Controllable Silver Plating on Silica for Surface-enhanced Raman Scattering

We proposed a facile and rapid method for preparing silica-silver core-shell(SSCS) substrates to use Ag electroless plating on SiO2@Au-seed particles.UV-Vis-NIR absorption spectrometer and SEM were employed to monitor the reaction process of the formation of Ag on the surfaces of silica beads,and the optical resonance of the substrate could shift from visible to NIR region.It has been found that surface-enhanced Raman scattering(SERS) enhancement changes with the electroless plating time and the SSCS substr...     

Correlation of surface-enhanced Raman spectroscopy and laser desorption-ionization mass spectrometry acquired from silver nanoparticle substrates

Applying complementary experiments, like laser desorption-ionization mass spectrometry (LDI-MS) and confocal surface-enhanced Raman microscopy, to the same physical sample location has the potential to elucidate the behavior of complex chemical and biochemical systems in ways that are not available to either method applied in isolation. In these experiments surface-enhanced Raman scattering (SERS) and LDI-MS are applied to the same sample spot using a common structure, deposited Ag colloids, both as ionization matrix and simultaneously as enhancing media for surface-enhanced Raman scattering of small organic molecules, dyes and lipids, and the behavior is compared. Three compounds-p-aminothiophenol (ATP), rhodamine 6G and cholesterol-which exhibit different strengths of interaction with Ag are examined in detail by correlated SERS and LDI-MS. The related mechanisms of nanoparticle-assisted desorption-ionization and Raman enhancement are explored by correlating mass and Raman spectra. The correlated spectra highlight the manner in which the different test compounds interact with plasmonic metal nanostructures. These coupled studies yield new insight into the transition of analyte from the metal-solution interface to gaseous ions, including, in the case of organothiols, a rich set of mixed clusters that provide chemical insight into the ion formation process.     

Gold nanoparticles assembling on smooth silver spheres for surface-enhanced Raman spectroscopy

A simple and cost-effective chemical method was introduced to assemble gold (Au) nanoparticles on smooth silver (Ag) spheres for realizing surface-enhanced Raman scattering (SERS) enhancement by the replacement reaction between chloroauric acid and Ag spheres. In addition, the Ag-Au core-shell spheres were fabricated when a certain amount of chloroauric acid was used in the reaction solution. We found that the Ag particles decorated with small Au nanoparticles demonstrated the strongest SERS enhancement, while Ag-Au core-shell spheres showed the weakest enhancement.     

Synthesis, characterization, and 3D-FDTD simulation of Ag@SiO2 nanoparticles for shell-isolated nanoparticle-enhanced Raman spectroscopy

Au-seed Ag-growth nanoparticles of controllable diameter (50-100 nm), and having an ultrathin SiO(2) shell of controllable thickness (2-3 nm), were prepared for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Their morphological, optical, and material properties were characterized; and their potential for use as a versatile Raman signal amplifier was investigated experimentally using pyridine as a probe molecule and theoretically by the three-dimensional finite-difference time-domain (3D-FDTD) method. We show that a SiO(2) shell as thin as 2 nm can be synthesized pinhole-free on the Ag surface of a nanoparticle, which then becomes the core. The dielectric SiO(2) shell serves to isolate the Raman-signal enhancing core and prevent it from interfering with the system under study. The SiO(2) shell also hinders oxidation of the Ag surface and nanoparticle aggregation. It significantly improves the stability and reproducibility of surface-enhanced Raman scattering (SERS) signal intensity, which is essential for SERS applications. Our 3D-FDTD simulations show that Ag-core SHINERS nanoparticles yield at least 2 orders of magnitude greater enhancement than Au-core ones when excited with green light on a smooth Ag surface, and thus add to the versatility of our SHINERS method.     

