Surface-enhanced Raman optical activity on adenine in silver colloidal solution

We report the collection of Raman optical activity (ROA) spectra of adenine in silver colloidal solution, that is, surface-enhanced Raman optical activity (SEROA) using considerably shorter data acquisition times, reduced excitation power, and lower concentration, as compared to classical ROA measurements on molecules of biological interest so far reported in the literature. These improvements in experimental parameters for ROA measurements can be explained by enhanced Raman signals in the local optical fields of the silver nanoparticles and by at least 1 order of magnitude higher values for circular intensity differences (CIDs), as compared to classical ROA that has been suggested before and theoretically discussed in terms of large field gradients near a metal surface. The measured ROA effect for adenine can be understood in terms of adsorption-induced chirality in the prochiral molecules on the silver nanoparticles. Surface-enhanced Raman optical activity offers potential capabilities for sensitive, rapid, stereochemical characterization of basic building blocks of biopolymers, such as amino acids and nucleosides, as well as biologically active molecules, in particular, also for probing organization and self-assembling of such molecules on metal surfaces.     

Surface-enhanced Raman scattering of dopamine at polymer-coated silver electrodes

Attenuation of dopamine surface-enhanced Raman scattering (SERS) spectra at silver electrodes by protein adsorption is described. Polymer-modified electrodes eliminate protein adsorption effects. Partially hydrolyzed cellulose acetate coatings prevent protein adsorption and allow transport of dopamine to and from the electrode surface. Dopamine SERS spectra from these electrodes are similar to those obtained at uncoated electrodes. Perfluorosulfonate (Nafion) coatings also prevent protein adsorption. However, dopamine transported to the electrode remains trapped inside the coating and cannot be removed.     

Surface-enhanced Raman scattering imaging of a single molecule on urchin-like silver nanowires

Urchin-like silver nanowires are prepared by reacting AgNO(3)(aq) with copper metal in the presence of cetyltrimethylammonium chloride and HNO(3)(aq) on a screen-printed carbon electrode at room temperature. The diameters of the nanowires are about 100 nm, and their lengths are up to 10 μm. Using Raman spectroscopy, the detection limit of Rhodamine 6G (R6G) on the urchin-like silver nanowire substrate can be as low as 10(-16) M, while the analytical enhancement factor is about 10(13). Raman mapping images confirm that a single R6G molecule on the substrate can be detected.     

Surface-enhanced Raman spectra of calf thymus DNA adsorbed on concentrated silver colloid

Raman and surface-enhanced Raman scattering (SERS) spectra of calf thymus DNA were investigated. We have carried out improvements to the silver colloid preparation method of Lee and Meisel in two respects. In one method, the silver sol was boiled with rapid stirring for over two hours. In the second method, the silver sol was concentrated by centrifugation before adding it to the DNA solution. The resulting hydrosol could be stored for 15 months because of its high stabilization. Structural information with respect to the phosphate backbone, deoxyribose, and four bases of DNA could be obtained before and after the DNA solutions were added to the concentrated Ag colloid substrate. The intensities of almost all characteristic bands assigned to various groups of the components of DNA were enhanced to a remarkable degree. The enhancement effect of the DNA solution at neutral pH 7.0 was obviously much better than that at acidic pH 3.4 or at alkaline pH 8.5. Intensity increases of the SERS bands of the DNA solution with time were observed. The SERS signals obtained 16 hours after the interaction of the Ag colloid with the DNA solution were much better than the SERS signals obtained just after the mixed liquid was prepared. This method can be widely used to store the Ag colloid for long times and to obtain the SERS spectra of DNA molecules, and it can further be used to study the adsorption behavior of solute biomacromolecules in different solvents.     

