Surface-enhanced Raman spectroscopic investigation on adsorption kinetic of carbon monoxide at the solid-gas interface.

A molecular-level understanding of CO adsorption behavior would be greatly beneficial to resolving the problem of CO poisoning in fuel cells and medical science. Herein, an efficient borrowing strategy based on surface enhanced Raman scattering (SERS) has been developed to investigate the adsorption behavior of CO at the gas-solid interface. A composite SERS substrate with high uniformity was fabricated by electrochemical deposition of optimal Pt over-layers onto an Au nanoparticle film. The results indicated that the linearly bonded mode follows the Langmuir adsorption curve (type I), while the multiply bonded did not. It took a longer time for the C-OM vibration to reach the adsorption equilibrium than that of C-OL. The variation tendency toward the Pt-COL frequency was in opposition to that of C-OL, caused by the chemical and dipole-dipole coupling effects. The increase in dynamic coupling effects of the CO molecules caused a blue shift in νCO and a red shift of the Pt-CO band, while its shielding effect on SERS intensity cannot be ignored. Additionally, higher pressure is more conducive for linear adsorption to achieve saturation. Density functional theory calculations were employed to explore the adsorption mechanisms. It should also be noted that the substrate with good recycling performance greatly expands its practical application value. The present study suggested that the SERS-based borrowing strategy shows sufficient even valuable capacity to investigate gas adsorption kinetics behavior.

Self-Assembled Large-Scale Monolayer of Au Nanoparticles at the Air/Water Interface Used as a SERS Substrate.

Self-assembly of metal nanoparticles has attracted considerable attention because of its unique applications in technologies such as plasmonics, surface-enhanced optics, sensors, and catalysts. However, fabrication of ordered nanoparticle structures remains a significant challenge. Thus, developing an efficient approach for the assembly of large-scale Au nanoparticles films for theoretical studies and for various applications is highly desired. In this paper, a facial approach for fabricating a monolayer film of Au nanoparticles was developed successfully. Using the surfactant polyvinylpyrrolidone (PVP), a large-scale monolayer film of well-ordered, uniform-sized Au nanoparticles was fabricated at the air/water interface. The film exhibited a two-dimensional (2D) hexagonal close-packed (HCP) structure having interparticle gaps smaller than 2 nm. These gaps generated numerous uniform "hot spots" for surface-enhanced Raman scattering (SERS) activity. The as-prepared monolayer film could be transferred to a solid substrate for use as a suitable SERS substrate with high activity, high uniformity, and high stability. The low spot-to-spot and substrate-to-substrate variations of intensity (<10%), the large surface enhancement factor (∼10(6)), and the high stability (∼45 days) make the substrate suitable for SERS measurements. Transfer of the monolayer film onto a glassy carbon electrode produced an Au electrode with clean, well-defined nanostructure suitable for electrochemical SERS measurements. The adsorption process of ionic liquids on the electrode with the monolayer film is similar to that on bulk metal electrodes. The present strategy provides an effective way for self-assembly of Au nanoparticles into well-defined nanostructures that may form optimal reproducible SERS substrates for quantitative analysis. It also provides an electrode with clean, well-defined nanostructure for electrochemical investigations.

[Surface Enhanced Raman Spectroscopic Studies on the Coupling Effect of Multilayer Au@SiO2 Film].

The SiO2 shell with the thickness of 4 nm was attached onto high surface enhanced Raman spectroscopy (SERS) active Au core nanoparticles to obtain Au@SiO2 core shell nanoparticles by the hydrolysis of sodium silicate solution with the boiling water bath. The inert shell of SiO2 isolated the direct interaction of Au nanoparticles and probe molecules. The stable, compact and uniform monolayer nanoparticles film was self assembled at water/oil interface, and one to six monolayers film was transferred to Si wafer as SERS substrates through layer by layer technique. The relationship between the SERS activities and layers of the monolayer nanoparticles film on Si surface was investigated. The SERS mapping was developed to determine the layers of the Au@SiO2 film. The coupling effect among the Au@SiO2 films was explored by changing the adsorption location of the probe on the multilayer films. The result revealed that the monolayer film was a favourable candidate with high-quality performances for the SERS application. The SERS signal was distributed on the surface with high uniformity at the same monolayer film, and it was enhanced in the intensity with the increase in film layers. It reached the maximun intensity as the film was over five layers. It indicated that the SERS signal was contributed mainly by the first five monolayers. The probe molecules were immobilized onto the first monolayer nanoparticles film, and the SERS signal from the probe approached to the maximum as the second monolayer covered the probe modified first nanoparticles film. It was dominated by the coupling effect ("hot spots") of the adjacent layers. The SERS signal decreased in intensity when the third layer was transferred onto the second layer, and it disappeared after the fouth layer was covered, mainly duo to the shield of the nanoparticles film to the incident laser and Raman signal. The preliminary results provided guidance for fabricating optimal SERS substrates.

