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.     

Ag nanosheet-assembled micro-hemispheres as effective SERS substrates

Large-scale Ag nanosheet-assembled micro-hemispheres, with sufficient hot spots on their surfaces, have been achieved on an indium tin oxide substrate via electrodeposition. Surface-enhanced Raman scattering (SERS) measurements demonstrate that the Ag nanosheet-assembled micro-hemispheres can serve as sensitive and reproducible SERS substrates.     

SERS and DFT study of nitroarenes adsorbed on metal nanoparticles

A combined SERS and DFT investigation has been performed for 2-amino,5-nitropyridine (ANP) adsorbed on silver colloidal nanoparticles in order to get a better insight into the adsorption mechanism of ANP on the silver surface. Both B3LYP and B3PW91 functionals were used in the DFT calculations on ANP in the anionic form (ANP⁻) and on different models of ANP⁻/silver surface complexes. A mixed basis set 6-311++G^**/LANL2DZ was used in the case of the ANP⁻/Ag⁺ complexes. From the comparison between the experimental and the computational data, it was evinced that ANP is adsorbed on the silver surface in the anionic form with a quinonoid electronic structure through the nitrogen atom of the imino group.     

Photocatalytic growth of dendritic silver nanostructures as SERS substrates

We report a one-step photocatalytic synthesis method of dendritic silver nanostructures. These self-organised structures show an excellent Raman enhancement enabling the detection of analytes from dilute solutions by surface-enhanced Raman spectroscopy.     

Multifunctional Fe3O4@mTiO2@noble metal composite NPs as ultrasensitive SERS substrates for trace detection

Multifunctional materials have become the development trend of current material preparation. We reported a typical layer-by-layer method for the fabrication of multifunctional Fe₃O₄@mTiO₂@noble metal triplex core-shell composite nanoparticle (NP), which is composed of a magnetic Fe₃O₄ particle as the core, a mesoporous TiO₂ interlayer and a layer of Ag nanoparticles or Au nanorods as the shell. The obtained Fe₃O₄@mTiO₂@noble metal composite NPs have shown excellent surface enhanced Raman scattering (SERS) sensitivity. Raman results present that the limit of detection (LOD) for crystal violet (CV), p-aminothiophnol (p-ATP) and p-mercaptobenzoic acid (p-MBA) of the Fe₃O₄@mTiO₂@noble metal composite NPs substrates are as low as 1.0 × 10⁻⁹ M, 1.0 × 10⁻¹² M and 1.0 × 10⁻⁹ M, respectively. In addition, the composite NPs also show high reproducibility and stability across the entire area with relative standard deviations (RSD) less than 15.00%. These highly sensitivity with good reproducibility can be attributed to the presence of plentiful “hot spots” produced by magnetic aggregation and target molecules enrichment by mesoporous TiO₂ adsorption for practical application. Fe₃O₄@mTiO₂@Ag composite NPs were used for thiram detection and the detection limit can reach to 5.0 × 10⁻⁸ M (about 0.012 ppm), which is lower than the maximal residue limit of 7 ppm in fruit prescribed by the U.S. Environmental Protection Agency. These multifunctional composite NPs provide easy separation, enrichment and trace detection of the analyte, exhibiting a great prospect as a potential SERS sensor in complex environments.     

Acetate stabilization of metal nanoparticles and its role in the preparation of metal nanoparticles in ethylene glycol

Acetate-stabilized ruthenium nanoparticles were prepared by the NaBH4 reduction of the metal precursor salt at room temperature. Nanoparticles with a mean diameter of 2.20 nm and a standard deviation of 1.03 nm could be obtained under experimental conditions. The Ru nanoparticles so obtained could be easily extracted to a toluene solution of alkylamine, giving rise to alkylamine-stabilized Ru nanoparticles with a mean diameter of 2.96 nm and a standard deviation of 0.92 nm. The new found role of acetate stabilization was used to formulate a mechanism for the formation of metal (Pt, Ru) nanoparticles in ethylene glycol. In this mechanism metal nanoparticles are stabilized in ethylene glycol by adsorbed acetate ions, which are produced as a product of the OH- catalyzed reaction between the metal precursor salt and ethylene glycol.     

Self-assembled metal colloid films: two approaches for preparing new SERS active substrates