Quantitative assessment of surface-enhanced resonance Raman scattering for the analysis of dyes on colloidal silver

Factors that affect quantitative analysis by surface-enhanced resonance Raman scattering (SERRS) have been investigated using azobenzotriazol and reactive dyes. Preaggregation of the silver colloid was the most effective method to obtain repeatable and reproducible scattering. Aggregation by poly(l-lysine) or spermine provided better precision than aggregation by sodium chloride or nitric acid. Repeatable quantitative analysis was achieved with the azobenzotriazol dyes. A linear calibration graph was obtained over different concentration ranges below 10(-)(8) M, depending on the nature of the colloid. Calculations estimate that 10(-)(8) M is the concentration at which monolayer coverage of the dye on the silver colloid is achieved. Above 10(-)(8) M, there was only a minor increase in the scattering intensity from the azobenzotriazol dyes. In contrast, the reactive dyes did not give a response proportional to concentration over the range studied. The different responses obtained for the two types of dye are believed to be caused by differences in the nature of the interaction of the molecules with the silver surface. The conclusion reached is that control of the colloid preparation, aggregation process, and surface chemistry are essential for successful quantitative analysis of dyes on colloidal silver by SERRS.     

Surface-enhanced Raman scattering dendritic substrates fabricated by deposition of gold and silver on silicon

This paper reports a study on the preparation of gold nanoparticles and silver dendrites on silicon substrates by immersion plating. Firstly, gold was deposited onto silicon wafer from HF aqueous solution containing HAuCl4. Then, the silicon wafer deposited gold was dipped into HF aqueous solution of AgNO3 to form silver coating gold film. Scanning electron microscopy reveals a uniform gold film consisted of gold nanoparticles and rough silver coating gold film containing uniform dendritic structures on silicon surface. By SERS (surface-enhanced Raman scattering) measurements, the fabricated gold and silver coating gold substrates activity toward SERS is assessed. The SERS spectra of crystal violet on the fabricated substrates reflect the different SERS activities on gold nanoparticles film and silver coating gold dendrites film. Compared with pure gold film on silicon, the film of silver coating gold dendrites film significantly increased the SERS intensity. As the fabrication process is very simple, cost-effective and reproducible, and the fabricated silver coating gold substrate is of excellent enhancement ability, spatial uniformity and good stability.     

Surface-enhanced Raman scattering substrate of silver nanoparticles depositing on AAO template fabricated by magnetron sputtering

In this report, we describe a fabrication process of low-cost and highly sensitive SERS substrates by using a simple anodizing setup and a low-energy magnetron sputtering method. The structure of the SERS substrates consists of silver nanoparticles deposited on a layer of anodic aluminum oxide (AAO) template. The fabricated SERS substrates are investigated by a scanning electron microscope (SEM), a transmission electron microscope (TEM), and a confocal Raman spectroscope. We have verified from the surface morphology that the fabricated SERS substrates consist of high-density round-shape silver nanoparticles where their size distribution ranges from 10 to 30 nm on the top and the bottom of nanopores. The surface-enhanced Raman scattering activities of these nanostructures are demonstrated using methylene blue (MB) as probing molecules. The detection limit of 10⁻⁸ M can be achieved from this SERS substrate.     

Surface-enhanced Raman scattering substrate of silver nanoparticles depositing on AAO template fabricated by magnetron sputtering

In this report, we describe a fabrication process of low-cost and highly sensitive SERS substrates by using a simple anodizing setup and a low-energy magnetron sputtering method. The structure of the SERS substrates consists of silver nanoparticles deposited on a layer of anodic aluminum oxide (AAO) template. The fabricated SERS substrates are investigated by a scanning electron microscope (SEM), a transmission electron microscope (TEM), and a confocal Raman spectroscope. We have verified from the surface morphology that the fabricated SERS substrates consist of high-density round-shape silver nanoparticles where their size distribution ranges from 10 to 30 nm on the top and the bottom of nanopores. The surface-enhanced Raman scattering activities of these nanostructures are demonstrated using methylene blue (MB) as probing molecules. The detection limit of 10⁻⁸ M can be achieved from this SERS substrate.     

Single-crystal silver nanowires: Preparation and Surface-enhanced Raman Scattering (SERS) property

Ordered Ag nanowire arrays with high aspect ratio and high density self-supporting Ag nanowire patterns were successfully prepared using potentiostatic electrodeposition within the confined nanochannels of a commercial porous anodic aluminium oxide (AAO) template. X-ray diffraction and selected area electron diffraction analysis show that the as-synthesized samples have preferred (220) orientation. Transmission electron microscopy and scanning electron microscopy investigation reveal that large-area and ordered Ag nanowire arrays with smooth surface and uniform diameter were synthesized. Surface-enhanced Raman Scattering (SERS) spectra show that the Ag nanowire arrays as substrates have high SERS activity.     

