Tailor-made metal nanoparticles as SERS substrates

In this contribution we summarize recent experiments with the objective to generate optimized substrates for surface-enhanced Raman spectroscopy (SERS). For this purpose, the well-established laser-assisted growth technique has been applied, which relies on a precise control of the growth kinetics of supported metal nanoparticles. With this method reproducible and stable SERS substrates with tailor-made optical properties possing best field enhancements were produced for specific excitation wavelengths and detection ranges. Optimization of the SERS substrates has been achieved by stabilizing the localized surface plasmon polariton resonance (SPR) of gold nanoparticles in the vicinity of the laser wavelength of λ=647 nm and λ=785 nm used for SERS excitation. After nanoparticle preparation, SERS spectra of pyrene were obtained using naturally grown nanoparticles and nanoparticles prepared by laser-assisted growth. The most important result is that the optimized substrates prepared by laser-assisted growth exhibit a significantly higher signal-to-noise ratio as compared to naturally grown nanoparticles. They are even better than substrates whose SPR has been tuned to the excitation wavelength by an elevated temperature during preparation. Another important observation is that all SERS spectra exhibit excellent reproducibility and the substrates do not show degradation during the measurements. Finally, the SERS enhancement factors due to the optimized substrates have been estimated and are on the order of 10⁵ to 10⁶.     

Adjustment and control of SERS activity of metal substrates by pressure

Metal pellets of silver and copper for surface‐enhanced Raman scattering (SERS) spectroscopy were prepared by compression with different pressures. It was found that the SERS activity of the pellet could be controlled by pressure. Enhanced Raman scattering properties of the metal pellets in the presence of adsorbed 4‐mercaptobenzoic acid (4‐MBA) with excitation at 632.8 or 514 nm could be obtained by choosing proper pressure of pellatization. The SERS peak intensity of the band at ∼1584 cm⁻¹ of 4‐MBA adsorbed on the metal pellets varies as a function of applied pressure, and which is about 1.2–32 times greater than when it is adsorbed on silver and copper particles. The calculated results of three‐dimensional finite‐difference time‐domain method (3D‐FDTD) are in good agreement with the experimental data. Moreover, no spurious peaks appear in the SERS spectra of the samples because no other chemicals are involved in the simple preparation process of the metal pellets, which will facilitate its use as an SERS‐active substrate for analytical purposes. In summary, SERS‐active metal pellets can be produced simply and cost effectively by the method reported here, and this method is expected to be utilized in the development of SERS‐based analytical devices. Copyright © 2009 John Wiley & Sons, Ltd.     

Adsorption and catalysis of flavonoid quercetin on different plasmonic metal nanoparticles monitored by SERS

Raman and surface‐enhanced Raman scattering spectroscopy were used to follow the chemical modification of quercetin (QUC) on silver nanoparticles. Different metallic systems were fabricated to check the influence of the interface, in terms of electric charge or total available surface, on the catalytic change undergone by QUC. The effect of QUC surface coverage was crucial to reveal information about the different orientation and the interaction mechanism with the metal at different concentrations of this flavonoid. Surface‐enhanced Raman scattering spectra of good quality of QUC were observed at concentrations down to 10^–8 M. Chemical modifications in the presence of nanostructure metal surfaces include oxidation followed by a subsequent polymerization via a condensation of rings whereas different chemical species have been recognized under different experimental conditions. The assignment of the new species formed on the metal surface was conducted. Copyright © 2012 John Wiley & Sons, Ltd.     

SERS activity of carbon nanotubes modified by silver nanoparticles with different particle sizes

A two-dimensional (2D) surface-enhanced Raman scattering (SERS) substrate is fabricated by decorating carbon nanotube (CNT) films with Ag nanoparticles (AgNPs) in different sizes, via simple and low-cost chemical reduction method and self-assembling method. The change of Raman and SERS activity of carbon nanotubes/Ag nanoparticles (CNTs/AgNPs) composites with varying size of AgNPs are investigated by using rhodamine 6G (R6G) as a probe molecule. Meanwhile, the scattering cross section of AgNPs and the distribution of electric field of CNTs/AgNPs composite are simulated through finite difference time domain (FDTD) method. Surface plasmon resonance (SPR) wavelength is redshifted as the size of AgNPs increases, and the intensity of SERS and electric field increase with AgNPs size increasing. The experiment and simulation results show a Raman scattering enhancement factor (EF) of 10⁸ for the hybrid substrate.     

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.     