Magnetic separation of heavy metal ions and evaluation based on surface-enhanced Raman spectroscopy: copper(II) ions as a case study.

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p-Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface-enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface-enhanced Raman spectroscopy bands from p-mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions.

[Preparation of core-shell magnetic nanoparticles and its application in separation and spectral detection].

Magnetic nanoparticles as well as core-shell magnetic nanocomposites are of great interest for researchers due to their potential applications in lots of areas. In the present review, the authors summarized several universal synthetic methods of nanocomposites and their specific properties. In the following, the authors focused on the applications of functionalized magnetic nanoparticles in separation and spectral detection, along with the introduction of some work in the authors' lab. At last, the questions remaining in magnetic nanoparticles and the application perspectives of magnetic nanocomposites were discussed.

[Fabrication of reproducible surface enhanced Raman scattering substrate and its application].

Gold nanoparticles were homogeneously coated with silica using the silane coupling agent (3-aminopropyl)-trimethoxysilane to functionalize the gold surface and sodium silicate solution as the precursor of silica. The shell thickness could be well controlled by changing the amount of sodium silicate, reaction temperature and time. The Au@SiO2 core-shell nanoparticles with a suitable silica shell thickness exhibited optimal SERS activity and were self-assembled onto an ITO substrate in order to get a stable and reproducible SERS substrate. The conditions for preparing SERS substrates can be optimized by investigating the relationship between the intensity of SERS signals and the thickness of silica shell. The reproducible SERS measurements were performed by using 1,4-BDT and 4,4'-bipyridine as probe molecules. Within a certain concentration range, the linear relationship between the SERS intensities and the logarithm of concentration was obtained. The results revealed that the Au@SiO2 substrate assembled on ITO surface could be developed as a reproducible substrate for the quantitative analysis.

[Study of regeneration based on SERS labelled immunoassay].

Labelled immunoassay by surface enhanced Raman scattering (SERS) has great research and application value. It combines SERS which has the high sensitivity and high selectivity with specific adsorption in immunology. The present paper mainly studies the regeneration about SERS labelled immunoassay, striving to develop the recycling value of it. The authors used glycine-HCl eluent for the sandwich structure including solid matrix antibody, antigen and labelled immuno-gold colloids, then the authors had got expected result. The complex of antibody and antigen would be separated by changing the pH scale. It could elute the most antigen and the labelled immuno-gold colloids. Also the authors could assemble it again and distinguish the characteristic SERS spectrum of the reporter molecules. Under this condition, we researched the stability and reusing of this technology. The authors found that it has better stability and it retained activity after 10 recycles of applications.

[Self-assembly of two kinds of nanoparticles and their surface enhanced Raman spectroscopic study].

Two kinds of nanoparticles (gold nanoparticles and Au core Pt shell nanoparticles) on silicon surfaces which were silanization were electrostatically self-assembled. The density of nanoparticles was controlled by changing the time of the substrate immersed in colloids. The substrate was characterized by scanning electron microscope (SEM), and the results indicated that Au and Au@Pt particles were dispersed on the substrate with mono/submonolayers. The authors used pyridine (Py) as a probing molecule, and surface enhanced Raman spectroscopy (SERS) effect was investigated on pure Au and Au-Au@Pt mixed nanoparticle surfaces under the excitation line of 632.8 nm. The results revealed that there is a significant shift of the two characteristic peaks of Py, but the enhancement factors of Au dropped off precipitously with the introduction of the Au@Pt nanoparticles. The authors attributed this effect to the introduction of metal d-states from the metal, which would serve effectively to quench the surface plasmon excitation necessary for large (electromagnetic) enhancements in Raman spectroscopy.