Surface-enhanced Raman detection of melamine on silver-nanoparticle-decorated silver/carbon nanospheres: effect of metal ions

Silver/carbon (Ag/C) core-shell nanospheres synthesized by a hydrothermal method were used as templates for fabricating silver nanoparticle-decorated Ag/C (Ag/C/AgNps) nanospheres. The particle size of Ag nanoparticles can be tuned by varying the concentration of Ag precursor. Detection of melamine molecules at concentrations as low as 5.0×10(-8) M shows that the Ag/C/AgNps nanosphere is a good SERS-active substrate. The effect of heavy metal ions on the detection of melamine is also investigated. It was found that the SERS spectrum profile of melamine is very sensitive to the presence of heavy metal ions: the peak positions of the SERS bands exhibit some apparent change with the kind of metal ion, showing a blue or red shift compared with those in the SERS spectrum of melamine; the SERS signal intensity decrease with increasing the concentration of metal ion.     

Surface-enhanced Raman scattering on nanodiamond-derived carbon onions

Annealing nanodiamonds(ND) at high temperatures up to 1700 ℃ is a common method to synthesize carbon onions. The transformation from NDs to carbon onions is particularly interesting because of carbon onions' potential in the field of tribology and their application in ultra-charge/discharge devices. In this paper, a novel surface-enhanced Raman scattering technique that involves coating the sample with nanoscopic gold particles is proposed to characterize the NDs after different annealing treatments. Conventional Raman and surfaceenhanced Raman spectra were obtained, and the changes of peak parameters as the function of annealing temperature were evaluated. It was found that the widths of the D and the G peaks decreased with increasing annealing temperature, reflecting an improved order in the sp~2-hybridized carbon during the transformation from NDs to carbon onions. After annealing at 1700 ℃, the sp~2?carbon was highly ordered, indicating desirable electrical conductivity and lubricity. With increasing annealing temperature, the D peak showed a blue shift of almost30 cm~(-1), while the G peak merely shifted by 5 cm~(-1). For annealing temperatures above 1100 ℃, an increase of intensity ratio ID/IGwas observed. Compared to the uncoated area, red shifts of 0.5-2 cm~(-1) and of 5-9 cm~(-1) for the G and D peaks, respectively, were detected for the gold-coated area, which was due to the coupling of the plasmons and the phonons of the samples.     

Surface-enhanced Raman scattering on single-wall carbon nanotubes

Exploiting the effect of surface-enhanced Raman scattering (SERS), the Raman signal of single-wall carbon nanotubes (SWNTs) can be enhanced by up to 14 orders of magnitude when the tubes are in contact with silver or gold nanostructures and Raman scattering takes place predominantly in the enhanced local optical fields of the nanostructures. Such a level of enhancement offers exciting opportunities for ultrasensitive Raman studies on SWNTs and allows resonant and non-resonant Raman experiments to be done on single SWNTs at relatively high signal levels. Since the optical fields are highly localized within so-called "hot spots" on fractal silver colloidal clusters, lateral confinement of the Raman scattering can be as small as 5 nm, allowing spectroscopic selection of a single nanotube from a larger population. Moreover, since SWNTs are very stable "artificial molecules" with a high aspect ratio and a strong electron-phonon coupling, they are unique "test molecules" for investigating the SERS effect itself and for probing the "electromagnetic field contribution" and "charge transfer contribution" to the effect. SERS is also a powerful tool for monitoring the "chemical" interaction between the nanotube and the metal nanostructure.     

