表面增强荧光研究进展

本文系统地介绍了金属表面增强荧光现象、产生机理及其应用.粗糙金属和超薄光滑金属表面均可表现出荧光增强效应,但这两种表面增强荧光产生的机理不同,所发出的荧光性质也不同.粗糙金属表面增强荧光的主要原因被认为是加快了处于基质表面附近的荧光物种的辐射衰减过程,而超薄光滑金属表面增强荧光则是激发态荧光物种与金属表面的等离子体耦合共振的结果.与粗糙金属表面增强荧光不同,超薄光滑金属表面增强荧光具有突出的方向性.金属表面增强荧光已经开始在DNA无损检测、荧光共振能量转移免疫分析等领域获得重要应用.     

表面增强荧光研究进展

本文系统地介绍了金属表面增强荧光现象、产生机理及其应用。粗糙金属和超薄光滑金属表面均可表现出荧光增强效应,但这两种表面增强荧光产生的机理不同,所发出的荧光性质也不同。粗糙金属表面增强荧光的主要原因被认为是加快了处于基质表面附近的荧光物种的辐射衰减过程,而超薄光滑金属表面增强荧光则是激发态荧光物种与金属表面的等离子体耦合共振的结果。与粗糙金属表面增强荧光不同,超薄光滑金属表面增强荧光具有突出的方向性。金属表面增强荧光已经开始在DNA无损检测、荧光共振能量转移免疫分析等领域获得重要应用。     

金纳米棒的光学性质研究进展

金纳米棒在紫外-可见-近红外(UV-Vis-NIR)波段具有独特的可调节表面等离子体共振(SPR)光学特性,其良好的稳定性、低生物毒性、亮丽的色彩和在催化、信息存储、生物医学等领域广阔的应用前景受到相关研究领域的广泛关注.结合已有的研究基础,本文主要综述了金纳米棒光学性质的研究进展,包括表面等离子体共振、局域场增强效应、共振耦合效应及荧光特性,并对金纳米棒的应用做了展望.     

银膜表面等离子体耦合辐射特性的仿真分析

表面等离子体耦合辐射(SPCE)是传统表面等离子体共振(SPR)的逆过程:当分子足够靠近金属薄膜表面时( < 200 nm),其受激辐射的能量可以耦合成SPR模式并定向辐射到棱镜中.由于具有场增强特性、高收集效率和优异的表面选择性, SPCE作为一种新的表面分析技术已经在荧光和拉曼光谱领域得到了有效的应用.本文采用光学互易定理简化传统SPCE的计算方法.通过计算,我们得到了SPCE一维和二维辐射功率密度分布,表面选择性,辐射角的波长色散特性,辐射角半峰宽与银膜厚度的关系.仿真结果与已报到的实验结果吻合良好,验证了该方法的有效性.     

等离子体增强上转换发光及其应用

稀土上转换纳米材料（UCNPs）是一类在近红外光激发下发出可见光的纳米材料。与有机荧光染料、量子点等发光材料相比,UCNPs具有化学稳定性高、光稳定性强、荧光寿命长、反斯托克斯位移大、发光谱带窄和光穿透深度大等诸多优点,在生物成像、传感器、激光器、光动力疗法和太阳能电池等领域有潜在的应用价值。但是由于UCNPs激活离子的吸收截面太小,导致其发光效率偏低,限制了UCNPs的进一步应用。因而如何提高上转换发光强度成为当前的研究热点。针对上述问题,本文系统阐述了金属表面等离子体共振（SPR）增强上转换发光领域的研究进展。首先介绍了SPR增强上转换发光的三种机制,随后重点介绍了化学法和物理法这两种SPR-UCNPs体系的构建方法以及其在太阳能电池、生物成像、生物检测、光热治疗和光催化等领域的应用。文章最后指出了SPR增强上转换发光领域存在的不足和未来的研究方向。     

纳米银对铕-吡啶-2,6-二羧酸配合物荧光增强效应的研究

研究了纳米银对分别以水、重水、乙醇和二甲基甲酰胺为溶剂的铕-吡啶-2,6-二羧酸(Eu(III)DPA)配合物溶液的荧光增强效应.研究结果表明,Eu(III)DPA溶液中加入纳米银,电偶极跃迁(5D0→7F2)和磁偶极跃迁(5D0→7F1)发射强度先增强而后逐渐下降,5D0→7F2的荧光增强效率高于5D0→7F1的荧光增强效率.在乙醇溶剂中纳米银对Eu(III)DPA溶液的荧光增强效应最大.在水或重水或乙醇溶剂中,Eu(III)DPA的不对称率明显提高,而在二甲基甲酰胺溶剂中几乎不变.分析认为,纳米银对Eu(III)DPA溶液荧光的影响与纳米银表面等离子体共振与激发态荧光中心强烈耦合以及表面等离子体再吸收有关.     