[UV-Vis studies on the course of reaction of Au/Ag alloy colloid with hydrogen tetrachloroaurate(III) hydrate].

Using citrate as protector, Au-Ag alloy nanoparticles with different molar ratios were prepared with hydrazine as the reducer. One plasmon band between monometallic Ag and Au was observed in their UV-Vis spectra. And the peak of alloy shifted linearly with the ratio of Au changing in the alloy. By UV-Vis spectra, the course of reaction of the alloy colloid with HAuCl4 was studied. The result shows that the UV-Vis spectra of the alloy colloid changed regularly with the adding volume of HAuCl4 increasing. And there is a linear interval in it with the change in the calculated ratio of Au. With the former studies, the course can be attributed to the dealloy of Au/Ag alloy.

[Study of surface enhanced raman spectra of SCN- adsorbed on the Au-Ag complex substrate].

Ag and Au nanoparticles were self-assembled on a silicon substrate simultaneously. The density of Ag and Au nanoparticles was controlled by changing the volume ratio of Au to Ag colloids. The substrate was characterized by UV-Vis diffuse reflectance and SEM, and the results indicated that Ag and Au nanoparticles were dispersed on the substrate with mono/submono layers. Using SCN as a probing molecule, surface enhanced Raman spectroscopic (SERS) effect was investigated on pure Au, pure Ag and Au-Ag mixed nanoparticle surfaces. After a series of calibration, the results revealed that the SERS spectral features of SCN from the mixture system were similar to those from the pure Ag nanoparticles, indicating the coupling effect between the Ag and Au nanoparticles, which results in the property of Au inclining to Ag.

[Studies of surface-enhanced Raman spectroscopy on bare Ti electrode].

Various roughening methods for the bare Ti electrode such as mechanical roughening, electrochemical oxidation-reduction method and chemical etching were tried to obtain surface-enhanced Raman spectra (SERS) successfully for the first time. The results of the experiments proved that mechanical roughening and electrochemical oxidation-reduction method could be successfully employed in roughening titanium electrode, however, surfaces roughened in such ways showed no SERS-activity in Raman detection. Finally, chemical etching with hydrofluoric acid was proved to be an effective way to get SERS-active titanium surface, and surface-enhanced Raman spectra of pyridine adsorbed on a titanium surface was observed for the first time. In order to get the most effective titanium surface, roughening conditions, including concentration of the acid, the time of etching and the external potential, were investigated. As illustrated, Raman activity varies with conditions changing in roughening processes and the most reasonable condition for roughening was indicated. The result showed that at the concentration of hydrofluoric acid 0.33% (Wt) and 5 min for etching, the most SERS-active rough titanium surface could be obtained. In addition, with an external potential to speed up corrosion, the surface of titanium electrode tended to form a thin film of oxide, which prevented further corrosion and caused SERS-activity decrease. Thus, in this paper, the surface-enhanced Raman spectra of pyridine (pyridine 0.01 mol L(-1), and electrolyte KCl 0.1 mol L(-1)) adsorbed on bare roughed Ti electrode were observed at open circuit potential. Referring to the calculations of enhancement factor of pyridine on electrode, the enhancement factor is about 102 on the roughened titanium electrode.

[Template preparation of metal-molecule-metal junction and its SERS investigation].

In the present paper, the authors reported the assembly and SERS studies of a simple device unit of a metal nanowire-molecule-metal nanoparticles junction in an anodic aluminum oxide (AAO) template. The AAO template was fabricated by two-step electrochemical oxidation. Metals were filled into the pores by AC deposition. Then the AAO template with metal nafiowires was immersed into the solution of 1,4-benzenedithiol (1,4-BDT), which was followed by the immersion into silver nanoparticles with appropriate diameter. 1,4-BDT served as the probe molecule for SERS detection as well as the molecule for linking the metal nanowires and metal nanoparticles. The simple junction of metal-molecule-metal embedded in AAO template was built successfully. The SERS effect of the junction was investigated through the dissolution of AAO template to expose the junctions in the same orientation (standing on the substrate vertically). The giant enhancement from the former junction might be attributed to the coupling effect in the junction. The authors' preliminary results revealed that SERS might be a characteristic tool for the junction and the construction on the junction will be beneficial to the investigation of the complex SERS mechanism.