In this paper, we propose two new approaches for preparing active substrates for surface-enhanced Raman scattering (SERS). In the first approach (method 1), one transfers AgI nanoparticles capped by negatively charged mercaptoacetic acid from a AgI colloid solution onto a quartz slide and then deoxidizes AgI to Ag nanoparticles on the substrate. The second approach (method 2) deoxidizes AgI to Ag nanoparticles in a colloid solution and then transfers the Ag nanoparticles capped by negatively charged mercaptoacetic acid onto a quartz slide. By transfer of the AgI/Ag nanoparticles from the colloid solutions to the solid substrates, the problem of instability of the colloid solutions can largely be overcome. The films thus prepared by both approaches retain the merits of metal colloid solutions while they discharge their shortcomings. Accordingly, the obtained Ag particle films are very suitable as SERS active substrates. SERS active substrates with different coverages can be formed in a layer-by-layer electrostatic assembly by exposing positively charged surfaces to the colloid solutions containing oppositely charged AgI/Ag nanoparticles. The SERS active substrates fabricated by the two novel methods have been characterized by means of atomic force microscopy (AFM) and ultraviolet-visible (UV-vis) spectroscopy. The results of AFM and UV-vis spectroscopy show that the Ag nanoparticles grow with the increase in the number of coverage and that most of them remain isolated even at high coverages. Consequently, the surface optical properties are dominated by the absorption due to the isolated Ag nanoparticles. The relationship between SERS intensity and surface morphology of the new active substrates has been investigated for Rhodamine 6G (R6G) adsorbed on them. It has been found that the SERS enhancement depends on the size and aggregation of the Ag particles on the substrates. Especially, we can obtain a stronger SERS signal from the substrate prepared by method 1, implying that for the metal nanoparticles capped with stabilizer molecules such as mercaptoacetic acid, the in situ deoxidization in the film is of great use in preparing SERS active substrates. Furthermore, we have found that the addition of Cl- into the AgI colloid solution changes the surface morphology of the SERS active substrates and favors stronger SERS enhancement.     

Ultrasensitive SERS nanoprobes for hazardous metal ions based on trimercaptotriazine-modified gold nanoparticles

Trimercaptotriazine-modified gold nanoparticles exhibit strong SERS effects, yielding vibrational profiles very sensitive to the presence of heavy metal ions. Because of the contrasting response observed for selected vibrational bands in the SERS profiles, they provide useful nanoprobes for Hg2+ and Cd2+ ions, allowing direct quantitative assays by employing relative peak intensity ratios instead of using internal standards.     

Thermal and plasma synthesis of metal oxide nanoparticles from MOFs with SERS characterization

Aluminum oxide (Al₂O₃) and chromium oxide (Cr₂O₃) nanoparticles were synthesized by thermolysis of metal-organic frameworks (MOFs). Further O₂ plasma treatment is required to obtain high crystalline quality metal oxides. The composition and morphology of metal oxide nanoparticles were confirmed by powder X-ray diffraction and scanning electron microscopy characterization, respectively. The quality of synthesized metal oxides was also examined by observing the surface-enhanced Raman scattering (SERS) spectra of methyl orange adsorbed on Al₂O₃ and Cr₂O₃. The observed SERS effect can be ascribed to charge-transfer (CT) resonance effect between methyl orange and metal oxide surfaces. UV–vis absorption spectra and DFT calculations of metal oxide- methyl orange complexes have confirmed that the observed SRS effect is due to CT resonance between the metal oxide nanoparticles and the adsorbed methyl orange molecules.     

A comparative study of gold nanocubes, octahedra, and rhombic dodecahedra as highly sensitive SERS substrates

Gold nanocubes, octahedra, and rhombic dodecahedra with roughly two sets of particle sizes have been successfully synthesized via a seed-mediated growth approach. All six samples were analyzed for comparative surface-enhanced Raman scattering (SERS) activity. All of these Au nanostructures were found to yield strong enhancement at a thiophenol concentration of 10(-7) M and are excellent SERS substrates. Rhombic dodecahedra with a rhombus edge length of 32 nm showed significantly better enhancement than the other samples and can reach a detection limit of 10(-8) M. Simulations of the binding energies of thiophenol on the different faces of gold and electric near-field intensities of these nanocrystals have been performed to evaluate the experimental results. Superior SERS activity of these nanocrystals can be expected toward the detection of many other molecules.     

Conical tungsten tips as substrates for the preparation of ultramicroelectrodes

Here we describe a simple method to prepare voltammetric microelectrodes using tungsten wires as a substrate. Tungsten wires have a high tensile modulus and enable the fabrication of electrodes that have small dimensions overall while retaining rigidity. In this work, 125 microm tungsten wires with a conical tip were employed. For the preparation of gold or platinum ultramicroelectrodes, commercial tungsten microelectrodes, completely insulated except at the tip, were used as substrates. Following removal of oxides from the exposed tungsten, platinum or gold was electroplated, yielding surfaces with an electroactive area of between 1 x 10-6 and 2 x 10-6 cm2. Carbon surfaces on the etched tip of tungsten microwires were prepared by coating with photoresist followed by pyrolysis. The entire electrode was then insulated with Epoxylite except the tip, yielding an exposed carbon surface with an area of around 4 x 10-6 to 6 x 10-6 cm2. All three types of ultramicroelectrodes fabricated on the tungsten wire had similar electrochemical behavior to electrodes fabricated from wires or fibers insulated with glass tubes.     

