SERS signal response and SERS/SERDS spectra of fluoranthene in water on naturally grown Ag nanoparticle ensembles

We present experimental results of the time‐dependent Raman signal response of fluoranthene adsorbed on a naturally grown Ag nanoparticle ensemble, which serves as surface enhanced Raman scattering (SERS) substrate. In addition, SERS characteristics such as the concentration‐dependent calibration curves and the limit of detection (LOD) for fluoranthene in distilled water will be shown. The SERS substrate was prepared by Volmer–Weber growth under ultrahigh vacuum condition and exhibits a plasmon resonance wavelength at 491 nm. For the measurement of SERS signal response and SERS/shifted excitation Raman difference spectroscopy spectra of fluoranthene in water, experimental Raman setup containing a microsystem light source with two emission wavelengths (487.61 nm and 487.91 nm) was used. We experimentally demonstrate that the maximum SERS intensity is achieved 9 min after changing the analyte concentration from 0 nmol/l to 600 nmol/l. This response time is explained by a time‐dependent adsorption of the probe molecules onto the nanoparticles. The LOD for fluoranthene in water was evaluated applying shifted excitation Raman difference spectroscopy (SERDS) at different molecule concentrations. For SERDS, two emission wavelengths of a prototype microsystem light source have been used for Raman excitation. The experimental results reveal that the LOD for the probe molecules is very low. Experimentally, we have detected a fluoranthene concentration of only 4 nmol/l, which is very close to our estimated LOD of 2 nmol/l. Thus, the presented Raman setup, with a SERS substrate, whose plasmon resonance coincides with the excitation wavelength for SERS measurements, is well suited for in‐situ trace detection of pollutant chemicals in water. Copyright © 2013 John Wiley & Sons, Ltd.     

Tuning SERS for living erythrocytes: Focus on nanoparticle size and plasmon resonance position

Surface‐enhanced Raman spectroscopy (SERS) is a unique technique to study submembrane hemoglobin (Hb_sm) in erythrocytes. We report the detailed design of SERS experiments on living erythrocytes to estimate dependence of the enhancemen t factor for main Raman bands of Hb_sm on silver nanoparticle (AgNP) properties. We demonstrate that the enhancement factor for ν 4/A1g, ν 10/B1g and A2g Raman bands of Hb_sm varies from 10⁵ to 10⁷ under proposed experimental conditions with 473 nm laser excitation. For the first time we show that the enhancement of Raman scattering increases with the increase in the relative amount of small NPs in colloids, with the decrease in AgNP size and with plasmon resonance shift to the shorter wavelength region. Obtained results can be explained by the ability of smaller AgNPs to get deeper into nano‐invaginations of the plasma membrane than larger AgNPs. This shortens the distance between small AgNPs and Hb_sm and, consequently, leads to the higher enhancement of Raman scattering of Hb_sm. The enhancement of higher wavenumber bands ν 10/B1g and A2g is more sensitive to AgNPs’ size and the relative amount of small AgNPs than the enhancement of the lower wavenumber band ν 4/A1g. This can be used for AgNP‐controlled enhancement of the desired Raman bands and should be taken into account in biomedical SERS experiments. Copyright © 2013 John Wiley & Sons, Ltd.     

Characterization of protein-conjugating kinetics based on localized surface plasmon resonance of the gold nanoparticle

The gold nanoparticle exhibits optical property of localized surface plasmon resonance (LSPR), which dynamically alters as the surface adsorbs new ligands. We carried out a semi-quantitative analysis with the method of multivariate curve resolution, observing that the adsorption of serum albumin on gold nanoparticle was best deciphered as two-mode competitive kinetics. Interestingly, for human serum albumin, the slower mode contributed considerably to the LSPR response of protein-conjugated surfaces, while in the case of bovine serum albumin the faster mode overwhelmed the slower one at high protein concentrations. The kinetic patterns were rationalized with diversity of biomolecular orientations on the nanoparticle surface. The simple but efficient protocol supports semi-quantitative analysis combining UV-vis spectroscopy with chemometrics method for distinguishing conjugation kinetics of different types of proteins on the surface of nanoparticles at nanomolar concentration.     

