with single gold film waveguide SPR sensor. The higher sensitivity, compact nature, and better evanescent field enhancement of this configuration provides the potential to biosensing applications.     

Effect of dielectric coating on the sensing capability of gold nanorods based on plasmonic band widening

The dielectric coating-induced widening of the longitudinal surface plasmon resonance (SPR) band of gold nanorods was investigated theoretically. The line width of the longitudinal SPR could be enlarged by increasing the thickness or the dielectric constant of the coated dielectric shell. The corresponding physical origin has been illuminated by the dielectric coating-enhanced anisotropic distribution of the surface charge. This dielectric coating-dependent widening of the longitudinal SPR presents a new biologic sensing picture based on tuning the line width of the plasmonic absorption band of metallic nanostructure.     

纳米银组装结构的表面增强荧光效应

采用表面自组装技术,在玻片表面构筑银纳米粒子二维组装结构.银纳米粒子组装结构的吸收光谱表明银粒子表面等离子体共振与粒子间电磁偶合密切相关,偶极子表面等离子体共振更为敏感而发生较大位移.在银纳米粒子组装结构上,荧光素分子的荧光得到极大增强,其表面增强效应强烈依赖于组装金属粒子的表面等离子体共振.     

Enhanced surface plasmon resonance imaging detection of DNA hybridization on periodic gold nanoposts

We explore periodic gold nanoposts as substrates for the enhanced surface plasmon resonance imaging (SPRi) detection of DNA hybridization. Rigorous coupled-wave analysis was used to model and design the nanopost-based SPRi biosensor. Arrayed gold nanoposts on gold-coated glass substrate, with various widths and periodicity, were fabricated using electron-beam lithography and characterized with scanning electron and atomic force microscopy. A scanning-angle SPRi apparatus was used to conduct the kinetic analysis of DNA hybridization on nanopost-based sensor surface and assess the corresponding SPR signal amplification. Experimental results showed that both the nanostructure size and period influenced the SPR signal enhancement; the optimized 30 nm height, 50 nm size, and 110 nm period nanoposts provided a fivefold SPR signal amplification compared with the plain 50 nm thick gold film used as control.     

Surface plasmon sensor with gold film deposited on a two-dimensional colloidal crystal

A sensor based on surface plasmon resonance (SPR) of plasmonic crystals fabricated via a colloidal-crystal-assisted templating method is studied. Plasmonic crystals are prepared by depositing a thin gold (Au) layer onto a two-dimensional array of polystyrene spheres self-assembled on a quartz substrate. The enhanced transmission as a result of the SPR of Au plasmonic crystals, which are immersed in different ambient liquids, are measured and compared with that of polystyrene (PS) microsphere templates of different sizes, both before and after removal of Au nanoprisms formed on the quartz substrate through pores among the spheres. It is found that the measured sensitivities exhibit a linear dependence on the refractive index of the surrounding medium and are linked to coupling effects between SPRs on the corrugated Au film and nanoislands. The feasibility of the SPR system in molecular monolayer detection is further demonstrated through a formation of alkanethiolate self-assembled monolayers on the Au film surface, which causes a 4 nm red-shift of the main SPR. PACS  07.07.Df; 73.20.Mf; 78.66.-w; 81.16.Dn     

SPR and SERS characteristics of gold nanoaggregates with different morphologies

In this study, surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS) characteristics of gold nanoaggregates with different morphologies are examined to elucidate the correlation between SPR and SERS of the object. Nanoaggregates, defined as random aggregates (hereafter RA), elongated aggregates (hereafter EA) and two-dimensional layered aggregates (hereafter 2DLA) are fabricated by immobilizing colloidal gold nanoparticles on glass substrates. The color variation observed in the RA and EA samples indicates the variation in localized SPR excitations excited on the samples. The RA sample mostly shows a broadened and shifted SPR peak centered at 570 nm in addition to another peak in the longer wavelength region (∼700 nm), whereas in the EA sample a weak blue-shifted peak is observed near 450 nm in addition to a broadened peak centered at 570 nm covering a trail for another one near 700 nm. In the case of the 2DLA sample, more than one SPR peaks are observed in the longer wavelength region. The SERS observation confirms million times higher enhancement at least in Raman intensity using the gold nanoaggregates adsorbed by dye molecules. The EA sample of gold nanoparticles shows ∼5 times higher enhancement in Raman signal compared to that of the RA and 2DLA sample.