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.     

Surface enhanced Raman scattering of neurotransmitter release in neuronal cells using antibody conjugated gold nanoparticles

This study demonstrated the potential feasibility of using antibody-conjugated gold nanoparticles as highly sensitive and homogeneous sensing probes for biological monitoring of neurotransmitters in neuronal cells. Bands at 1152 and 1322 cm(-1) were also similar to SERS of metal catecholates, and could be assigned to catechol ring vibration and carbon-oxygen stretches.     

Preparation of silver nanoparticles by photo-reduction for surface-enhanced Raman scattering

A substrate for surface-enhanced Raman scattering (SERS) has been developed. Based on the surface-catalyzed reduction of Ag⁺ by citrate on the silver nanoparticles surface under light irradiation, small silver seeds on a quartz slide can be enlarged. The optical properties and characteristics of the silver films have been investigated by ultraviolet-visible spectroscopy, scan electron microscope and atomic force microscopy (AFM). The results indicate that the particle size and shape are different at different reduction time. At the first 3 h, some triangular and hexagonal nanoparticles formed; with the reduction proceeding, the shape of the silver particles became irregular and the size became larger. The silver films obtained are very suitable as SERS active substrate. The relationship between SERS intensity and the reduction time has been investigated for 1,4-bis[2-(4-pyridyl)ethenyl]-benzene molecule adsorbed on the silver film. The SERS intensity reached a maximum at 8 h reduction. The AFM measurements indicate that roughness features with an average size of 100 nm are present on the surface, which yielded the strongest SERS signal. Pyridine was used as a probe molecule to investigate the enhancement factor (EF) of the silver films. According to the formalism of Tian and co-workers, the EF of the silver films is estimated to be 3.4 × 10⁵. The silver film that can remain active for more than 50 days would seem to be suitable for various analytical applications.     

Metal-coated magnetic nanoparticles for surface enhanced Raman scattering studies

We report the optimization and usage of surfactantless, water dispersible Ag and Au-coated gboldsymbolgamma–Fe₂_{boldsymbol 2}O₃_{boldsymbol 3} nanoparticles for applications in surface-enhanced Raman scattering (SERS). These nanoparticles, with plasmonic as well as super paramagnetic properties exhibit Raman enhancement factors of the order of 10⁶ (10⁵) for Ag (Au) coating, which are on par with the conventional Ag and Au nanoparticles. Raman markers like 2-naphthalenethiol, rhodamine-B and rhodamine-6G have been adsorbed to these nanoparticles and tested for nonresonant SERS at low concentrations. Further, to confirm the robustness of Ag-coated nanoparticles, we have performed temperature-dependent SERS in the temperature range of 77–473 K. The adsorbed molecules exhibit stable SERS spectra except at temperatures $boldsymbol >$boldsymbol >323 K, where the thermal desorption of test molecule (naphthalenethiol) were evident. The magnetic properties of these nanoparticles combined with SERS provide a wide range of applications.     

Temperature dependence of silver nanostructure for surface enhanced Raman scattering application

We study the fabrication and application of the fractal silver nanostructure using an electrochemical process. Scanning electron microscope and high resolution transmission electron microscope images show the morphology of silver nanostructure can be well controlled via the various reaction times. The surface enhanced Raman scattering of 10 microM aqueous Rhodamine 6G (R6G) solutions conducted in as-fabricated silver nanostructure achieved an enhancement factor approximately 10(5) at room temperature. Meanwhile, an approximately 10(4) enhancement factor of SERS signal can be kept under 200 degrees C in present study. This study can help us to integrate the nano-metals and nano-particles for advanced nano devices.     

Superhydrophobicity and surface enhanced Raman scattering activity of dendritic silver layers

Dendritic silver nanostructured surface has been prepared on copper substrate by a simple replacement reaction. It was observed that morphology of the silver surface became much rough with reaction time, from initial nanosized clusters to nanostructured dendrites. The silver surface modified with dodecanethiol showed great superhydrophobicity. It was also found that the dendritic silver nanostructured surface demonstrated highly sensitive surface enhanced Raman scattering (SERS) character. It is expected that the dendritic silver surface may be applied as molecular probe and biological sensing.     

Reproducible surface-enhanced Raman scattering spectra of bacteria on aggregated silver nanoparticles

Surface-enhanced Raman scattering (SERS) is proven to be a powerful technique for rapid identification and discrimination of microorganisms. However, due to the heterogeneous nature of the samples, the acquisition of reproducible spectra hinders the further development of the technique. In this study, we demonstrate the influence of the experimental conditions on SERS spectra. Then, we report a simple sample preparation method coupled with a light microscope attached to a Raman spectrometer to find a proper spot on the sample to acquire reproducible SERS spectra. This method utilizes the excited surface plasmons of the aggregated silver nanoparticles to visualize the spots on the sample. The samples are prepared using the concentrated silver colloidal solutions. The collection time for one spectrum is 10 s and each spectrum is a very good representative of the other spectra acquired from the same sample. The nature of the surface charge of the silver nanoparticles influences the spectral features by determining the strength of the interactions between nanoparticles and bacteria and the aggregation properties of the nanoparticles. Although increasing the colloid concentration in the sample resulted in reproducible spectra from arbitrary points on the sample, a great variation from sample to sample prepared with the different colloidal solution concentrations is observed.     