金纳米球壳表面等离激元共振波长调谐特性研究

理论研究了金纳米球壳的几何结构参数, 及物理参量对局 域表面等离激元共振波长调谐特性的影响. 结果表明, 随着壳层厚度的增大, 球壳消光共振峰先蓝移后红移, 高阶峰转向时对应的壳层厚度比低阶峰大, 且该厚度与球壳内径的比值随内径尺寸的增大而减小, 随内核材料或外界环境介电常数的增大而增大, 散射共振峰也有类似的移动规律. 利用电子杂化效应和相位延迟效应对该现象进行了理论解释.     

Broadband tunability of surface plasmon resonance in graphene-coating silica nanoparticles

Graphene decorated nanomaterials and nanostructures can potentially be used in military and medical science applications. In this article, we study the optical properties of a graphene wrapping silica core–shell spherical nanoparticle under illumination of external light by using the Mie theory. We find that the nanoparticle can exhibit surface plasmon resonance(SPR) that can be broadly tuned from mid infrared to near infrared via simply changing the geometric parameters. A simplified equivalent dielectric permittivity model is developed to better understand the physics of SPR, and the calculation results agree well qualitatively with the rigorous Mie theory. Both calculations suggest that a small radius of graphene wrapping nanoparticle with high Fermi level could move the SPR wavelength of graphene into the near infrared regime.     

Localized surface plasmon resonance of silicon compounds adsorbed on silver nanoparticles

A simple method to produce silver nanoparticles on a glass surface from silver nanolayer deposited by magnetron sputtering and thermal annealed is presented. Localized surface plasmon resonance of nanoparticles shows a red shift depending on the silver nanolayer thickness, the refractive index and the thickness of an ultra-thin silicon compound adsorbed on the surface. A highly enhanced Raman spectrum of the characteristic groups of a silicon compound adsorbed on the nanoparticles surface was obtained.     

Ag nanoparticles obtained by pulsed laser ablation in water: surface properties and SERS activity

We studied the surface properties and reactivity of silver nanoparticles obtained by picosecond or nanosecond pulsed laser ablation in water and with 1064‐nm wavelength. Ultraviolet–visible spectroscopy results and subsequent modelling by Mie theory indicated the presence of an oxide layer on the nanoparticle surface, which favours the colloidal stability, but reduces the interaction with the environment. The oxide layer is also responsible for the reduced surface enhanced Raman spectroscopy (SERS) activity of these colloids with respect to those obtained by chemical reduction. However, SERS activation can be efficiently obtained by addition of chloride ions to the colloids, leading to SERS enhancement factors that are comparable with those of the chemically prepared counterparts. Copyright © 2015 John Wiley & Sons, Ltd.     

Fiber optic sensor based on surface plasmon resonance with nanoparticle films

This paper reports on a novel design of a fiber optic surface plasmon resonance (SPR) sensor based on nanoparticle metal film. The performance of the proposed sensor in terms of its signal-to-noise ratio (SNR) and sensitivity under different conditions related to the film with spherical gold nanoparticles embedded in a host material is theoretically analyzed. In particular, the effect of the parameters such as gold particle size, film thickness, and refractive index of host material is studied and the possible explanation, whenever required, is given. The numerical results presented in this paper leads to fulfill the requirement of significant optimization of the important design parameters to achieve a high SNR and sensitivity of a fiber optic SPR sensor with nanoparticle films.     