Silver nanoparticles embedded temperature-sensitive nanofibrous membrane as a smart free-standing SERS substrate

To develop a smart free-standing surface enhanced Raman scattering(SERS) substrate,silver nanoparticles(AgNPs) embedded temperature-sensitive nanofibrous membrane was fabricated by electrospinning their aqueous solution containing the copolymer poly(N-isopropylacrylamide-co-Nhydroxymethylacrylamide),followed by heat treatment to form crosslinking structure within its constituent nanofibers.To avoid negative effect of the additive like stabilizer and the reactant like reductant on their SERS efficiency,the AgNPs were in-situ synthesized through reducing Ag~+ions dissolved in the polymer solution by ultraviolet irradiation.The prepared hybrid nanofibrous membrane with high stability in aqueous medium can reach its swelling or deswelling equilibrium state within 15 seconds with the medium temperature changing between 25℃and 50℃alternately.When it was used as a free-standing SERS substrate,10~(-12) mol/L of 4-nitrothiophenol in aqueous solution can be detected at room temperature,and elevating detection temperature can further lower its low detection limit.Since its generated SERS signal has desirable reproducibility,it can be used as SERS substrate for quantitative analysis.Moreover,the hybrid membrane as SERS substrate is capable of real-time monitoring the reduction of 4-nitrothiophenol into 4-aminothiophenol catalyzed by its embedded AgNPs,and the detected intermediate indicates that the reaction proceeds via a condensation route.     

Silver nanoparticles embedded temperature-sensitive nanofibrous membrane as a smart free-standing SERS substrate

Silver nanoparticles (AgNPs) embedded temperature-sensitive nanofibrous membrane as SERS substrate is capable of real-time monitoring the reduction of 4-nitrothiophenol into 4-aminothiophenol catalyzed by its embedded AgNPs, and the detected intermediate indicates that the reaction proceeds via a condensation route.     

Nonaqueous synthesis of metal oxide nanoparticles: Short review and doped titanium dioxide as case study for the preparation of transition metal-doped oxide nanoparticles

The liquid-phase synthesis of metal oxide nanoparticles in organic solvents under exclusion of water is nowadays a well-established alternative to aqueous sol–gel chemistry. In this article, we highlight some of the advantages of these routes based on selected examples. The first part reviews some recent developments in the synthesis of ternary metal oxide nanoparticles by surfactant-free nonaqueous sol–gel routes, followed by the discussion of the morphology-controlled synthesis of lanthanum hydroxide nanoparticles, and the presentation of structural peculiarities of manganese oxide nanoparticles with an ordered Mn vacancy superstructure. These examples show that nonaqueous systems, on the one hand, allow the preparation of compositionally complex oxides, and, on the other hand, make use of the organic components (initially present or formed in situ) in the reaction mixture to tailor the morphology. Furthermore, obviously even the crystal structure can differ from the corresponding bulk material like in the case of MnO nanoparticles. In the second part of the paper we present original results regarding the synthesis of dilute magnetic semiconductor TiO₂ nanoparticles doped with cobalt and iron. The structural characterization as well as the magnetic properties with special attention to the doping efficiency is discussed.     

Hierarchical structure of SERS substrates possessing the silver ring morphology

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Hyperbranched polyglycidol assisted green synthetic protocols for the preparation of multifunctional metal nanoparticles

Biocompatible hyperbranched polyglycidol (HBP) has been demonstrated to be an effective reducing and stabilizing agent for the synthesis of highly water-soluble monometallic (Au, Ag, Pt, Pd, and Ru) and bimetallic (Au/Pt, Au/Pd, and Au/Ru) nanoparticles (NPs), which provides a general and green protocol to fabricate metal NPs. The HBP-assisted reduction of metal ions follows an analogous polyol process. The reduction reaction rate increases sharply by increasing the temperature and the molecular weight of HBP. The size of NPs is controllable simply by changing the concentration of the metal precursor. High molecular weight HBP is favorable for the formation of NPs with uniform size and improved stability. By utilizing hydroxyl groups in the HBP-passivation layer of Au NPs, TiO(2)/Au, GeO(2)/Au, and SiO(2)/Au nanohybrids are also fabricated via sol-gel processes, which sets a typical example for the creation of versatile metal NPs/inorganic oxide hybrids based on the as-prepared multifunctional NPs.     

Simple synthesis of zwitterionic diblock copolymers for the application on metal nanoparticles preparation

AB diblock copolymers of poly(2-(dimethylamino)ethyl metharylate-block-potassiurn acrylate) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The structure of the block polymer was determined by the nuclear magnetic resonance (NMR) spectroscopy and the gel permeation chromatography. Moreover, it has also been shown that the diblock copolymers exhibit aggregate as function of the pH according to the result of ¹H-NMR spectroscopy, FT-IR absorption spectra, UV-vis transmittance spectroscopy, transmission electron microscopy and ultrasonic particle size analyzer. The result was attributed that such AB diblock copolymers were tailored to undergo pH-induced self-assembly. Furthermore, the aggregate can be as template of metal nanoparticles preparation, and the sizes of the aggregate, in turn, strongly control nanoparticle sizes.