纳米银对铕配合物荧光性质的影响(英文)

研究了纳米银对稀土铕-吡啶-2,6-二羧酸配合物(Eu(Ⅲ)C7H5NO4,Eu(Ⅲ)DPA)的荧光性质的影响。随着纳米银浓度增加,荧光强度先增强而后逐渐下降。较大粒径的纳米银使Eu(Ⅲ)DPA荧光增强效率较大,且达到最大荧光增强效率所需的纳米银浓度较低。在高浓度Eu(Ⅲ)DPA溶液体系中,纳米银导致荧光猝灭。电偶极子跃迁发射荧光增强效率大于磁偶极子跃迁发射荧光增强效率。分析认为,纳米银对Eu(Ⅲ)DPA荧光性质的影响与表面等离子体共振与激发态荧光中心强烈耦合以及表面等离子体再吸收有关。同时,纳米银对铕配合物的不对称率有影响,其影响因素与局域电磁场增强,折射率以及配位场有关。     

纳米银对铕配合物荧光性质的影响

本文研究了纳米银对稀土铕-吡啶-2,6-二羧酸配合物（Eu（Ⅲ）C₇H₅NO₄,Eu（Ⅲ）DPA）的荧光性质的影响。随着纳米银浓度增加,荧光强度先增强而后逐渐下降。较大粒径的纳米银使Eu（Ⅲ）DPA荧光增强效率较大,且达到最大荧光增强效率所需的纳米银浓度较低。在高浓度Eu（Ⅲ）DPA溶液体系中,纳米银导致荧光猝灭。电偶极子跃迁发射荧光增强效率大于磁偶极子跃迁发射荧光增强效率。分析认为,纳米银对Eu（Ⅲ）DPA荧光性质的影响与表面等离子体共振与激发态荧光中心强烈耦合以及表面等离子体再吸收有关。同时,纳米银对铕配合物的不对称率有影响,其影响因素与局域电磁场增强,折射率以及配位场有关。     

纳米银对表面吸附镝配合物的荧光增强效应研究

研究了不同粒径的纳米银对镝配合物(乙二胺四乙酸配合物)的光谱学性质影响。当配合物溶液的pH值范围为4.0～6.0时,加入纳米银,可观察到大量的纳米银聚集体形成,而在吸收光谱的长波处出现一个新的吸收峰,随着纳米银浓度的增加,该吸收峰逐渐红移,同时,镝配合物的荧光强度增强。实验结果表明,纳米银粒子对镝配合物的荧光增强效应及荧光增强因子与纳米银粒子的浓度和粒径密切相关。随着纳米银浓度的增加,配合物的荧光强度先增强而后又逐渐降低。小粒径的纳米银对镝配合物的荧光增强因子较小。本文从纳米银粒子的聚集效应、局部电磁场增强效应及光吸收效应等方面探讨了纳米银对表面吸附镝配合物的+荧光增强效应机理。     

纳米ZnO的表面增强拉曼散射效应来源研究

表面增强拉曼光谱（SERS）的广泛应用源于优良的基底,目前主要局限在粗糙贵金属及胶体纳米颗粒材料.而半导体的光谱高稳定性和再现性,使其成为制备SERS基底的新型材料,但对于其SERS增强机理的研究仍存在极大挑战.本工作以典型的形貌新颖、尺寸均一的扫帚状n型纳米半导体ZnO为SERS基底材料,通过调节激发光的波长和选用具有不同对位取代基的对硝基苯硫酚（PNTP）、苯硫酚（TP）、对氨基苯硫酚（PATP）为探针分子,系统地研究了纳米ZnO的SERS增强行为,估算了其表面增强因子（EF）,分离了化学增强作用中非共振增强效应和电荷转移效应对SERS的贡献.研究表明三种分子在不同激发光作用下的增强因子为10至35,其中PNTP分子约10倍的增强主要来自于因吸附而造成极化率变化的非共振增强效应,TP和PATP分子20~35倍的增强则是由非共振增强效应与光子驱动电荷转移效应共同作用所致,光子能量越高,SERS增强效应越强.且因分子与ZnO间电荷转移的速率较慢导致ZnO表面电荷转移增强效应较贵金属低1~2个数量级.本研究结果为新型半导体SERS基底的制备及调控提供了新思路.     