SERS characterization of metallic silver nanoparticle self‐assembly within thin films

Clusters of silver nanoparticles are generated by the thermally initiated reduction of silver carboxylates (long‐chain fatty acids) in the thin polymer films. The size, shape, and aggregation of these nanoparticles are affected by the reduction reaction in the presence of capping agents. In order to understand the mechanism(s) controlling the silver structure formation, it is essential to understand the surface coordination chemistry occurring during this process. We now report the first application of surface‐enhanced Raman spectroscopy (SERS) to directly characterize adsorbates on the surfaces of silver nanoparticles within a thin film imaging construction containing multiple components. In addition, SERS investigation of model silver substrates was used to confirm the identify of specific adsorbates of silver complexes. This is a powerful tool for revealing the chemistry involved with the control of silver nanoparticle aggregation during thermally induced metallic silver formation within thin films. Both the catechol‐reducing agent and the phthalazinone (PAZ) particle aggregation agent are observed on the metallic silver surface at the initial particle formation and during its crystal growth. However, careful attention to excitation wavelength is required in order to observe all the surface species. PAZ appears to be more effective at stabilizing individual silver particles than other aggregation agents investigated. An understanding of the roles of the aggregation/reducing agents in the growth and aggregation of silver nanoparticles is important for preparing different types of silver particles for specific applications including silver‐based thermal imaging systems. Copyright © 2008 John Wiley & Sons, Ltd.     

Study of electrical field distribution of gold-capped nanoparticle for excitation of localized surface plasmon resonance

The specific optical characteristics which can be observed from noble metal nanostructured materials such as nanoparticles and nanoislands have wide variety of applications such as biosensors, solar cells, and optical circuit. Because, these noble metal nanostructures induce the increment of light absorption efficiency by the enhancing effect of electrical field from localized surface plasmon resonance (LSPR) excitation. However, the enhancing effects of electrical field from LSPR using simple structured noble metal nanostructures for several applications are not satisfactory. To realize the more effective light absorption efficiency by the enhancing effect of electrical field, quite different noble metal nanostructures have been desired for applying to several applications using LSPR. In this study, to obtain the more effective enhancing effect of electrical field, conditions for LSPR excitation using a gold-capped nanoparticle layer substrate are computationally analyzed using finite-difference time-domain (FDTD) method. From the previous research, LSPR excitation using such gold-capped nanoparticle layer substrates has a great potential for application to high-sensitive label-free monitoring of biomolecular interactions. For understanding of detailed LSPR excitation mechanism, LSPR excitation conditions were investigated by analyzing the electrical field distribution using simulation software and comparing the results obtained with experimental results. As a result of computational analysis, LSPR excitation was found to depend on the particle alignment, interparticle distance, and excitation wavelength. Furthermore, the LSPR optical characteristics obtained from the simulation analysis were consistent with experimentally approximated LSPR optical characteristics. Using this gold-capped nanoparticle layer substrate, LSPR can be excited easily more than conventional noble metal nanoparticle-based LSPR excitation without noble metal nanoparticle synthesis. Hence, this structure is detectable a small change of refractive index such as biomolecular interactions for biosensing applications.     

Manipulated localized surface plasmon resonances in silver nanoshells coated with a spherical anisotropic layer

<正>The influences of the anisotropy of the outer spherically anisotropic(SA) layer on the far-field spectra and nearfield enhancements of the silver nanoshells are investigated by using a modified Mie scattering theory.It is found that with the increase of the anisotropic value of the SA layer,the dipole resonance wavelength of the silver nanoshell first increases and then decreases,while the local field factor(LFF) reduces.With the decrease of SA layer thickness, the dipole wavelength of the silver nanoshell shows a distinct blue-shift.When the SA layer becomes very thin,the modulations of the anisotropy of the SA layer on the plasmon resonance energy and the near-field enhancement are weakened.We further find that the smaller anisotropic value of the SA layer is helpful for obtaining the larger near-field enhancement in the Ag nanoshell.The geometric average of the dielectric components of the SA layer has a stronger effect on the plasmon resonance energy of the silver nanoshell than on the near-field enhancement.     

