Insight into Multiphase Interlayer Molecular Packing and Stepwise Phase Transition in 4-(Phenylazo)benzoate Anion-Intercalated Layered Zinc Hydroxide.

The properties of layered intercalation hybrids are closely related to interlayer molecular packing. To develop functional intercalation hybrids, it is essential to gain deep insights into interlayer molecular packing. This work reports a new comprehensive insight into the controllable multiphase interlayer molecular packing in 4-(phenylazo)benzoate anion-intercalated layered zinc hydroxide (LZH-4-PAB intercalation hybrids). The new insight breaks up the general understanding that the interlayer molecular packing of anions is usually single-phase, lacking diversity and controllability. Furthermore, it uncovers an interesting stepwise rather than the generally expected continuous phase transition of the interlayer molecular packing. The intercalated 4-PAB anions initially organize into the horizontal monolayer packing (θ = 0°, Phase I), which stepwise transforms to the tilted interdigitated antiparallel bilayer packing (θ ≈ 50°, Phase II) along with an increased intercalation loading and eventually to the vertical interdigitated antiparallel bilayer packing (θ = 90°, Phase III). The LZH-4-PAB hybrids exhibited a greatly enhanced interlayer molecular packing-dependent UV-vis absorption. This study provides helpful guidance for developing property-tailored intercalation hybrids. It may attract new interest in more layered intercalation hybrids. New and rich intercalation chemistry might be discovered in more functional intercalation hybrids beyond the 4-PAB anion-intercalated layered zinc hydroxide.

MoS2/Au Heterojunction Catalyst for SERS Monitoring of a Fenton-like Reaction.

Fenton technology is one of advanced oxidation process (AOP) methods to treat wastewater through chemical oxidation. Due to the limitations of classical iron-based catalysts, it is still challenging to find suitable catalysts for Fenton-like reactions. Here, MoS2/Au heterojunctions were successfully synthesized by reduction of chloroauric acid in the solution of layered MoS2 prepared by hydrothermal method. As a model molecule, methylene blue (MB) was used as the species to be degraded to evaluate the performance of the catalyst. It was determined by UV-visible spectra that the optimal catalyst can be obtained when MoS2 (mg): HAuCl4 (wt. % mL) is 2:2. The Fenton-like reaction process was monitored by introducing highly sensitive surface enhanced Raman spectroscopy (SERS). The results show that MB can be degraded by 83% in the first 10 min of the reaction, indicating that MoS2/Au has good catalytic performance. In addition, as a fingerprint spectrum, SERS was used to preliminarily analyze the molecular structure changes during the degradation process. The result showed that C-N-C bond was easier to break than the C-S-C bond. NH2 group and the fused ring were destroyed at the comparable speed at the first 30 min. In terms of application applicability, it was showed that MB degradation had exceeded 95% at all the three pH values of 1.4, 5.0, and 11.1 after the reaction was carried out for 20 min. The test and analysis of the light environment showed that the catalytic efficiency was significantly improved in the natural light of the laboratory compared to dark conditions. The possible mechanism based on ·OH and ·O2- from ESR data was proposed. In addition, it was demonstrated to be a first-order reaction from the perspective of kinetics. This study made a positive contribution to broaden of the applicable conditions and scope of Fenton-like reaction catalysts. It is expected to be used as a non-iron catalyst in practical industrial applications. From the perspective of detection method, we expect to develop SERS as a powerful tool for the in situ monitoring of Fenton-like reactions, and to further deepen our understanding of the mechanism.

Real-time tracking of colloidal stability based on collision behaviors probed by surface-enhanced Raman spectroscopy.

HYPOTHESIS: The dynamic behaviors of colloidal particles have already been considered as one of the key issues in their practical application, such as aggregation and dispersion. However, it is still remained significant challenge in developing the real time techniques to capture their dynamic tracks. The nano/subnanometer scale gap generated during the colloidal collisions served as the critical location for amplifying the Raman signal, so called as gap ("hot spots") based surface enhanced Raman spectroscopy (SERS). The alternating reversible "spike" of SERS intensity and irreversible step in baseline intensity are contributed to the preferred stability and the aggregation of colloid respectively. EXPERIMENTS: A facile approach is developed to track colloidal stability in real-time based on collisions and SERS. The effects of particle concentration, the dispersion medium, and solution pH on colloidal stability are systematically investigated, and the SERS intensity of a simulated single-like "hot spot" was calculated by combining a SEM position with SERS mapping technology to estimate the intensity of single-particle collision. FINDINGS: The colloidal particles exhibited higher stability in the solution with lower particle concentration, higher viscosity and neutral medium. The SERS intensity of single-particle collision was estimated to be about 2.06 × 10-7 counts, and the average number of collisions for the 0.13 mmol/dm3 SiO2@Ag solution was about 1.11 × 108 times/spike in the "spikes" with SERS intensity of 23.0 cps. It is believed that the SERS based strategy would be developed as a promising tool for obtaining the deeper insight into the nature of collisions in the colloidal science.