Surface-enhanced spectra on D-gluconic acid coated silver nanoparticles

Coated silver (Ag) colloids synthesized with D-glucose permit the observation of surface-enhanced fluorescence (SEF) and surface-enhanced resonance Raman scattering (SERRS) of the rhodamine B (RhB) molecule. The organic coating formed during the synthesis of the Ag nanostructures was identified by its surface-enhanced Raman scattering (SERS) spectrum as D-gluconic acid. The RhB molecule is used to exemplify the distance dependence of SEF and SERRS on the coated Ag nanostructures. The fluorescence enhancement factor for RhB on D-gluconic acid coated silver nanoparticles was determined experimentally and estimated using a simple model. Further support for the plasmon enhancement is obtained from the fact that the measured fluorescence lifetime of RhB on the silver coated with D-gluconic acid is shorter than that found on a glass surface. A very modest enhancement factor is obtained, as expected for very short distance between RhB and the metal surface. Given the very thin metal-fluorophore separation, estimated from the size of the D-gluconic acid, the energy transfer or fluorescence quenching is still efficient and the SEF enhancement is just overcoming the energy transfer. Therefore, both SEF and SERRS are observed. Notably, the aggregation of coated nanoparticles also increases the enhancement factor for SEF.     

Part II: surface-enhanced Raman spectroscopy investigation of methionine containing heterodipeptides adsorbed on colloidal silver

Surface-enhanced Raman scattering (SERS) spectra of methionine (Met) containing dipeptides: Met-X and X-Met, where X is: L-glycine (Gly), L-leucine (Leu), L-proline (Pro), and L-phenylalanine (Phe) are reported. Using pre-aggregated Ag colloid we obtained high-quality SERS spectra of these compounds spontaneously adsorbed on colloidal silver. Additionally, we measured Raman spectra (RS) of these heterodipeptides in a solid state as well as in acidic and basic solutions. The RS and SERS spectra of Met-X and X-Met presented in this work appear to be different. One of the most prominent and common features in the SERS spectra of all these dipeptides is a band in the 660-690 cm(-1) range that is due to the C-S stretching, v(CS), vibration of Met. This suggests that all the abovementioned compounds adsorb on the silver surface through a thioether atom. On the other hand, the SERS spectra of X-Met show clearly that not only the S atom but also the carboxylate group interact with the colloid surface as manifested by the enhancement of bands in the 920-930 and 1380-1396 cm(-1) regions. These bands are ascribed to the v(C-COO(-)) and v(sym)(COO(-)) vibrations, respectively. Additionally, a SERS spectrum of Phe-Met indicates that the interaction of the thioether atom, amine group, and aromatic side chain with the silver surface is favorable and may dictate the orientation and conformation of adsorbed peptide.     

Adsorption of S-S containing proteins on a colloidal silver surface studied by surface-enhanced Raman spectroscopy

We present a Raman and surface-enhanced Raman scattering (SERS) study of the following proteins containing S-S group(s): alpha chymotrypsin (alpha-CHT), insulin, lysozyme, oxytocin (OXT), Streptomyces subtilisin inhibitor (SSI), and trypsin inhibitor (STI). The SERS study is performed in order to understand the adsorption mechanism of the above-mentioned proteins on a colloidal silver surface. The SERS spectra presented here show bands associated mainly with aromatic amino acid vibrations. In addition, two distinct vibrations of the -C-S-S-C- fragment are observed in the Raman and SERS spectra, i.e., nu(SS) and nu(CS). The enhancement of the nu(SS) vibration in the SERS spectra yields evidence that the intact disulfide bridge(s) is (are) located near the silver surface. This finding is supported by the presence of the nu(CS) mode(s). The presence of nus(COO-) and nu(C-COO-) in the SERS spectra in the 1384-1399 cm(-1) and 909-939 cm(-1) regions, respectively, indicate that the negatively charged COO- groups (aspartic and glutamic acids) assist in the binding on the positively charged silver surface. The Raman amide I and III bands observed in the 1621-1633 and 1261-1289 cm(-1) ranges, respectively, indicate that the alpha-helical conformation is favored for binding to the surface over the random coil or beta-sheet conformations. In addition, the presence of the imino group of Trp and/or His indicates that these amino acid residues may also bind to the silver sol.     

