Surface-enhanced Resonance Raman Scattering Substrate Research Articles

Au@Ag nanorods for analysis of dyes by SERS spectroscopy

We report on surface-enhanced Raman scattering (SERS) activity of bimetallic core-shell Au@Ag nanorods. These nanostructures feature four plasmon maxima in the UV-visible range. Their application for SERS analysis enables matching individual optical properties of organic analytes using the optimal excitation wavelength resonant both for plasmon nanostructures and analytes. It promotes higher sensitivity of surface-enhanced resonance Raman scattering (SERRS) of specific analytes. The intensity of SERRS spectrum is higher up to 2 orders of magnitude for alizarin and up to 4 times for malachite green as compared to the corresponding SERS spectra. Thus Au@Ag nanorods can be used as a single SERRS substrate for sensitive analysis of a number of dyes.

A Poly Adenine-Mediated Assembly Strategy for Designing Surface-Enhanced Resonance Raman Scattering Substrates in Controllable Manners.

In this article, we introduce a Poly adenine (Poly A)-assisted fabrication method for rationally designing surface-enhanced resonance Raman scattering (SERRS) substrates in controllable and reliable manners, enabling construction of core-satellite SERRS assemblies in both aqueous and solid phase (e.g., symmetric core (Au)-satellite (Au) nanoassemblies (Au-Au NPs), and asymmetric Ag-Au NPs-decorated silicon wafers (Ag-Au NPs@Si)). Of particular significance, assembly density is able to be controlled by varying the length of the Poly A block (e.g., 10, 30, and 50 consecutive adenines at the 5' end of DNA sequence, Poly A10/A30/A50), producing the asymmetric core-satellite nanoassemblies with adjustable surface density of Au NPs assembly on core NPs surface. Based on quantitative interrogation of the relationship between SERRS performance and assemble density, the Ag-Au NPs@Si featuring the strongest SERRS enhancement factor (EF ≈ 10(7)) and excellent reproducibility can be achieved under optimal conditions. We further employ the resultant Ag-Au NPs@Si as a high-performance SERRS sensing platform for the selective and sensitive detection of mercury ions (Hg(2+)) in a real system, with a low detection limit of 100 fM, which is ∼5 orders of magnitude lower than the United States Environmental Protection Agency (USEPA)-defined limit (10 nM) in drinkable water. These results suggest the Poly A-mediated assembly method as new and powerful tools for designing high-performance SERRS substrates with controllable structures, facilitating improvement of sensitivity, reliability, and reproducibility of SERRS signals.

Regenerative silver nanoparticles for SERRS investigation of metmyoglobin with conserved heme pocket

Shell isolated silver nanoparticles with an ultrathin silica layer (Ag@SiO2NPs) are used as a surface-enhanced resonance Raman scattering (SERRS) substrate for probing metmyoglobin (metMb) in aqueous solution. The ultrathin silica layer protects metMb from reaching the bare silver surface and conserves the heme pocket during SERRS analysis with a Raman enhancement factor (EFSERS) of 4.78 × 104. In spite of the good SERRS enhancement, the interaction between the protein and Ag@SiO2NPs is weak enough to separate them by centrifugation in such a way that both are regenerated in their original form and can be reused. Using Ag@SiO2NPs as the SERRS substrate, the lowest detection limit of 2 nM was achieved for metMb whilst conserving the native structure of the heme centre.

An investigation into the simultaneous enzymatic and SERRS properties of silver nanoparticles

Investigation into the use of artificial enzymes has become an increasingly popular area of research due to the numerous advantages offered in comparison to protein enzymes. One particular area of research interest involves the use of metal nanoparticles as artificial enzymes. The peroxidase-like activity of a variety of nanoparticles has recently been shown and their use in a range of assay formats for the detection of various analytes has been explored. Herein the enzyme mimicking activity of silver nanoparticles is investigated using the peroxidase substrate 3,3',5',5'-tetramethylbenzidine (TMB). The peroxidase-like nature of these nanoparticles can be used in combination with surface enhanced resonance Raman scattering (SERRS) to provide a novel spectroscopic method of analysis. Negatively charged silver nanoparticles were investigated in combination with TMB using SERRS and it was found that upon formation of the oxidation intermediate of TMB, small clusters of positively charged nanoparticles were formed. The enzyme like behaviour of silver nanoparticles along with their use as a SERRS substrate is combined to demonstrate a simple and rapid method for the direct detection of hydrogen peroxide with a detection limit of 100 nM.