Construction of a HPLC-SERS hyphenated system for continuous separation and detection based on paper substrates.

The achievement of high-throughput separation and high-sensitivity detection of complex samples has been one of the most challenging issues in the field of analytical science. The application of a single technology alone could not satisfy the above requirements. The combination of technologies with the capability of high-efficiency separation and high-sensitivity structural-recognition is highly desired to meet the technical requirements. Herein, an automatic high-performance liquid chromatography (HPLC)-surface enhanced Raman spectroscopy (SERS) hyphenated system using paper substrates as the "interface" was constructed to achieve efficient separation and real-time detection. A homogeneous Au nanoparticle was printed on the hydrophobic filter paper with the inkjet technology. The prepared substrates served as a linkage for the continuous realization of HPLC and SERS functions. The complex system was separated by HPLC, and the effluents were loaded onto automatically and continuously replaceable paper substrates for real time SERS measurements. The continuous rapid separation and real-time detection of various two-component mixtures were achieved with the separation efficiency and detection sensitivity of each technology. The results demonstrated that the HPLC-SERS hyphenated system exhibited the complementary capability of the on-line separation and continuous structural identification of illegal additives in real samples. The detection sensitivity was increased by an order of magnitude to reach 10-5 mol dm-3, and the efficiency and accuracy for the separation and identification on the multi-components samples were higher than those of the individual HPLC or SERS technology. It is believed that the continuous paper substrate-based HPLC-SERS hyphenated system would be developed as a promising technique for the separation and identification of multi-components mixtures with high throughput.

Real-time visualization of the Suzuki reaction using surface enhanced Raman spectroscopy and a moveable magnetic nanoparticle film.

Utilizing a moveable Fe3O4@Au film, an operando SERS strategy was developed successfully for visualizing Suzuki reaction processes. The feasibility and generality were verified by using the reaction of 3-bromopyridine and phenylboronic acid as a probe.

Real-Time Monitoring of Surface Effects on the Oxygen Reduction Reaction Mechanism for Aprotic Na-O2 Batteries.

Discharging of aprotic sodium-oxygen (Na-O2) batteries is driven by the cathodic oxygen reduction reaction in the presence of sodium cations (Na+-ORR). However, the mechanism of aprotic Na+-ORR remains ambiguous and is system dependent. In-situ electrochemical Raman spectroscopy has been employed to study the aprotic Na+-ORR processes at three atomically ordered Au(hkl) single-crystal surfaces for the first time, and the structure-intermediates/mechanism relationship has been identified at a molecular level. Direct spectroscopic evidence of superoxide on Au(110) and peroxide on Au(100) and Au(111) as intermediates/products has been obtained. Combining these experimental results with theoretical simulation has revealed that the surface effect of Au(hkl) electrodes on aprotic Na+-ORR activity is mainly caused by the different adsorption of Na+ and O2. This work enhances our understanding of aprotic Na+-ORR on Au(hkl) surfaces and provides further guidance for the design of improved Na-O2 batteries.

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.

The moveable "hot spots" effect in an Au nanoparticles-Au plate coupled system.

Surface-enhanced Raman spectroscopy (SERS) is mainly contributed by "hot spots". Due to the huge electromagnetic enhancement, "hot spots" have wide applications in surface analysis and surface catalysis. The in-depth research on the "hot spots" effect is conducive to understanding SERS enhancement mechanisms and designing substrates with high enhancement. At present, the investigation on the "hot spots" effect is mainly based on theoretical simulation and simple experimental models. However, little attention has been paid to the SERS substrates with practical applications. The main reason is that it is difficult to construct a suitable coupled model with great uniformity and sensitivity, which led to the lack of comparability of SERS intensities from different spots or substrates. In this work, Au nanoparticle mono-/bi-layer films coupled with Au single-crystal plate systems were constructed to investigate the distribution and transformation of "hot spots" dependent on the excitation wavelength by a single or dual probe-modified strategy, in which one or two types of molecules with distinct characteristic peaks were modified in different enhanced gaps. The results demonstrated that the wavelength that drove the transformation of the coupling mode from the "particle-particle" mode to the "particle-surface" mode was around 638 nm in the Au nanoparticle monolayer film (Au MLF) covered Au plate system. As the second naked Au MLF was transferred onto the first Au MLF, "hot spots" were transferred to the "particle-particle" gap between the upper and lower Au MLFs with a 638 nm laser as the excitation line. This work offers a novel avenue to investigate the "hot spots" effect in the complex multidimensional nanostructures, which is beneficial for the development of theoretical research and practical applications of SERS.