Suppressed Blinking in Single Quantum Dots (QDs) Immobilized Near Silver Island Films (SIFs)

In this report, we use single-molecule spectroscopic method to study emission behaviors of streptavidin conjugated quantum dots immobilized on biotinylated-BSA (bovine serum albumin) monolayer near non-continuous rough silver nanostructure. We observed greatly reduced blinking and enhanced emission fluorescence of quantum dots next to silver island films.     

Surface-enhanced Raman and fluorescence joint analysis of soil humic acids

Surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) combined emissions were used in this work to the analysis of humic acids (HA). This study examined HA structure at different pH and HA concentrations and assessed the structural differences taking place in HA as a result of various amendment trials. Raman and fluorescence emissions behave in opposite ways due to the effect of the metal surface on the aromatic groups responsible for these emissions. The information afforded by these techniques can be successfully employed in the structural and dynamic analysis of these important macromolecules. The surface-enhanced emission (SEE) spectra, that is the sum of the Raman and the fluorescence emissions, were acquired by using both macro- and micro-experimental configurations in order to apply imaging and confocal Raman and fluorescence spectroscopy techniques on the analysis of HA.     

Metallic-Nanostructure-Enhanced Fluorescence of Single Flavin Cofactor and Single Flavoenzyme Molecules

The enzyme cofactors are intrinsically fluorescent and participate directly in the single molecule enzymology studies. Due to photobleaching, one cannot follow kinetics continuously by cofactor fluorescence for more than several minutes typically. Modification of spectral properties of fluorophores, such as the amplification of emission intensity, can be achieved through coupling with surface plasmons in close proximity to metallic nanostructures. This process, referred to as metal-enhanced fluorescence, offers promise for a range of applications, including bioassays, sensor technology, microarrays, and single-molecule studies. Here, we demonstrated up to a 100-fold increase in the emission of the single cofactors and flavoenzymes near silver nanostructures. Amplified fluorescence of different types of flavins and flavoenzymes has been interpreted by using time-resolved single molecule fluorescence data. The results show considerable promise for the studies of enzyme kinetics using the intrinsic fluorescence from the cofactors.     

Multicolor directional surface plasmon-coupled chemiluminescence

In reports over the past several years, we have demonstrated the efficient collection of optically excited fluorophore emission by its coupling to surface plasmons on thin metallic films, where the coupled luminescence was highly directional and polarized. This phenomenon is referred to as surface plasmon-coupled emission (SPCE). In this current study, we have extended this technique to include chemiluminescing species and subsequentially now report the observation of surface plasmon-coupled chemiluminescence (SPCC), where the luminescence from chemically induced electronic excited states couples to surface plasmons in thin continuous metal films. The SPCC is highly directional and predominantly p-polarized, strongly suggesting that the emission is from surface plasmons instead of the luminophores themselves. This indicates that surface plasmons can be directly excited from chemically induced electronic excited states and excludes the possibility that the plasmons are created by incident excitation light. This phenomenon has been observed for a variety of chemiluminescent species in the visible spectrum, ranging from blue to red, and also on a variety of metals, namely, aluminum, silver, and gold. Our findings suggest new chemiluminescence sensing strategies on the basis of localized, directional, and polarized chemiluminescence detection, especially given the wealth of assays that currently employ chemiluminescence-based detection.     

Metal-enhanced fluorescence of carbon nanotubes

The photoluminescence (PL) quantum yield of single-walled carbon nanotubes (SWNTs) is relatively low, with various quenching effects by metallic species reported in the literature. Here, we report the first case of metal enhanced fluorescence (MEF) of surfactant-coated carbon nanotubes on nanostructured gold substrates. The photoluminescence quantum yield of SWNTs is observed to be enhanced more than 10-fold. The dependence of fluorescence enhancement on metal-nanotube distance and on the surface plasmon resonance (SPR) of the gold substrate for various SWNT chiralities is measured to reveal the mechanism of enhancement. Surfactant-coated SWNTs in direct contact with metal exhibit strong MEF without quenching, suggesting a small quenching distance for SWNTs on the order of the van der Waals distance, beyond which the intrinsically fast nonradiative decay rate in nanotubes is little enhanced by metal. The metal enhanced fluorescence of SWNTs is attributed to radiative lifetime shortening through resonance coupling of SWNT emission to the reradiating dipolar plasmonic modes in the metal.     