Interfacial deposition of Ag on Au seeds leading to AucoreAgshell in organic media

A seed mediated procedure for the synthesis of hydrophobic Au(core)Ag(shell) nanoparticles in toluene is demonstrated. The reaction proceeds by way of the interfacial reduction of silver ions by 3-pentadecylphenol followed by their deposition on hydrophobized Au nanoparticles. Such a hitherto unreported interfacial seeded growth reaction leads to the formation of phase pure Au(core)Ag(shell) nanoparticles that retain the hydrophobicity of the seed particles and remain stable in toluene. Such core-shell structures are however not formed in the aqueous phase. The core-shell architecture was verified using TEM analysis and the formation process was studied by recording the UV-vis spectra of the organic phase nanoparticles as a function of time. TEM kinetics also showed gradual increase in the silver layer thickness. Conclusive evidence was however obtained on examination of the HRTEM images of the products formed. Elemental analysis using X-ray photoelectron spectroscopy of the Au(core)Ag(shell) nanostructure revealed the presence of metallic silver. Moreover changing the surface capping of the Au seed does not affect the formation of the Au(core)Ag(shell) nanostructure.     

Bimetallic (Ag)Au nanoparticles prepared by the seed growth method: two-dimensional assembling, characterization by energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and surface enhanced raman spectroscopy, and proposed mechanism of growth

Layered core-shell bimetallic silver-gold nanoparticles were prepared by overdeposition of Au over Ag seeds by the seed-growth method using tetrachloroauric acid, with hydroxylamine hydrochloride as the reductant. The effects of pH, reduction rate, and seeding conditions on the morphology and surface plasmon extinction of the bimetallic nanoparticles were investigated. Nanoparticles prepared by a rapid reduction in the neutral ambient and assembled into two-dimensional nanoparticulate films by adsorption of 2,2'-bipyridine were characterized by energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, surface-enhanced Raman scattering spectroscopy, and transmission electron microscopy. The results are consistent with Ag core and Ag/Au-alloyed shell composition of the nanoparticles. Evidence of the presence of Ag on the surface of the nanoparticles, of enrichment of the Ag/Au alloy shell by Ag toward or at the nanoparticle surface, and of modification of the nanoparticle surface by adsorbed chlorides is also provided. Reduction of the size of the Ag seeds, alloying of Ag and Au in the shell of the nanoparticles, and modification of their surfaces by adsorbed chlorides are tentatively attributed to positive charging of the nanoparticles during the electrocatalytic overdeposition of Au over Ag seeds.     

Effect of pH on the synthesis and properties of luminescent SiO2/calcium phosphate:Eu3+ core-shell nanoparticles

A novel method for the synthesis of luminescent SiO(2)/calcium phosphate (CaP):Eu(3+) core-shell nanoparticles (NPs) was developed via a sol-gel route followed by annealing at a temperature of 800 °C. The object of this study was the investigation of the effect of pH on the formation of a CaP shell around the silica core. The resulting annealed NPs exhibited an amorphous SiO(2) core and a crystalline luminescent shell. The formation of a CaP layer was possible at pH below 4.5 and above 6.5 during the coating step. The crystal structure of the shell was studied by X-ray diffraction analysis. Hydroxyapatite (HAp) and α-tricalcium phosphate were detected as crystal phases of the surrounding layer. However, NPs produced under basic conditions exhibited a higher crystallinity of the CaP layer than did samples coated at pH below 4.5. In the pH interval between 4.5 and 6.5, no shell growth but the formation of secondary NPs containing CaO and Ca(OH)(2) was observed. Furthermore, SiO(2)/CP:Eu(3+) core-shell NPs were investigated by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy. The resulting HAp-coated NPs were successfully tested by a cell-culture-based viability assay with respect to a later application as a luminescent marker for biomedical applications.     