FDTD simulation study of size/gap and substrate-dependent SERS activity study of Au@SiO_2 nanoparticles

We use Au@SiO_2 nanoparticles(NPs) to systematically and comprehensively study the relationship between nanostructure and activity for surface-enhanced Raman scattering. Calculation simulation using the finite different time domain method verifies the experiment results and further reveals that the particle size and the distance between the NPs play vital roles in the surface-enhanced Raman scattering(SERS). Furthermore, in order to better simulate the real experiment, a Au@SiO_2 nanosphere dimer is placed on the silicon substrate and Au substrate, separately. The simulation results show that the large EM field coupling is due to the "hot spots" transferred from the NP–NP gaps to NP–surface of metal gaps,meanwhile, more "hot spots" occur. We also find that the signal intensity strongly depends on the position of the probe molecule. This work provides a better understanding of EM field enhancement.     

SDS bubbles functionalized with Gold nanoparticles and SERS applications

We present a method of incorporation of gold nanoparticles in SDS (sodium dodecyl sulfate) bubbles with a low polydispersity index (monodispersed nanoparticles). Both the bubbles and nanoparticles maintained their structural and morphologic properties after functionalization. The bubbles present a radio of 0.38 mm with a standard deviation of±0.018 mm. The gold nanoparticles were obtained with sucrose as the catalytic agent and ascorbic acid as the reducing agent. The nanoparticles display several geometric morphologies as well as sizes inferior to 50 nm, as observed in the images obtained with Transmission Electron Microscopy (TEM). The optical properties were studied by optical absorption spectroscopy. The absorption band linked to the surface plasmon resonance (SPR) is located at 550 nm before and after the functionalization of the bubbles. Moreover, microscopic bubbles with a diameter smaller than 1 µm with the ability to stabilize nanoparticles in their surface were found in isolated regions of the sample. Additionally, the Surface Enhancement Raman Spectroscopy (SERS) properties of the colloid were analyzed with common drugs.     

Frontiers of Plasmonics

Plasmonics, an important branch of nanooptics, has seen its prosperous development and exciting applications during the past years [1 3]. Surface plasmons （SPs）, the light-driven collective oscillation of free electrons in metals, include the localized type （localized surface plasmons, LSPs） and propagating type （surface plasmon polaritons, SPPs）. The most charming characteristics of SPs are the strong confinement of electromagnetic （EM） field （and thus EM enhancement） and long range propagation of EM energy （in case of SPPs）. Based on these characters, intriguing applications in many fields have been found, for example, single molecule spectroscopy using surface- enhanced Raman scattering （SERS） [4-7], ultrasensitive detection of chemical and biological species using localized surface plasmon resonance （LSPR） sensor [8, 9], spaser that stems from the amplification of resonant SPs in the cavity of metal nanostructures [10-12], superlens that utilizes the sub-wavelength concentration of SPs [13, 14], and plasmonic circuits that are based on the propagation modulation of SPPs [15-17].     

Mixing thiols on the surface of silver nanoparticles: preserving antibacterial properties while introducing SERS activity

The purpose of the study was to prepare and characterize nanosuspensions that can maintain high and extended supersaturation to improve the dissolution and absorption of poorly soluble 10-hydroxycamptothecin (10-HCPT). 10-HCPT oral nanosuspensions (HCPT-Nanosuspensions) were produced on a laboratory-scale by microprecipitation- high pressure homogenization method. The particle morphology and the physical state were studied using transmission electron microscopy, X-ray powder diffraction (XRPD), and differential scanning calorimetry (DSC). Supersaturated dissolution tests were carried out with the paddle method. Caco-2 cell experiments were performed to imitate the oral absorption. The in vivo pharmacokinetics studies were undertaken in rats following oral administration. The 10-HCPT nanoparticles were 135 nm in dimension before lyophilization and were claviform or lump in shape. XRPD and DSC both confirmed that a portion of 10-HCPT was present in a crystalline state in nanosuspension. Supersaturated dissolution tests showed HCPT-Nanosuspensions could maintain high supersaturated level for an extended period time. The cell experiment on HCPT-Nanosuspensions showed a significantly higher uptake and greater membrane permeability compared with the other formulations. The pharmacokinetic test exhibited HCPT-Nanosuspensions had a similar pharmacokinetic performance with 10-HCPT solution. In conclusion, highly and extendedly supersaturated HCPT-Nanosuspensions have been prepared which could result in high peak concentration (C _max) and great exposure (AUC) after oral administration.

