A controlled and reproducible pathway to dye-tagged, encapsulated silver nanoparticles as substrates for SERS multiplexing

Silver nanoparticles tagged with dyes and encapsulated within a silica layer, offer a convenient potential substrate for performing multiplexed surface-enhanced Raman scattering (SERS) analysis. In contrast to our earlier work with gold particles, aggregation of silver particles is found to be mostly independent of dye addition, allowing for a reproducible preparation in which aggregation is actively induced by the addition of NaCl. Separating the aggregation step eliminates competitive binding between the dyes and silica-coating reagents, enabling the efficient use of a wide variety of weakly binding dyes to conveniently generate robust, high-intensity SERS substrates at a variety of excitation frequencies.     

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。     

Synthesis and characterization of surface-enhanced Raman scattering tags with Ag/SiO2 core-shell nanostructures using reverse micelle technology

A novel simplified method for synthesis of surface-enhanced Raman scattering tags has been reported. This synthesis method is based on reverse micelle technique using Igepal CO-520 as a surfactant and the mixed solution of silver nitrate and rhodamine dyes with isothiocyanate group as water pool followed by hydrazine hydrate reduction and TEOS polymerization leading to the formation of silica layer surrounding the silver core. Compared to the method reported in literature, the proposed methodology eliminates the necessity of vitrophilic pretreatment and makes it possible to complete all different processes including the preparation of silver nanoparticles, the conjugation of dye molecules and the formation of silica shell in the microreactor. The nanoparticle-based surface-enhanced Raman tags obtained are composed of silver core conjugated with rhodamine dyes and an encasing silica shell. Both the dyes themselves and the Ag/SiO2 core-shell nanoparticles without the encapsulation of dyes exhibit no Raman signals. However, the Ag/SiO2 core-shell nanoparticles exhibit strong Raman signals when encapsulated with these dyes. This is due to the appearance of fluorescence quenching and surface-enhanced Raman scattering effect resulting from the conjugation of dyes and silver core. The Raman tags were characterized using transmission electron microscopy (TEM), UV-visible absorption spectrometry, and Raman spectrometry.     

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.     

Ag|kCl|六氢吡啶体系表面增强喇曼散射效应的猝灭和恢复

在简述近年来电化学体系中表面增强喇曼散射(SERS)活性位置研究的实验结果和有关论述后, 着重报道作者在Ag/KCl/六氢吡啶体系中, Ag-Cl振动峰和六氢吡啶诸振动峰的强度, 在一定电位范围内电极被施加负脉冲电位后的同步下降, 以及采用氧化还原循环(ORC)处理得到同步恢复等新的实验结果, 并对上述体系中表面络合物的构成及其在SERS中的作用作了进一步的论证。     

Phospholipid membrane encapsulation of nanoparticles for surface-enhanced Raman scattering

Lipid-encapsulated surface-enhanced Raman scattering (SERS) nanoparticles, with promising applications in biomedical diagnostics, were produced. Gold nanoparticles, 60 nm in diameter, were coated with a ternary mixture of DOPC, sphingomyelin, and cholesterol. The lipid layer is versatile for engineering the chemical and optical properties of the particles. The stability of the lipid-encapsulated particles is demonstrated over a period of weeks. The versatility of the layer is demonstrated by the incorporation of three different Raman-active species using three different strategies. The lipid layer was directly observed by TEM, and the SERS spectrum of the three dye species was confirmed by Raman spectroscopy. UV-vis absorption and dynamic light scattering provide additional evidence of lipid encapsulation. The encapsulation is achieved in aqueous solution, avoiding phase transfer and possible contamination from organic solvents. Furthermore, when fluorescent dye-labeled lipids were employed in the encapsulant, the fluorescence and SERS activity of the particles were controlled by the use of dissolved ions in the preparation solution.     

Resonance-enhanced Raman scattering by aggregated 2,2′-cyanine on colloidal silver

The Raman scattering spectrum of 2,2′-cyanine on colloidal silver metal particles is discussed. Preliminary assignments of some of the vibrational Raman bands to the motions of specific chromophoric units are presented and multiplet character of some bands is discussed. Enhanced Raman scattering of 2,2′-cyanine occurs when the laser radiation is tuned to the J-aggregate absorption feature at 575 nm. The enhancement in Raman intensity is the result of a diminution of fluorescence intensity, as well as a quantitative increase in Raman scattering intensity, and is distinct from other types of enhancement phenomena (e.g., resonance Raman of monomeric solution dye, and surface-enhanced Raman scattering (SERS)). The resonance Raman enhancement, due to excitation at the frequency corresponding to the J-aggregate absorption, is found to be 2 × 10⁺³.     