Quantitative Enhanced Raman Scattering of Labeled DNA from Gold and Silver Nanoparticles

Surface-enhanced resonance Raman scattering (SERRS) from silver nanoparticles using 514.5-nm excitation has been shown to offer huge potential for applications in highly sensitive multiplexed DNA assays. If the technique is to be applied to real biological samples and integrated with other methods, then the use of gold nanoparticles and longer wavelengths of excitation are desirable. The data presented here demonstrate that dye-labeled oligonucleotide sequences can be directly detected by SERRS using gold nanoparticles in a quantitative manner for the first time. The performance of gold and silver nanoparticles as SERRS substrates was assessed using 514.5-, 632.8-, and 785-nm excitation and a range of 13 commercially available dye-labeled oligonucleotides. The quantitative response allowed the limit of detection to be determined for each case and demonstrates that the technique is highly effective, sensitive, and versatile. The possibility of excitation at multiple wavelengths further enhances the multiplexing potential of the technique. The importance of effectively combining the optical properties of the nanoparticle and the dye label is demonstrated. For example, at 632.8-nm excitation, the dye BODIPY TR-X and gold nanoparticles make a strong SERRS combination with very little background fluorescence. This study allows the choice of nanoparticle and dye label for particular experimental setups, and significantly expands the applicability of enhanced Raman scattering for use in many disciplines.

Quantitative analysis of mitoxantrone by surface-enhanced resonance Raman scattering.

Mitoxantrone is an anticancer agent for which it is important to know the concentration in blood during therapy. Current methods of analysis are cumbersome, requiring a pretreatment stage. A method based on surface-enhanced resonance Raman scattering (SERRS) has been developed using a flow cell and silver colloid as the SERRS substrate. It is simple, sensitive, fast, and reliable. Both blood plasma and serum can be analyzed directly, but fresh serum is preferred here due to reduced fluorescence in the clinical samples available. Fluorescence is reduced further by the dilution of the serum in the flow cell and by quenching by the silver of surface-adsorbed material. The effectiveness of the latter process is dependent on the contact time between the serum and the silver. The linear range encompasses the range of concentrations detected previously in patient samples using HPLC methods. In a comparative study of a series of samples taken from a patient at different times, there is good agreement between the results obtained by HPLC and SERRS with no significant difference between them at the 95% limit. The limit of detection in serum using the final optimized procedure for SERRS was 4.0 x 10(-11) M (0.02 ng/mL) mitoxantrone. The ease with which the SERRS analysis can be carried out makes it the preferred choice of technique for mitoxantrone analysis.

Preparation of Stable, Reproducible Silver Colloids for Use as Surface-Enhanced Resonance Raman Scattering Substrates

A flow system for the production of stable, reproducible batches of silver colloid for use as substrates for surface-enhanced resonance Raman spectroscopy (SERRS) is described. The colloids were prepared by borohydride reduction of silver nitrate and subsequent stabilization was achieved by adding trisodium citrate. The batches of colloid produced were analyzed using UV-visible spectroscopy and their suitability for use as SERRS substrates was assessed using 3,5-dimethoxy-4-(5′-azobenzotriazole)phenylamine as the analyte. SERRS analysis was carried out using a flowcell. Using the method described, batches of silver colloid were prepared that were stable for at least five months and when used as SERRS substrates resulted in a relative standard deviation in SERRS intensity of 3,5-dimethoxy-4-(5′-azobenzotriazole)phenylamine of 6.6% between colloid batches. The robustness of the system for production of stable, reproducible colloids was assessed using experimental design. The final method proposed enables reproducible, time-stable colloid to be made in a simple manner, thus eliminating one of the major problems associated with the use of SERRS detection in analytical procedures.

SERRS. In situ substrate formation and improved detection using microfluidics.

Surface-enhanced resonance Raman scattering (SERRS) of a model derivative of TNT was detected using a microflow cell designed within the framework of the lab-on-a-chip concept, using only the analyte and readily available reagents. The SERRS substrate, silver colloid, was prepared in situ, on-chip, by borohydride reduction of silver nitrate. The silver colloid was imaged within the chip using a white light microscope in either transmission or, due to the high reflectivity of the colloid, reflection mode. A fine stream of colloid approximately 30 microm in width was formed in a 250-microm-wide channel at the point where the colloid preparation reagents met. The chip was designed to produce a concentrated stream of colloid within a laminar regime, such that particles did not readily disperse into the fluid. One result of this was to reduce the effective volume of analysis. Attempts to deliberately disrupt this stream with microstructured pillars, fabricated in the fluidic channels, were unsuccessful. The chip was also designed to have the appropriate dimensions for detection using a modern Raman microscope system, which collects scattering from a very small volume. A dye derived from TNT was used as a model analyte. Quantitative behavior was obtained over 4 orders of magnitude with a detection limit of 10 fmol. This performance is between 1 and 2 orders of magnitude better than that achieved using a macroflow SERRS cell. The technique has the added advantage that both reagent consumption and effluent production are greatly reduced, leading to reduced operating costs and a decreased environmental impact