     

Investigation of metal nanoparticles produced by laser ablation and their catalytic activity

Polydiphenylsilylenemethylene (PDPhSM) thin films, which are difficult to fabricate by conventional methods because of their insolubility and high melting point, have been synthesized by using laser-ablated metal nanoparticles for the thermal ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC) in this paper. TPDC was first evaporated on silicon substrates and then exposed to metal (Pt, Cu and Ag) nanoparticles deposition by laser ablation prior to heat treatment. The catalytic activity of Pt, Cu and Ag nanoparticles has been studied. The results showed that the mean diameter of Pt nanoparticles was the smallest, Cu nanoparticles the moderate and Ag nanoparticles the biggest, while the polymerization efficiency for Pt nanoparticles was the highest, Cu nanoparticles the moderate and Ag nanoparticles the lowest. In addition, the penetration behaviours of Pt, Cu and Ag nanoparticles into the TPDC monomer films during laser ablation were different due to the particle size or the chemical interaction between metal nanoparticles and TPDC molecules.     

Preparation of SERS active Ag nanoparticles encapsulated by phospholipids

A cost‐effective way of fabricating lipid‐coated surface‐enhanced Raman spectroscopy (SERS) substrate having reproducible high SERS activity was proposed. Ag nanoparticle embedded in 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPC) and 1,2‐dioleoyl‐3‐trimethylammonium‐propane (DOTAP) membranes was produced by direct deposition of a 5‐nm‐thick layer of Ag onto the solid‐supported phospholipid membrane, and subsequent dissolution of the Ag nanoparticle‐embedded membrane in iso‐octane allowed easy one‐pot fabrication of DOPC‐ or DOTAP‐coated Ag nanoparticles. In particular, DOTAP produced nearly monodisperse lipid‐encapsulated Ag nanoparticles (9 nm in diameter) exhibiting reproducible high SERS activity (detecting up to 10 nM of rhodamine 6G and 0.5 μM of glutathione). In addition, the process was modified to incorporate variety of Raman active molecules (rhodamine 6G, malachite green, 4‐aminothiopheonol, 4‐mercaptopyridine) into the particle‐encapsulating lipid bilayer. The DOTAP/Raman dye‐coated Ag nanoparticles also generated high SERS activity to enable potential application of the DOTAP/Raman dye‐coated Ag nanoparticles feasible in different areas. Copyright © 2014 John Wiley & Sons, Ltd.     

SERS activity of Au nanoparticle films

The core-shell gold nanoparticle film is fabricated by using nanolithography and self-assembly monolayer technology. The film exhibits unique optical properties and has strong surface enhanced Raman scattering （SERS） activity. The relationship between nanostructure and surface electrical field is studied by employing pyridine as the SERS probe. It is found that particle size and inter-particle space are important factors. The enhancement ratio is measured to be more than 10^4.     

SERS activity of Au nanoparticles coated on an array of carbon nanotube nested into silicon nanoporous pillar

A novel composite structure, Au nanoparticles coated on a nest-shaped array of carbon nanotube nested into a silicon nanoporous pillar array (Au/NACNT/Si-NPA), was fabricated for surface-enhanced Raman scattering (SERS). The morphology of the Au/NACNT/Si-NPA composite structure was characterized with the aid of scanning electron microscopy, X-ray diffraction instrumentation and Transmission electron microscopy. Compared with SERS of rhodamine 6G (R6G) adsorbed on SERS-active Au substrate reported, the SERS signals of R6G adsorbed on these gold nanoparticles were obviously improved. This was attributed to the enlarged specific surface area for adsorption of target molecules brought by the nest-shaped CNTs structure.     

SERS activity of gas-evaporated silver particles

We have produced silver particles by the gas-evaporation technique and investigated their SERS activity. The enhancement factor is determined quantitatively by measuring the Raman intensity of copper phthalocyanine molecules deposited onto the particle layer. It is shown that the particle layer is a good SERS enhancer, which yields an enhancement of ～ 4 × 10³. It is also shown that a five-fold increase in the enhancement factor is obtained, when the particle layer is coated with a 30 nm silver film. The enhancement presently observed seems to arise from the electromagnetic effects, namely, the excitation of localized surface plasmons for the bare particle layer and that of extended surface plasmons for the silver-coated particle layer.     

Foundations of Plasmonics

Plasma physics is a very mature field, studied extensively for well over a century. The cross-disciplinary field of plasmonics (electromagnetics of metallic nanostructures), on the other hand, with its potential for an extraordinary light control through novel class of materials and the resulting applications, has become very fashionable only recently. Inevitably, as a result of this rapid development, the deep connections with the mother discipline, the plasma physics, have sometimes been overlooked. The goal of this work is to review some of these basic connections, which are relevant, and ultimately helpful for researchers in the new field. We focus on the solid-state structured plasmas and address the issue of classical versus quantum treatments. We discuss the little known subtleties of the surface plasmons at metallic surfaces (e.g. multipole plasmons) and their consequences on plasmonics of the textured metallic films. Plasmonics of nanoparticles has been preceded by studies of plasma effects in metallic clusters and semiconducting quantum dots (QDs). In this context, we discuss the little known connection between the Mie resonance in metallic particles and the collective resonance in wide parabolic quantum wells (QWs) and QDs. Researchers dealing with plasmonics of thin films can benefit from earlier studies of plasmons in the semiconductor modulation doped heterojunctions and QWs, with its rich spectrum of intersubband and two-dimensional plasmons. In non-equilibrium plasmonic systems, generation of plasmons can be stimulated, leading to the exciting possibility of the plasmon instability. Extraordinarily complex is the plasmonics of carbon nanotubes and graphene, with its numerous van Hove, one- and three-dimensional plasmons, and we discuss how the plasmonics of metamaterials can benefit from this complexity. Finally, we discuss a few applications, which could directly benefit from plasmonics, including medical and the novel class of solar cells.     