Surface enhanced Raman spectroscopic studies on the adsorption behaviour of nitric oxide on a Ru covered Au nanoparticle film.

Nitric oxide (NO) is very interesting because of its effects on air pollution and especially biological systems. The adsorption behavior of NO molecules has fundamental importance with great technical challenges due to complex processes and species identification. Herein, the NO adsorption behavior on a Ru surface has been investigated using well-designed surface enhanced Raman spectroscopy (SERS) substrates. A Au nanoparticle monolayer film on ITO was employed as the electrode and Ru layers were electrochemically deposited. The internal SERS effect from the Au nanoparticles with high sensitivity and the metallic surfaces of Ru with practical application were integrated into a composite Au/Ru substrate. The molecular adsorption and dissociation of NO were observed simultaneously by SERS. A competitive relationship between adsorption and dissociation was observed at higher NO pressure, and the 3-fold and 2-fold bridge and top adsorption configurations appeared on the surface and were associated with different ν NO vibrational frequencies. The results indicated that 3-fold bridge sites are preferred for dissociation over other structures. The dissociation of NO produced adsorbed atomic nitrogen and oxygen species to form Ru-N and Ru-O bonds, respectively. The dissociation process, especially for linear NO, was site dependent and blocked at higher pressure or coverage. Due to the change in adsorption energy and coverage, a conversion of the adsorption configuration from bridge to top was observed in the initial stage of NO adsorption, and this was followed by a mixture of bridge and top configurations of NO and dissociated species. A two-step dissociation mechanism and the steps of NO adsorption were proposed. The present study suggested that the SERS technique with appropriate attractive metal overlayers provided a significant and possibly even a valuable approach to explore adsorption behavior and kinetics at gas-solid interfaces.

Surface-enhanced Raman spectroscopic identification in fingerprints based on adhesive Au nanofilm.

The visualization and acquisition of information on substances within fingerprints have attracted considerable interest owing to their practical application in forensic science. There are still some challenges in the transfer and imaging of fingerprints and the extraction of residues. Here, a facile approach was successfully developed for transferring and recovering the pattern of fingerprints, which is based on surface-enhanced Raman spectroscopy (SERS) and an adhesive Au nanofilm (ANF). The reproducibility of SERS effects and the adhesive quality of the ANF enabled the transfer, recovery of the pattern and extraction of chemical residues from living/latent fingerprints. The results demonstrated that the pattern of living fingerprints, including ridges, furrows and sweat pores, was recovered on the basis of SERS mapping of the vibrational band of amino acids from endogenous protein substances. The dye rhodamine 6G (R6G) was employed as a developing agent to enhance the visualization of fingerprints by SERS mapping of the band at 1360 cm-1. Moreover, exogenous residues, such as cotinine (COT) and methylene blue (MB), were also detected by SERS. Their distribution in fingerprints was also determined, although it was not associated with the pattern of fingerprints. This indicated that the extraction process based on the adhesive ANF could be applied to transfer fingerprints from a crime scene to the laboratory for precise identification via structural information on chemical residues and the pattern image of fingerprints. It is anticipated that the adhesive ANF when combined with an ultrahigh-sensitivity SERS technique could be developed as a promising tool for the visualization of fingerprints and monitoring of trace chemical residues for crime tracking in forensic science.

Observing the dynamic "hot spots" on two-dimensional Au nanoparticles monolayer film.

Interparticle spacing was controlled by evaporating water on 2D Au nanoparticles arrays. Relationships among SERS effect, SPR catalysis, and gap distance were experimentally and theoretically studied.

Improving the sensitivity of immunoassay based on MBA-embedded Au@SiO2 nanoparticles and surface enhanced Raman spectroscopy.