Surface-enhanced Raman scattering (SERS) characterization of trace organoarsenic antimicrobials using silver/polydimethylsiloxane nanocomposites

Organoarsenic drugs such as roxarsone and 4-arsanilic acid are poultry feed additives widely used in US broilers to prevent coccidosis and to enhance growth and pigmentation. Despite their veterinary benefits there has been growing concern about their use because over 90% of these drugs are released intact into litter, which is often sold as a fertilizing supplement. The biochemical degradation of these antimicrobials in the litter matrix can release significant amounts of soluble As(III) and As(V) to the environment, representing a potential environmental risk. Silver/polydimethylsiloxane (Ag/PDMS) nanocomposites are a class of surfaceenhanced Raman scattering (SERS) substrates that have proven effective for the sensitive, reproducible, and field-adaptable detection of aromatic acids in water. The work presented herein uses for the first time Ag/PDMS nanocomposites as substrates for the detection and characterization of trace amounts of roxarsone, 4-arsanilic acid, and acetarsone in water. The results gathered in this study show that organoarsenic species are distributed into the PDMS surface where the arsonic acid binds onto the embedded silver nanoparticles, enhancing its characteristic 792 cm(-1) stretching band. The chemisorption of the drugs to the metal facilitates its detection and characterization in the parts per million to parts per billion range. An extensive analysis of the distinct spectroscopic features of each drug is presented with emphasis on the interactions of the arsonic acid, amino, and nitro groups with the metal surface. The benefits of SERS based methods for the study of arsenic drugs are also discussed.     

五种磺胺类药物残留的快速测定

采用反相高效液相色谱法(RP-HPLC),同时快速测定五种磺胺类药物残留。在Waters Nova-Pak C18 柱上,用紫外或PDA检测器,流速1.0 mL/min,柱温35℃,于267 nm波长处检测,流动相为5 mmol/L NaH2PO4 溶液-乙腈溶液(体积比为70∶30),磷酸调pH 3.0。完成整个色谱分离只须3.5 min,比原来的11 min大大减少了分离时间。     

Surface-enhanced Raman scattering on gold nanotrenches and nanoholes

Dependent effects on edge-to-edge distance and incidence polarization in surface-enhanced Raman Scattering (SERS) were studied in detection of 4-mercaptopyridine (4-MPy) molecules absorbed on gold nanotrenches and nanoholes. The gold nanostructures with controllable size and period were fabricated using electron-beam lithography. Large SERS enhancement in detection of 4-MPy molecules on both nanostructred substrates was observed. The SERS enhancement increased exponentially with decrease of edge-to-edge distance for both the nanotrenches and nanoholes while keeping the sizes of the nanotrenches and nanoholes unchanged. Investigation of polarization dependence showed that the SERS enhancement of nanotrenches was much more sensitive to the incidence polarizations than that of nanoholes.     

五种磺胺类药物残留的快速测定

采用反相高效液相色谱法(RP-HPLC),同时快速测定五种磺胺类药物残留。在Waters Nova--Pak C18柱上,用紫外或PDA检测器,流速1．0mL／min,柱温35U,于267nm波长处检测,流动相为5mmol／LNaH2PO4溶液-乙腈溶液(体积比为70：30),磷酸调pH3．0。完成整个色谱分离只须3．5min,比原来的11min大大减少了分离时间．     

Part III: Surface-enhanced Raman scattering of amino acids and their homodipeptide monolayers deposited onto colloidal gold surface

Surface-enhanced Raman scattering (SERS) spectra were measured for monolayers of various amino acids: L-methionine (Met), L-cysteine (Cys), L-glycine (Gly), L-leucine (Leu), L-phenylalanine (Phe), and L-proline (Pro) and their homodipeptides (Met-Met, Cys-Cys, Gly-Gly, Leu-Leu, Phe-Phe, and Pro-Pro) deposited onto a colloidal gold surface. Orientation of amino acids and their homodipeptides, as well as specific-competitive interactions of their functional groups with the gold surface, were predicted by detailed spectral analysis of the obtained SERS spectra. The analysis performed allowed us to propose a particular surface geometry for each amino acid and homodipeptide on the gold surface. In addition, we compared the structures of these molecules adsorbed on colloidal gold and silver surfaces.