Predicting the binding capability of benzothiazoline-2-thione and its derivatives with gold: a DFT and FT-Raman combined studies.

The activities of chemical systems can be evaluated successfully by combining vibrational spectroscopic analysis and quantum chemical calculation based on density functional theory (DFT). Two tautomers of 5-fluorobenzo[d]thiazole-2(3H)-thione (FBTT), 7H-[1,3]dioxolo[4',5',4,5]benzo[1,2-d]thiazole-6-thione (DBTT) and 5-chloro-6-methylbenzo[d]thiazole-2(3H)-thione (CMBTT) were investigated by FT-Raman spectroscopy and DFT calculations at B3LYP/6-311+G** level. The molecular properties and activity relationships were determined by the HOMO energies, Mulliken charges and the binding energies with metal. It is concluded that three derivatives exhibited stable conformation of the thione form both in the isolated powder monomers and in their complexes with gold. The binding capability with gold was in the order of DBTT>BTT approximately CMBTT>FBTT. The derivatives with the electron-donor substitutes in benzene ring were favorable to metal for the p-pi conjugate effect.

[Progress in labeled immunoassay based on SERS].

Labeled immunoassay utilizing surface-enhanced Raman spectroscopy (SERS) is a new-style research technology. The discovery and confirmation of surface-enhanced Raman spectroscopy have made Raman spectroscopy a powerful tool in many research fields. SERS has the advantages such as high sensibility and selectivity, also it is suitable for the study of liquid substance. In recent years, it has shown potential application future in biomedical field, and also developed fast in labeled immunoassay. The principle, specialty, problem and recent advances of labeled immunoassay based on SERS were reviewed in terms of detection limits, non-specific adsorption and multi-analyte immunoassay. The latest advancement in the improvement of detection limits was summarized, along with the introduction of some work in our lab, as well as expatiating on the effect of non-specific adsorption. Finally, the development trends and application perspectives were discussed.

[Preparation and surface enhanced raman spectroscopic studies on Au-Ag alloy nanoparticles].

Using citrate as protector, Au-Ag alloy nanoparticles with different molar ratios were prepared by using hydrazine as the reducer, One plasmon band between that of monometallic Ag and Au observed in their UV-Vis spectra indicated the formation of Au-Ag alloy nanoparticles. TEM results showed diameters about 25 nm and homogeneous color of the alloy nanoparticles without clear core-shell contrast. By using Pyridine as the probe molecules, SERS studies were performed. The results indicated the spectra of Pyridine adsorbed on alloy is different from that of Ag and Au.

[Surface enhanced Raman spectroscopic studies on the coadsorption of N-methylimidazole and 2,2'-bipyridine at Cu electrode].

The adsorption behavior and coadsorption of N-methylimidazole (NMIM) and 2,2'-bipyridine(2,2'-bipy) at copper electrode were investigated by in situ electrochemical surface enhanced Raman spectroscopy (SERS) in the acetonitrile solution. In situ SERS studies revealed that NMIM can adsorb stably onto Cu electrode in a quite different potential range, but the potential range for adsorbing 2,2'-bipy is narrow. With the introduction of 2,2'-bipy into the solution, the SERS could be divided into three parts: (a) under -0.8 V, NMIM molecule adsorption, (b) near the open potential, 2,2'-bipy molecule adsorption with cis-conformation, (c) at positive potential region, both NMIM and 2,2'-bipy were coadsorbed at Cu surface, and the SERS data also suggested that the NMIM bound to copper surface with a tilted orientation, while the 2,2'-bipy was adsorbed through cis-conformation to the surface.

[Surface-enhanced Raman spectroscopic studies on the thiophenol adsorbed on novel Ag-Au alloy nanoparticles].