Concentration-dependent surface-enhanced Raman scattering of 2-benzoylpyridine adsorbed on colloidal silver particles

Surface-enhanced Raman scattering (SERS) of 2-benzoylpyridine (2-BP) adsorbed on silver hydrosols has been investigated. It has been observed that with a small change in the adsorbate concentration, the SER spectra of 2-BP show significant change in their features, indicating different orientational changes of the different part of the flexible molecule on the colloidal silver surface with adsorbate concentration. The time dependence of the SER spectra of the molecule has been explained in terms of aggregation of colloidal silver particles and co-adsorption and replacement kinetics of the adsorbed solute and solvent molecules on the silver surface. The broad long-wavelength band in the absorption spectra of the silver sol due to solute-induced coagulation of colloidal silver particles is found to be red-shifted with the increase in adsorbate concentration. The surface-enhanced Raman excitation profiles indicate that the resonance of the Raman excitation radiation with the new aggregation band contributes more to the SERS intensity than that with the original sol band.     

Effect of laser illumination oxidation-reduction cycles upon surface-enhanced Raman scaterring from silver electrodes

The intensity of surface-enhanced Raman scattering (SERS) from thiocyanate and chloride adsorbed on silver electrodes is shown to depend critically on whether the electrode is illuminated during the oxidation-reduction cycle used to pretreat the electrode. The value and magnitude of the photoeffect is dependent upon the type of surface vibrational mode, the adsorbate and the wavelength of the radiation during the ORC. The effects are attributed to the production of SERS active clusters of Ag atoms by photoreduction of the Ag(I) phase films during the ORC.     

银纳米微球和银纳米棒自组装膜的制备及SERS研究

采用硼氢化钠还原硝酸银,用振荡器在不同转速下振荡得到单分散的银纳米微球和银纳米棒,再将银纳米微球及银纳米棒自组装于被3-氨丙基-三甲氧基硅烷(APTMS)修饰的玻璃基片上,制得了具有表面增强拉曼(SERS)活性的基底,分别以罗丹明6G(R6G)和罗丹明B(RB)为探针分子对这两种基底进行SERS活性检测,结果发现这两种基底均为较理想的SERS衬底。     

Silver Nano Islands Enhanced Raman Scattering on Large Area Grating Substrates Fabricated by Two Beam Laser Interference

The authors preparedlarge area surface-enhanced Raman scattering(SERS) active substrates with tunable enhancement. First the large area gratings were fabricated by scanning a photoresist with two-beam laser interference and subsequently they were coated with silver nano islands via vacuum evaporation. SERS active metal island grating substrates with four different periods(300, 400, 515 and 600 nm) and Ag nano islands uniformly coated on an area of 2.5 cm×0.5 cm were obtained. The measured SERS spectra reveal the tuning effect of the period on the Raman signals period. The highest enhancement(ca. 10⁵) for Rhodamine 6G(R6G) as probing molecule is associated with a period of 515 nm due to the perfect matching of surface plasmons and Raman excitation line. A good reproducibility of SERS signals with almost the same SERS intensity at different spots was observed on all the larger area Ag island grating substrates.     

Vibrational spectra of isomeric pyridinic carboxylic acids in solid state and in solution and their SERS studies in silver sol

Raman spectroscopic studies of three isomeric pyridinic carboxylic acids, viz. picolinic, nicotinic and iso-nicotinic acid in solid state, in aqueous solution and in silver hydrosol, in the frequency range 900–1750 cm⁻¹, have been made. Assignments of the observed bands have been proposed in relation to the molecular forms present in solid state and in solution. Different degrees of intensity enhancements of the Raman bands in surface-enhanced Raman scattering (SERS) have been observed in all the three isomeric molecules. In iso-nicotinic acid, the intensity enhancement has been found to be minimum. Comparisons of Raman spectra in aqueous solution with those due to SERS in silver sol indicate that picolinic and nicotinic acid adsorb perpendicularly to the sol surface whereas in iso-nicotinic acid it occurs via donation of a π-electron of the aromatic ring, i.e. the plane of the ring lies parallel to the surface of the sol.     