Enhanced fluorescence of Cy5-labeled oligonucleotides near silver island films: a distance effect study using single molecule spectroscopy

We investigated fluorescence enhancements and lifetime reductions of Cy5 probe molecules at various distances from the deposited silver island film surface using single molecule spectroscopic methods. The proximity of fluorophore molecules to the surface was controlled by alternating layers of biotinylated bovine serum albumin (BSA-biotin) and avidin, followed by binding of Cy5-labeled oligonucleotides to the top of a BSA-biotin layer structure. We observed dramatically varied brightness of fluorophores with distances from metal structures as well with reduced blinking in the presence of silver island films. In addition, distributions of fluorescence lifetimes and apparent emission intensities from individual molecules indicate an inhomogeneous nature of local matrix surface near metallic nanostructures. These studies illustrate the exclusive information that is otherwise hidden in ensemble measurements.     

Combined SPR and SERS microscopy in the Kretschmann configuration

A novel hybrid spectroscopic technique is proposed, combining surface plasmon resonance (SPR) with surface-enhanced Raman scattering (SERS) microscopy. A standard Raman microscope is modified to accommodate the excitation of surface plasmon-polaritons (SPPs) on flat metallic surfaces in the Kretschmann configuration, while retaining the capabilities of Raman microscopy. The excitation of SPPs is performed as in standard SPR-microscopy; namely, a beam with TM-polarization traverses off-axis a high numerical aperture oil immersion objective, illuminating at an angle the metallic film from the (glass) substrate side. The same objective is used to collect the full Kretschmann cone containing the SERS emission on the substrate side. The angular dispersion of the plasmon resonance is measured in reflectivity for different coupling conditions and, simultaneously, SERS spectra are recorded from Nile Blue (NB) molecules adsorbed onto the surface. A trade-off is identified between the conditions of optimum coupling to SPPs and the spot size (which is related to the spatial resolution). This technique opens new horizons for SERS microscopy with uniform enhancement on flat surfaces.     

Angular-dependent metal-enhanced fluorescence from silver colloid-deposited films: opportunity for angular-ratiometric surface assays

We describe an exciting opportunity for Metal-Enhanced Fluorescence (MEF)-based surface assays using an angular-ratiometric approach to the observed enhanced emission from fluorophores in close proximity to silver colloids deposited on glass substrates. This approach utilizes the radiationless energy transfer (coupling) between the excited states of the fluorophore and the induced surface plasmons of the silver colloids, and the subsequent angular-dependent fluorescence emission from the fluorophore-silver colloid system. Since MEF is related to surface plasmons' ability to scatter light, angular-dependent light scattering from three different silvered surfaces and glass substrates were investigated using two common excitation angles, 45 and 90 degrees . The scattered light from silvered surfaces with a high loading was observed at wider angles on both sides of the glass substrates, while forward scattering (from the back of the glass) was dominant for the silvered surfaces with low loading, as explained by both Mie and Rayleigh theories. When silver colloids were placed between the fluorophore and glass interface, the coupled fluorescence emission through the higher refractive index glass (and in air), increased in an angular-dependent fashion, following closely the angular-dependent light scattering pattern of the silver colloids themselves. Similar observations for fluorescence emission from fluorophores deposited onto glass surfaces alone were made, but at much narrower angles on both sides of the fluorophore-glass interface and were simply explained by Lambert's cosine law. As the loading of silver on glass was increased, the enhanced fluorescence emission was observed at wider angles (towards 0 and 180 degrees ) at both sides of the silvered surfaces. Glass surfaces without silver colloids were used as control samples to demonstrate the benefits of MEF for enhancing fluorescence signatures in an elegant, angular-dependent fashion. Finally, the utility of the angular-dependent MEF phenomenon for intensity-based angular-ratiometric surface assays is demonstrated.     

Surfaced-enhanced cellular fluorescence imaging

The novel and burgeoning technique of surfaced-enhanced cellular fluorescence imaging has tremendous potential in the monitoring and investigation of intracellular processes at the single-molecular level, for instance, high-resolution cellular imaging, long-term in vivo observation of cell trafficking, tumor targeting, and diagnostics. The success hinges on the development and fabrication of plasmonic nanostructured surfaces with size and shape compatible with cell interactions because they are crucial to enhanced cellular imaging. In this review, the mechanism of surface-enhanced cellular fluorescence imaging is discussed in view of metal-enhanced fluorescence. The design of nanostructured surfaces with evenly distributed plasmonic fields suitable for enhanced cellular fluorescence imaging such as nanoparticle superlattice coatings, lithographically-based substrates, and alumina-templated surface are described.