Investigation on SERS of different phase structure TiO2 nanoparticles

In this paper, anatase and rutile TiO₂ nanoparticles as well as their mixed crystal phase structure TiO₂ nanoparticles were synthesized by a sol‐hydrothermal method, and were served as active substrates for surface‐enhanced Raman scattering (SERS) study. The results show that the 4‐mercaptobenzoic acid probe molecules exhibit different degree SERS enhancements on the surface of different phase structure TiO₂ nanoparticles. The mixed crystal structure TiO₂ with an appropriate proportion of anatase and rutile phase is favourable to SERS enhancement of adsorbed molecules. These are mainly attributed to the contributions of the TiO₂‐to‐molecule charge transfer mechanism and the mixed crystal effect. Copyright © 2015 John Wiley & Sons, Ltd.     

Chemical and structural properties of ternary post-transition metal oxide thin films: InZnO,InGaO and GaZnO

The chemical states of ternary post-transition metal oxide thin films of InGaO, GaZnO and InZnO were investigated using X-ray photoelectron spectroscopy. Detailed binding energy (BE) analyses revealed certain evolution in chemistry in the ternary oxides compared to the reference binary oxides of In₂O₃, ZnO, or Ga₂O₃. In particular, O 1s BEs were changed with the compositions, which suggests that the charge transfer (CT) between In³⁺/Ga³⁺/Zn²⁺ and O²⁻ ions is significant. Results of extended X-ray absorption fine structure analyses further showed that the first shell coordination (cation–O bond) is roughly maintained even though the ternary oxide films were structurally disordered. This implies that the CT process via O²⁻ ions can influence the charge reconstructions in the ternary oxide systems.     

量子等离激元管中窥豹

等离激元是金属中自由电子的集体振荡,其在物理,生物、化学、能源、信息等领域具有重要的应用前景.近些年来对等离激元量子效应研究的深入开展使得等离激元研究迈入了新阶段.本文首先简要介绍了等离激元的两个基本特性:光压缩效应和局域电场增强效应;随后回顾了量子等离激元方面的最新的进展,包括量子纠缠效应,量子尺寸效应,量子遂穿效应,等离激元在台阶势垒处的反射与激发,等离激元对电子相干效应的增强;最后对量子等离激元研究进行了总结和展望.     

Diamine-linked array of metal (Au,Ag) nanoparticles on glass substrates for reliable surface-enhanced Raman scattering (SERS) measurements

Metal (Au, Ag) nanoparticles (M NPs) (ca. 30–40 nm) prepared by citrate reduction method were arrayed on amine-terminated glass substrates using diamine linkers with different chain lengths. 1,4-diaminobutane (C-4 diamine) produced the uniform and densely-packed array of M NPs on glass substrates at appropriate concentration ranges, whereas diamine linkers with longer chain lengths (C-8 and C-12 diamines) produced more heterogeneous and aggregated array of M NPs. When compared to Ag NPs, Au NPs demonstrated more controllable and higher packing density due to their mono-dispersed size and higher affinity to diamine linkers. Uniformly arrayed M NPs (Au, Ag) on glass substrates exhibited high enhancement factors in SERS measurements of o-chlorothiophenol probes. Au NPs arrayed substrates exhibited an approximate power-law linearity of Raman intensity with probe concentrations (from 10⁻⁷ M to 10⁻⁴ M), demonstrating more reliable SERS substrates than Ag arrayed substrates with higher SERS activity.     

液相法制备金属纳米粒子

液相法是在均相溶液中，利用各种途径引发化学反应，通过均相或异相成核及随后的扩散生长而制备出粒径分布窄且表面功能化的纳米尺度材料．介绍了液-液两相法、反相胶束、高温液相法等制备单分散金属纳米粒子的方法和高温液相法制备金属纳米粒子的影响因素，以及近年来在金属纳米粒子的制备和性能研究上的进展，尤其是Co等多种磁性纳米粒子的制备、磁性研究．