A facile chemical approach for preparing a SERS active silver substrate

This communication describes a new surface-enhanced Raman scattering (SERS) active silver substrate prepared by iodination of the evaporated silver foil. After iodination, the morphology of the silver substrate undergoes a self-evolution process in which it displays accordingly the UV-vis absorption shift as well as the AFM topological test. Rhodamine 6G (R6G) is used as the probe molecule to evaluate the enhancement efficiency of the silver substrate at different self-evolution time intervals. The SERS intensity of R6G increases up to ～29-fold and reaches a maximum after the substrate evolved for 24 h. This method is feasible for the production of an efficient SERS silver substrate.     

Single-step multiplex detection of toxic metal ions by Au nanowires-on-chip sensor using reporter elimination

We have developed a Au nanowires (NWs)-on-chip surface-enhanced Raman scattering (SERS) multiplex sensor that can sensitively detect multiple toxic metal ions. Most importantly, the reporter elimination method simplified the detection procedure to a single step, which has been much desired for remote environmental monitoring. This sensor has several notable features. First, it shows high reproducibility based on well-defined single-crystalline Au NWs. Second, single-NW-sensors that can detect a specific metal ion are combined for multiplex sensing of metal ions. Third, when a sample solution is put onto the NWs-on-chip sensor, a decrease in the SERS signal of a specific NW-sensor identifies the target metal ion. Simple, rapid, sensitive and quantitative detection of metal ions becomes possible through the measurement of the SERS signals. We successfully detected ions of mercury (Hg(2+)), silver (Ag(+)), and lead (Pb(2+)) coexisting in the same solution by using this sensor.     

Ag/Si-NPA基底上共吸附R6G和CV的表面增强拉曼散射

以硅纳米孔柱阵列(Si-NPA)为基底, 采用浸渍沉积技术制备了具有较高表面增强拉曼散射(SERS)活性的Ag/Si-NPA衬底, 并采用扫描电子显微镜和透射电子显微镜对其表面形貌和结构进行了表征. 在此基础上, 选择罗丹明6G(R6G)和结晶紫(CV)2种生物染料分子并采用不同的混合吸附程序对其共吸附状态下的SERS光谱进行了探测. 结果表明, 当2种分子的溶液浓度均为10^-7 mol/L时, 无论采用何种浸渍吸附程序, 其SERS谱中CV的特征拉曼峰都被R6G完全掩盖. 对溶液采用错级配置(R6G和CV的浓度分别为10^-9和10^-7 mol/L)后, 所测SERS谱上获得了分别对应于R6G和CV的分离良好、相对强度匹配、分辨率高的2个SERS特征峰组, 从而有利于简化现实混合探测过程中对SERS特征峰的指认和判断.     

The solvent trapping or co-adsorbing effect during the self-assembly monolayer studied by surface-enhanced Raman scattering

The possibility of solvent molecules being trapped within the monolayer interior during the self-assembly of 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecules from alcoholic solution, or co-adsorbing together with the solute molecules onto the silver surface was verified by means of surface-enhanced Raman scattering (SERS). Variations of the relative intensity of the solvent bands to the concentrations of the solution were investigated. To a certain range of the concentration, the smaller the concentration is, the larger the relative intensity of the solvent bands is. A new method for obtaining the SERS spectra of the organic compounds that are insoluble in water was developed in our laboratory, which also provides further evidence for the solvent trapping or co-adsorbing effect.     

CHEMICALLY DEPOSITED SILVER FILM USED AS A SERS-ACTIVE OVER-COATING LAYER FOR POLYMER FILM*

When colloidal silver particles were chemically deposited onto polymer film as an over-coating layer, surface-enhanced Raman scattering (SERS) spectra could be collected for the surface analysis. SERS measurements of liquid crystalfilm were successfully performed without disturbing the surface morphology.     

Surface-enhanced Raman spectroscopy of free bilirubin and bilirubin complexes with transition metals iron(II), nickel(II) and cobalt(II)

The surface-enhanced Raman scattering (SERS) spectra of free bilirubin and bilirubin complexes with transition metals [iron(II), nickel(II) and cobalt(II)] are investigated on colloidal silver. Free bilirubin is found to be adsorbed on colloidal silver at the lactam and dicarboxylate oxygens. The addition of some transition metal ions results in rapid, square planar complex formation and the complex ratio of bilirubin with the metal ion is 1:1.