Quantitative model for the change of optical resonance in neural activity detection systems based on surface plasmon resonance

The mechanism of neural activity detection using the surface plasmon resonance (SPR) phenomenon was theoretically explored in this paper. Investigating the mechanism of SPR neural recordings has been difficult due to the complex relationship between different physiological and physical processes such as excitation of a nerve fiber and coherent charge fluctuations on the metal surface. This paper examines how these different processes may be connected by introducing a set of compartmental theoretical models that deal with the molecular scale phenomena; Poisson-Boltzmann (PB) equation, which was used to describe the ion concentration change under the time varying electrostatic potential, Drude-Lorentz electron model, which was used to describe electron dynamics under the time varying external forces, and a Fresnel's three-layered model, which expresses the reflectivity of the SPR system in terms of the dielectric constants. Each physical theoretical model was numerically analyzed using the finite element method (FEM) formulated for the PB equation and the Green's method formulated for the Drude-Lorentz electron equation. The model predicts that the ionic thermal force originating from the opening of the K⁺ ion channel is fundamental for modifying the dipole moment of the gold's free electron; thus, the reflectivity is changed in the SPR system. The discussion was done also on important attributes of the SPR signal such as biphasic fluctuation and the electrical noise-free characteristics.     

Surface plasmon resonance sensors based on Ag-metalized nanolayer in microstructured optical fibers

Surface plasmon resonance sensors based on Ag-metalized nanolayer in microstructured optical fibers are theoretically analyzed by using finite element method (FEM). In our simulations we use Drude-Lorentz model to describe the metal dielectric constant. The numerical results show that the sensitivity of Ag-metalized SPR sensor could reach 1167 nm/RIU and corresponding resolution is 8.57×10⁻⁵ RIU. Compared to conventional Au-metalized SPR sensors the performance of our device is obviously better.     

金银三层纳米管局域表面等离激元共振特性研究

相对于单一金属纳米材料,二金属复合纳米材料具有更大的潜在应用价值.基于时域有限差分方法,研究了SiO₂-Ag-Au和SiO₂-Au-Ag二金属三层纳米管的消光光谱,并对其局域表面等离激元共振(Localized Surface Plasmon Resonance,LSPR)特性进行了分析.研究发现,内核尺寸变大将导致上述两种金属纳米管LSPR峰红移;内层金属及外层金属壳层厚度增大均会导致其LSPR峰蓝移.银壳厚度变化对纳米管LSPR的调制作用大于金壳厚度变化造成的影响.上述现象可以利用等离激元杂化理论及自由电子和振荡电子变化的竞争机制进行分析.     

Influence of groove depth and surface profile on fluorescence enhancement by grating-coupled surface plasmon resonance

The fluorescence intensity of a sample placed on a metal grating pattern is enhanced due to excitation by the electric field of the grating-coupled surface plasmon resonance (GC-SPR). The dependence of the enhancement on groove depth and surface profile was studied with the aim of improving the sensitivity of fluorescence detection. The enhancement was found to depend on the groove depth, with intensity most enhanced on grating substrate of about 20 nm depth, which produced an intensity about 30 times greater than that on a flat borosilicate glass substrate. Rigorous coupled wave analysis calculation showed that the shape of the groove influenced GC-SPR, suggesting that controlling not only the depth but also the shape of the grating surface profile can be an important factor in improving the sensitivity of detection by fluorescence microscopy.     

Self‐assembled silver nanoparticle monolayer on glassy carbon: an approach to SERS substrate

In this paper, the fabrication of an active surface‐enhanced Raman scattering (SERS) substrate by self‐assembled silver nanoparticles on a monolayer of 4‐aminophenyl‐group‐modified glassy carbon (GC) is reported. Silver nanoparticles are attached to the substrate through the electrostatic force between the negatively charged silver nanoparticles and the positively charged 4‐aminophenyl groups on GC. The active SERS substrate has been characterized by means of tapping‐mode atomic force microscopy (AFM), indicating that large quantities of silver nanoparticles are uniformly coated on the substrate. Rhodamine 6G (R6G) and p‐aminothiophenol (p‐ATP) are used as the probe molecules for SERS, resulting in high sensitivity to the SERS response, with the detection limit reaching as low as 10⁻⁹ M . This approach is easily controlled and reproducible, and more importantly, can extend the range of usable substrates to carbon‐based materials for SERS with high sensitivity. Copyright © 2007 John Wiley & Sons, Ltd.     