Traditional "sandwich" structure immunoassay is mainly based on the self-assembly of "antibody on solid substrate-antigen-antibody with nanotags" architectures, and the sensitivity of this strategy is critically depended on the surface enhanced Raman scattering (SERS) activities and stability of nanotags. Therefore, the rational design and fabrication on the SERS nanotags attracts the common interests to the bio-related detecting and imaging. Herein, silica encapsulated Au with mercaptobenzoic acid (MBA) core-shell nanoparticles (Au-MBA@SiO2) are fabricated instead of the traditional naked Au or Ag nanoparticles for the SERS-based immunoassay on human and mouse IgG antigens. The MBA molecules facilitate the formation of continuous pinhole-free silica shell and are also used as SERS labels. The silica shell is employed to protect MBA labels and to isolate Au core from the ambient solution for blocking the aggregation. This shell also played the similar role to BSA in inhibiting the nonspecific bindings, which allowed the procedures for constructing "sandwich" structures to be simplified. All of these merits of the Au-MBA@SiO2 brought the high performance in the related immunoassay. Benefiting from the introduction of silica shell to encapsulate MBA labels, the detection sensitivity was improved by about 1-2 orders of magnitude by comparing with the traditional approach based on naked Au-MBA nanoparticles. This kind of label-embedded core-shell nanoparticles could be developed as the versatile nanotags for the bioanalysis and bioimaging.

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.

Controlling dynamic SERS hot spots on a monolayer film of Fe3O4@Au nanoparticles by a magnetic field.

A large surface-enhanced Raman scattering (SERS) effect is critically dependent on the gap distance of adjacent nanostructures, i.e., "hot spots". However, the fabrication of dynamically controllable hot spots still remains a remarkable challenge. In the present study, we employed an external magnetic field to dynamically control the interparticle spacing of a two-dimensional monolayer film of Fe3O4@Au nanoparticles at a hexane/water interface. SERS measurements were performed to monitor the expansion and shrinkage of the nanoparticles gaps, which produced an obvious effect on SERS activities. The balance between the electrostatic repulsive force, surface tension, and magnetic attractive force allowed observation of the magnetic-field-responsive SERS effect. Upon introduction of an external magnetic field, a very weak SERS signal appeared initially, indicating weak enhancement due to a monolayer film with large interparticle spacing. The SERS intensity reached maximum after 5s and thereafter remained almost unchanged. The results indicated that the observed variations in SERS intensities were fully reversible after removal of the external magnetic field. The reduction of interparticle spacing in response to a magnetic field resulted in about one order of magnitude of SERS enhancement. The combined use of the monolayer film and external magnetic field could be developed as a strategy to construct hot spots both for practical application of SERS and theoretical simulation of enhancement mechanisms.

Inhibiting plasmon catalyzed conversion of para-nitrothiophenol on monolayer film of Au nanoparticles probed by surface enhanced Raman spectroscopy.

The plasmon catalyzed surface reaction has been attracted considerable attention due to its promising application in heterogeneous catalysis. This kind of plasmon catalysis played bilateral roles in driving the unconventional reactions or destructing the surface molecule layer. The acceleration or inhibition on this catalysis is still remained significant challenge. In this paper, monolayer film of Au nanoparticles was fabricated at air/water interface as substrates both for surface enhanced Raman spectroscopy (SERS) and plasmon catalyzed surface reaction. The influence from several issues, involving surfactants, coadsorption species, the solvent and water, were systemically investigated to probe the acceleration and inhibition on the plasmon catalysis reaction. The concentration and molecular weight of surfactant polyvinylpyrrolidone (PVP) exhibited significant influence in the reactive activity for the plasmon catalyzed dimerization of para-nitrothiophenol (PNTP) to p,p'-dimercaptoazobenzene (DMAB). A suitable molecular weight of 10,000 and concentration of 10mg/mL were beneficial for improving the conversion efficiency of PNTP to DMAB. The higher molar ratio of coadsorbed 1-octanethiol and the aprotic solvents resulted in the inhibition of dimerization because 1-octanethiol occupied the surface sites to isolate the adsorbed PNTP molecules with a larger distance and lack of proton source. The plasmon catalysis occurred in ionic liquids suggested that water was essential for the dimerization of PNTP, in which it was used to accelerate the reaction rate and severed as the hydrogen source.

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.

Stacking faults enriched silver nanowires: facile synthesis, catalysis and SERS investigations.

A facile approach based on seed-mediated method for synthesis of stacking faults enriched Ag nanowires (SFEANWs) was successfully developed. SFEANWs were formed and attached onto the seed (α-Fe2O3/Au) surfaces through the reduction of AgNO3 by ascorbic acid (AA) in the presence of sodium polyacrylate (PAANa). Their length can be tuned with different concentrations of AgNO3 or PAANa. According to the effects of seeds and PAANa, the plausible growth mechanism of SFEANWs was discussed. The catalytic activity of SFEANWs comparing with fivefold twinned Ag nanowires (FFTANWs) was evaluated through reducing p-nitrophenol by NaBH4. The activation energy of the classical reaction catalyzed by SFEANWs was calculated through the Arrhenius equation. In addition, these SFEANWs exhibited excellent surface enhanced Raman scattering (SERS) activities due to the hot spots located in the cross of the twist wires. The detection limit of by SERS for 1,4-benzenedithiol (1,4-BDT) was estimated about 10(-7) mol/L.