Ag-Au alloy seeds were prepared by the simultaneous reduction of Ag and Au salts. The seeds were grown via NH2OH x HCl-growth method to obtain novel Ag-Au alloy nanoparticles with diameters of 40-60 nm. The nanoseeds and novel nanoparticles were characterized by UV-Vis spectroscopy and TEM respectively. The observation of one surface plasma resonance absorption band, the redshift in their frequencies, and the uniform color of the nanoparticles shown in TEM images indicated the formation of alloy structure for both the nanoseeds and the novel nanoparticles. By using thiophenol (TP) as probe molecules, SERS studies were performed on the novel nanoparticles. The absorption bands of the nanoparticles red shifted with the addition of TP, and new bands were detected in the near infrared region, which were attributed to the aggregation of TP covered nanoparticles. With the excitation line of 632. 8 nm, the SERS intensity of TP on Au was most largely enhanced, and that on alloy nanoparticles were increased as X(Au) increased.

[Study on surface-enhanced Raman spectroscopy of Co6 films on Ag electrodes].

The thin films of C60 on Ag electrodes were studied by in situ surface-enhanced Raman spectroscopy (SERS) in acetonitrile solution and water solution respectively. The influence of C60 from bulk solution on the SERS of the adsorbed C60 was removed by pre-forming C60 films on the electrode. The results indicate that the split of some relevant Raman bands was attributed to the loss of vibrational degeneracy due to the lowering of the C60 molecular symmetry. Moreover, the surface selection rule was extended because of the influence of the surface electromagnetic field in which some forbidden modes became Raman-active. The results were similar to that of C60 molecules adsorbed on Ag electrode in the solution of C60. A weak band at about 348 and 311 cm(-1) was observed for the C60 films in acetonitrile solution and in aqueous solution respectively, which could be assigned to the interaction of C60 and Ag electrode surface.

Synthesis of AgcoreAushell bimetallic nanoparticles for immunoassay based on surface-enhanced Raman spectroscopy.

Layered core-shell bimetallic silver-gold nanoparticles were prepared by coating Au layers over Ag seeds by a seed-growth method. The composition of Ag100-xAux particles can vary from x=0 to 30. TEM and SEM images clearly show that the bimetallic nanoparticles are of core-shell structure with some pinholes on the surface. Strong surface-enhanced Raman (SER) signals of thiophenol and p-aminothiophenol have been obtained with these colloids. It was found that the SERS activity of aggregated colloids critically depends on the molar ratio of Ag to Au. With the increase of the Au molar fraction, the SERS activity enhances first and then weakens, with the maximal intensity being 10 times stronger than that of Ag colloids. The AgcoreAushell nanoparticles were then labeled with monoclonal antibodies and SERS probes and used for immunoassay analysis. In the proposed system, antibodies immobilized on a solid substrate can interact with the corresponding antigens to form a composite substrate, which can capture reporter-labeled AgcoreAushell nanoparticles modified with the same antibodies. The immunoreaction between the antibodies and antigens was demonstrated by the detection of characteristic Raman bands of the probe molecules. AgcoreAushell bimetallic nanoparticles, as a new SERS active and biocompatible substrate, will be expected to improve the detection sensitivity of immunoassay.

Effect of intrinsic properties of metals on the adsorption behavior of molecules: benzene adsorption on Pt group metals.

Investigation of benzene adsorption on different metal surfaces closer to a practical system appears to be a very important intermediate stage to utilize the conclusion obtained on single-crystal surfaces. In this paper, we studied the electrochemical adsorption behaviors of benzene on roughened Pt group electrodes using surface enhanced Raman spectroscopy (SERS). The effects of potential, surface roughness, and benzene concentration were investigated. Significant difference in surface Raman spectra of benzene on Ru, Rh, Pd, and Pt surfaces were found. On Pt surfaces, the parallel-chemisorbed benzene, the vertical dissociated chemisorbed benzene, and the physisorbed benzene were observed, evidenced by the ring vibration mode appearing at 872, 1012, and 991 cm(-1), respectively. On Pd, only parallel-chemisorbed benzene and physisorbed benzene were found. On Rh and Ru, the SERS signals were mainly from the parallel-chemisorbed benzene, with an extremely weak signal from the physisorbed benzene. The potential dependent study reveals that the parallel-chemisorbed species interacts strongest with the substrate, while the physisorbed species can be easily removed at positive potentials. The models for the adsorbed benzene were given to account for the different types of benzene on these Pt group metals. The difference in the atomization heat of the four metals was used to interpret the different interaction strength of benzene with Pt group metals.