半壳结构金纳米膜的局域表面等离子体共振效应

采用纳米模版印刷术和化学自组装技术制备了半壳结构的金粒子膜.利用场发射扫描电子显微镜和光谱仪等测试手段对样品的结构和光学性质进行了分析.研究发现，该结构的金膜所具有独特的局域表面等离子体共振效应取决于样品的粒子大小、间距等微观结构，且其峰值吸收波长对其周围环境介质的介电常数变化十分敏感.实验结果表明，粒子排列均匀的亚单层膜结构是控制光学性质稳定的关键. 关键词： 局域表面等离子体共振 半壳结构 纳米模版印刷术     

金纳米球壳对的局域表面等离激元共振特性分析

应用有限元方法, 研究金纳米球壳对的几何结构参数及物理参量对其表面等离激元共振的散射及消光光谱的影响, 并根据等离激元杂化理论进行了理论分析. 结果表明, 随着金壳厚度的增加, 金纳米球壳对的散射及消光共振峰先发生蓝移而后红移, 而随着金纳米球壳间隙的减小, 或者随着金纳米球壳的内核尺寸或内核介质折射率的增大, 散射及消光共振峰均发生红移; 随着金壳厚度或内核尺寸减小, 或者随着内核介质折射率增大, 金纳米球壳对的散射与消光共振强度减弱, 而随着金壳间隙的减小, 金纳米球壳对的散射共振强度先增强后减弱, 而消光共振强度逐渐增强, 数值模拟与理论分析一致.     

Localized surface plasmon resonance scattering imaging and spectroscopy for real-time reaction monitoring

Abstract

In the last decade, plasmonic nanoparticles-based scattering imaging and spectroscopy has introduced the analysis and sensing to the single nanoparticle and molecule level, such as the biomolecules adsorption process and the quantitative detection of small molecules and ions. Recently, this technology has also been focus on the real-time and in-situ reaction monitoring, which is a new emerging branch of the single-nanoparticle imaging, revealing the reaction dynamic information and the related controlling factors. In this mini-review, recent applications of plasmon resonance scattering imaging and spectroscopy in the real-time reaction monitoring in the past 5?years are highlighted and discussed.     

利用Ag@SiO_2纳米粒子等离子体共振增强发光二极管辐射功率的数值研究

金属纳米粒子利用其局域表面等离子体共振效应(LSPR),可以增强附近荧光分子的自发辐射速率,因而在光学传感、光电器件等领域中具有潜在的应用价值.金属纳米粒子的LSPR与其自身的材料、形状、尺寸以及周围环境介质密切相关,这影响着纳米粒子在具体器件中的应用.本文利用三维时域有限差分法,研究了相同体积的球形、椭球形、立方形与三棱柱形银纳米粒子对薄膜发光二极管辐射功率的影响;计算了不同形状银纳米粒子对偶极子光源辐射功率和薄膜器件光出射强度的增强,并结合LSPR效应讨论了辐射功率变化的物理机理.研究结果表明:银纳米粒子自身形状尖锐程度的增加有利于提高LSPR的共振强度;同时纳米粒子的形状影响了LSPR共振电场与薄膜器件中偶极子辐射电场之间的耦合作用,其中立方形纳米粒子因为能实现最强的耦合作用而对器件的辐射功率增强最大.在此基础上进一步讨论了不同薄膜材料对LSPR共振及光源辐射功率的影响,发现较高的材料折射率有利于增强金属纳米粒子的LSPR与器件的耦合作用,从而改善发光二极管性能.