基于Au/SiO2纳米粒子的结晶紫表面增强拉曼特性研究

采用自组装-化学镀法制备了以SiO2为核,Au为壳层的核壳结构纳米粒子(Au/SiO2),以生物染色剂结晶紫为探针分子,研究了Au/SiO2的表面增强拉曼散射(SERS)效应,并考察了Cl-对SERS增强效应的影响。实验表明,Cl-对SERS有明显的增强效果,这主要是由于Cl-的加入使得Au/SiO2发生团聚,产生大量"热点",从而使SERS增强效果进一步加强。以Au/SiO2(5×1010 mL-1)为活性基底,KCl(0.01 mol/L)为额外增强剂,在水溶液中实现了对结晶紫(CV)的痕量检出,最低检测浓度可达到5×10-10mol/L。     

Surface-enhanced Raman scattering measurements on silver nanoparticles covered with differently formed platinum films

Gold and silver electromagnetic nanoresonators covered by a thin layer of platinum are often used to study adsorption of various molecules on “model platinum surfaces” with surface-enhanced Raman scattering (SERS) spectroscopy. In this contribution spectra of pyridine adsorbed on films formed from core–shell Ag@Pt and Ag@Ag–Pt nanoparticles and pure Pt or Ag nanoparticles were measured using a confocal Raman microscope. The SERS spectra of pyridine adsorbed on alloy Ag@Ag–Pt nanoparticles could not be obtained as a linear combination of spectra measured on pure Ag and Pt surfaces. In other words, for silver electromagnetic nanoresonators covered by platinum there is no simple correlation between the “quality” of the deposited Pt layer and the relative intensity of SERS bands characteristic for adsorbate interacting with silver. The SERS spectra accumulated from various places of a film formed from Ag@Pt or Ag@Ag–Pt nanoclusters may differ significantly. Using Ag@Pt nanoparticles with practically negligible amount of Ag on the surface (as per the stripping measurement), it is possible to record SERS spectrum in which the contribution characteristic for pyridine adsorbed on the Ag surface is well visible. It means that, even for macroscopic samples of core–shell Ag–Pt nanoparticles, averaging of many spectra measured at various locations of the sample should be carried out to characterize reliably their properties.     

Synthesis and optical properties of three-dimensional porous core-shell nanoarchitectures

Three-dimensional porous core-shell nanostructures consisting of gold skeletons and silver shells were fabricated by controllable electroless plating. Optical properties of the 3D nanocomposite with a heterogeneous interface exhibit a significant shell-thickness dependence. The porous core-shell structure with an optimized shell thickness of approximately 3-5 nm exhibits a considerable improvement in surface-enhanced Raman scattering. This study has important implications in the functionalization of nanoporous metals by surface modification.     

Facile synthesis of silver core - silica shell composite nanoparticles

Combining metal nanoparticles and dielectrics (e.g. silica) to produce composite materials with high dielectric constant is motivated by application in energy storage. Control over dielectric properties and their uniformity throughout the composite material is best accomplished if the composite is comprised of metal core - dielectric shell structured nanoparticles with tunable dimensions. We have synthesized silver nanoparticles in the range of 40-100nm average size using low concentration of saccharide simultaneously as the reducing agent and electrostatic stabilizer. Coating these silver particles with silica from tetraalkoxysilanes has different outcomes depending on the alcoholic solvent and the silver particle concentration. A common issue in solution-based synthesis of core-shell particles is heterogeneous nucleation whereupon two populations are formed: the desired core-shell particles and undesired coreless particles of the shell material. We report the formation of Ag@SiO(2) core-shell particles without coreless silica particles as the byproduct in 2-propanol. In ethanol, it depends on the silver surface area available whether homogeneous nucleation of silica on silver is achieved. In methanol and 1-butanol, core-shell particles did not form. This demonstrates the significance of controlling the tetraalkoxysilane hydrolysis rate when growing silica shells on silver nanoparticles.     