Surface enhanced Raman spectroscopic studies on magnetic Fe3O4@AuAg alloy core-shell nanoparticles.

A facile approach has been developed to fabricate multifunctional Fe3O4@AuAg alloy core-shell nanoparticles, owning the magnetism of the core and the surface enhanced Raman spectroscopy (SERS) activities of the alloy shell. By changing the amount of HAuCl4 and AgNO3, Fe3O4@AuAg alloy nanoparticles with different component ratios of Au and Ag were successfully prepared. The surface plasmon resonance of the composition was linearly tuned in a wide range by varying the molar fraction of Ag and Au, suggesting the formation of AuAg alloy shell. SERS and magnetic enrichment effects were investigated by using thiophenol (TP) as the probe molecule. The SERS intensity was strongly dependent on the molar ratios of Au and Ag and the excitation line. Enrichment for the molecules with low concentration and on line SERS monitoring experiments were performed through combining the magnetism of the core and the SERS effect of the alloy shell. The results revealed that the magnetic enrichment efficiency was dramatically increased due to the strong magnetism of Fe3O4 core. In addition, the Fe3O4@AuAg nanoparticles were also used in the microfluidic chip to continuously detect different flowing solution in the channel. The detection time and amount of analyte were successfully decreased.

The effect of triphenylphosphane on corrosion inhibition of benzotriazole at Ag electrode monitored by SERS in nonaqueous solution.

The corrosion inhibition behavior of benzotriazole (BTAH) on Ag electrodes and the influence of triphenylphosphane (pph(3)) were investigated by electrochemical method, in situ surface-enhanced Raman spectroscopy (SERS) and direct electrochemical synthesis of surface complexes in nonaqueous solution. The results indicated that the BTA(-) ion was coordinated to the Ag surface to form a highly cross-linked surface polymer complex of [Ag(BTA)](n), which suppressed the dissolution and oxidation of Ag effectively. The introduction of a neutral ligand of pph(3) blocked the surface coordination processes of BTAH with the Ag electrode. It resulted in a decrease of inhibition efficiency to Ag surface. The ligand of pph(3) played a negative role on the corrosion inhibition of BTAH to the Ag electrode. The SERS results were well consistent with the cyclic voltammetry and polarization curves measurements. For modeling, two different surface complexes were prepared in acetonitrile with and without pph(3) by direct electrochemical synthesis. A polymer-like complex of [Ag(BTA)](n) attached to the Ag surface was obtained in the absence of pph(3), which suppressed the dissolution and oxidation of Ag effectively. A new binuclear compound, Ag(2)(BTA)(2)(pph(3))(4), was produced in acetonitrile with pph(3) and the final coordination process occurred in solution leading to difficulties in forming a compact surface film, thus decreasing the corrosion inhibition efficiency of BTAH. The role of pph(3) and the mechanism were proposed.

Tunable fabrication on iron oxide/Au/Ag nanostructures for surface enhanced Raman spectroscopy and magnetic enrichment.

A facile approach was developed to prepare novel multifunctional Fe(2)O(3)/Au/Ag nanostructures integrated with isolated functions involving magnetic and optical properties. The Fe(2)O(3)/Au/Ag hybrid nanoparticles with different thicknesses of Ag shell were prepared by adjusting the amount of the AgNO(3). Surface structures were varied from the rough with pinhole to smooth and pinhole free surfaces with increasing amounts of AgNO(3). The surface plasmon resonance was tuned in a very wide region from that of Au to Ag. Surface enhanced Raman scattering (SERS) effects were also investigated, employing thiophenol (TP) and aminothiophenol (PATP) as probe molecules. It was revealed that the SERS intensity was strongly depended on the molar ratio of Ag and Au. With an increase in the Ag molar fractions, SERS signals were enhanced to the maximum due to the surface plasmon resonance of the pinhole structure. The magnetic enrichment for on line SERS monitoring the molecules with low concentration was performed based on the magnetic core and the SERS activity of the bimetallic shells. This enrichment procedure improved efficiently the limits of the SERS detection. It was shown that the multicomponent nanoparticles have potential applications in the fields of optical devices and magnetic separation.