Electrochemical deposition of silver nanoparticles in multiwalled carbon nanotube-alumina-coated silica for surface-enhanced Raman scattering-active substrates

The work presents a novel surface-enhanced Raman scattering (SERS)-active surface prepared by electrochemical deposition of silver nanoparticles in multiwalled carbon nanotube (MWCNT)–alumina-coated silica (ACS) nanocomposite. The formation of Ag nanoparticles in MWCNT–ACS nanocomposite was investigated by scanning electron microscopy. It shows that Ag nanoparticles with a diameter of about 100–200 nm in the MWCNT–ACS nanocomposite and some Ag nanoparticles aggregated to form interconnected aggregates. The Ag–MWCNT–ACS-coated indium tin oxide substrate has a considerable effect on the Raman spectra with improvements of more than four times of magnitude as compared with the Ag-coated indium tin oxide substrate. The present methodology demonstrates that the composite composed of Ag, MWCNT, and ACS is suitable for potential plasmonic devices.     

内部具有可移动金核的中空银纳米颗粒的制备、表征及其表面增强拉曼效应

采用振荡法和种子生长技术制备出核壳结构的Au@SiO2纳米颗粒及夹层结构的Au@SiO2@Ag纳米颗粒, 用HF将Au@SiO2@Ag NPs夹层的SiO2溶解, 得到内部带有粒径为30 nm的可移动金核、壳层厚度约为30 nm的中空银纳米颗粒(Au@air@Ag NPs). 用扫描电子显微镜和透射电子显微镜对所得到的纳米微球的形貌进行了表征, 并以罗丹明B为探针分子研究了Au@air@Ag 纳米颗粒的表面增强拉曼(SERS)效应, 发现Au@air@Ag 纳米颗粒是一种可应用于SERS的理想材料.     

Synthesis of multifunctional metal- and metal oxide core@mesoporous silica shell structures by using a wet chemical approach

We demonstrate a facile wet chemical approach for fabricating spherical metal/metal-oxide core@mesoporous silica shell hybrid nanoparticles with different core and shell thicknesses. Vertically aligned mesoporous silica (mSiO(2) ) shells were fabricated over the pre-synthesized spherical SiO(2) nanoparticles through a three-step strategy: 1)?synthesis of core materials, 2)?covering the core with an organic-inorganic composite layer, and 3)?removing the organic template through calcinations in air. The mechanisms of hybrid structure formation are proposed. The multifunctional nature of the hybrid structures could be induced by incorporating guest ions/molecules, such as Ag, Mn, and TiO(2) , into the pores of an mSiO(2) shell. Mn and TiO(2) cluster- incorporated composite structures have been tested to be antioxidizing agents and effective photocatalysts through electron spin resonance, radical scavenging tests, and the photocatalytic degradation of rhodamine B. The possibility of incorporating several hetero-element guest clusters in these mesoporous composite particles makes them highly attractive for multifunctional applications.     

Synthesis of p-aminothiophenol-embedded gold/silver core-shell nanostructures as novel SERS tags for biosensing applications

We describe a novel surface-enhanced Raman scattering (SERS) tag that is based on Au/Ag core-shell nanostructures embedded with p-aminothiophenol. The Au/Ag core-shell sandwich nanostructures demonstrate bright and dark stripe structure and possess very strong SERS activity. Under optimum conditions, the maximum SERS signal was obtained with a 10?nm thick Ag nanoshell, and the enhancement factor is 3.4?×?10⁴ at 1077?cm^?1. After conjugation to the antibody of muramidase releasing protein (MRP), the Au/Ag core-shell nanostructures were successfully applied to an SERS-based detection scheme for MRP based on a sandwich type of immunoassay.

A two-color-change, nanoparticle-based method for DNA detection

Herein, we describe the detailed synthesis of Ag/Au core-shell nanoparticles, the surface-functionalization of these particles with thiolated oligonucleotides, and their subsequent use as probes for DNA detection. The Ag/Au core-shell nanoparticles retain the optical properties of the silver core and are easily functionalized with thiolated oligonucleotides due to the presence of the gold shell. As such, the Ag/Au core-shell nanoparticles have optical properties different from their pure gold counterparts and provide another “color” option for target DNA-directed colorimetric detection. Size-matched Ag/Au core-shell and pure gold nanoparticles perform nearly identically in DNA detection and melting experiments, but with distinct optical signatures. Based on this observation, we report the development of a two-color-change method for the detection and simultaneous validation of single-nucleotide polymorphisms in a DNA target using Ag/Au core-shell and pure gold nanoparticle probes.     

Bifunctional AgCl/Ag composites for SERS monitoring and low temperature visible light photocatalysis degradation of pollutant

With the assistance of Polyvinylpyrrolidone (PVP), AgCl/Ag composites were fabricated in N, N-Dimethylformamide (DMF) solvent via a photoactivated route. The size of AgCl particles was in the range of 500 nm to 1 μm and the Ag particle's diameter was about 10–20 nm. Different from those core–shell structures reported before, the Ag nanoparticles were dispersed uniformly both on the surface and in the body of AgCl particles. The generation of such kind of composites was resulted from the reducing ability of DMF and light irradiation during the formation of AgCl particles. The as-obtained AgCl/Ag composites presented great activity for both surface-enhanced Raman scattering (SERS) detection and visible light photocatalytic degradation of organic dyes. Additionally, the AgCl/Ag composites could maintain high photocatalytic activity even though the ambient temperature was as low as 15 °C and recycle photocatalysis experiments indicated that the photocatalyst exhibited higher stability. Such kind of AgCl/Ag composites holds great potential for environmental monitoring devices and pollutant treatments.     

Biocompatible core-shell nanoparticle-based surface-enhanced Raman scattering probes for detection of DNA related to HIV gene using silica-coated magnetic nanoparticles as separation tools

A novel, highly selective DNA hybridization assay has been developed based on surface-enhanced Raman scattering (SERS) for DNA sequences related to HIV. This strategy employs the Ag/SiO₂ core-shell nanoparticle-based Raman tags and the amino group modified silica-coated magnetic nanoparticles as immobilization matrix and separation tool. The hybridization reaction was performed between Raman tags functionalized with 3′-amino-labeled oligonucleotides as detection probes and the amino group modified silica-coated magnetic nanoparticles functionalized with 5′-amino-labeled oligonucleotides as capture probes. The Raman spectra of Raman tags can be used to monitor the presence of target oligonucleotides. The utilization of silica-coated magnetic nanoparticles not only avoided time-consuming washing, but also amplified the signal of hybridization assay. Additionally, the results of control experiments show that no or very low signal would be obtained if the hybridization assay is conducted in the presence of DNA sequences other than complementary oligonucleotides related to HIV gene such as non-complementary oligonucleotides, four bases mismatch oligonucleotides, two bases mismatch oligonucleotides and even single base mismatch oligonucleotides. It was demonstrated that the method developed in this work has high selectivity and sensitivity for DNA detection related to HIV gene.     

Au/Ag核-壳结构纳米粒子的制备及其SERS效应

随着大量有关表面增强拉曼散射 (SERS)的实验和理论研究的开展 ,金属纳米粒子作为一类重要的 SERS增强介质 ,已引起了人们浓厚的研究兴趣 [1] .而 Au和 Ag作为最常用的活性基底物质 ,更是研究的热点 [2 ,3 ] .最近 ,美国印第安那大学的 Nie等 [4 ] 在单个银纳米粒子上 ,观察到高达 1 0 14 ～ 1 0 15的SERS因子 .同时 ,他们的另外一项工作表明银纳米粒子的形状和大小对 SERS活性有很大影响 [5] .但是 ,由于 Ag溶胶制备的重复性较差 ,且粒度分布不均匀 ,通过控制银颗粒大小而调控 SERS活性是相当困难的[6] .与 Ag相比 ,Au在可见光…