Surface enhanced Raman scattering spot tests: a new insight on Feigl's analysis using gold nanoparticles

Traditional Feigl's spot tests can be greatly improved with the aid of gold nanoparticles and Raman probes, by monitoring the changes in the surface enhanced Raman scattering (SERS) of the analytes directly applied on a filter paper previously impregnated with the selective organic reagent. As a proof of concept, diphenylthiocarbazone (dithizone) was treated with citrate stabilized gold nanoparticles and employed in paper spot tests for a variety of transition and heavy metal ions. Below 10(-5) mol L(-1), only mercury(II) ions were able to displace the dithizone molecules from the "coordination shell" of the gold nanoparticles, leading to a systematic decay of the Raman signals. Because of the huge enhancement of the dithizone vibrational peaks, the SERS spot tests allowed the detection of picograms of Hg(2+) ions.     

Surface enhanced coherent anti-stokes Raman scattering on nanostructured gold surfaces

Coherent anti-Stokes Raman spectroscopy (CARS) is a well-known tool in multiphoton imaging and nonlinear spectroscopy. In this work we combine CARS with plasmonic surface enhancement on reproducible nanostructured surfaces. We demonstrate strong correlation between plasmon resonances and surface-enhanced CARS (SECARS) intensities on our nanostructured surfaces and show that an enhancement of ～10(5) can be obtained over standard CARS. Furthermore, we find SECARS to be >10(3) times more sensitive than surface-enhanced Raman Spectroscopy (SERS). We also demonstrate SECARS imaging of molecular monolayers. Our work paves the way for reliable single molecule Raman spectroscopy and fast molecular imaging on plasmonic surfaces.     

Surface enhanced Raman scattering on long-range ordered noble-metal nanocrescent arrays

Long-range ordered noble-metal nanocrescent arrays of different sizes and shapes have been successfully fabricated by using both nanoimprint lithography and e-beam lithography techniques. Large surface enhanced Raman scattering (SERS) enhancements in the detection of rhodamine 6G (R6G) molecules on these arrays have been observed and attributed to the enhancement of the local electromagnetic (EM) fields near individual nanocrescents. Electromagnetic enhancement factors for crescents of different shapes are computed using the discrete dipole approximation and compared with experimental measurements of the R6G Raman intensities. It is found that the maximum values of SERS intensity appear at an intermediate value of the crescent eccentricity and the observed behaviour is related to the spatial distributions of the enhancement of the local EM field (hot spots).     

Active control of silver nanoparticles spacing using dielectrophoresis for surface-enhanced Raman scattering

We demonstrate an active microfluidic platform that integrates dielectrophoresis for the control of silver nanoparticles spacing, as they flow in a liquid channel. By careful control of the nanoparticles spacing, we can effectively increase the surface-enhanced Raman scattering (SERS) signal intensity based on augmenting the number of SERS-active hot-spots, while avoiding irreversible aggregation of the particles. The system is benchmarked using dipicolinate (2,6-pyridinedicarboxylic acid) (DPA), which is a biomarker of Bacillus anthracis. The validity of the results is discussed using several complementing characterization scenarios.     

Surface enhanced Raman scattering from porous gold nanofibers of different diameters

Porous gold nanofibers of different diameters from 43 to 219 nm were fabricated using electrochemical deposition techniques. Gold-silver alloy were electrochemically deposited in the form of nanofibers within the porous alumina templates of various diameters and only a silver phase was chemically removed using nitric acid. Field-emission scanning electron microscope images of the resulting nanofibers show a high-quality nanoporous network with homogeneous pores. A notable surface-enhanced Raman scattering (SERS) has been observed for all porous gold nanofibers of which scattering efficiencies are distinctly higher than that of the smooth solid gold nanofibers without porosity. As the diameter of porous gold nanofibers decreases, the observed SERS efficiency gradually increases. Controlled fabrication of lateral width of gold nanofibers reveals promising application for high efficient and stable molecular sensing platforms.     

Type I collagen-templated assembly of silver nanoparticles and their application in surface-enhanced Raman scattering

Silver nanoparticles (Ag NPs) are one of the active substrates that are employed extensively in surface-enhanced Raman scattering (SERS), and aggregations of Ag NPs play an important role in enhancing the Raman signals. In this paper, we fabricated two kinds of SERS-active substrates utilizing the electrostatic adsorption and superior assembly properties of type I collagen. These were collagen-Ag NP aggregation films and nanoporous Ag films. Two probe molecules, 4-aminothiophenol (4-ATP) and methylene blue (MB), were studied on these substrates. These substrates showed reproducible SERS intensities with relative standard deviations (RSDs) of 8-10% and 11-14%, respectively, while the RSDs of the traditional thick Ag films were 12-28%. Also, the intensities for the 4-ATP spectrum on the collagen-templated nanoporous Ag film were approximately one order higher than those on the DNA-templated Ag?film.     

Control of enhanced Raman scattering using a DNA-based assembly process of dye-coded nanoparticles

Enhanced Raman scattering from metal surfaces has been investigated for over 30 years. Silver surfaces are known to produce a large effect, and this can be maximized by producing a roughened surface, which can be achieved by the aggregation of silver nanoparticles. However, an approach to control this aggregation, in particular through the interaction of biological molecules such as DNA, has not been reported. Here we show the selective turning on of the surface enhanced resonance Raman scattering effect on dye-coded, DNA-functionalized, silver nanoparticles through a target-dependent, sequence-specific DNA hybridization assembly that exploits the electromagnetic enhancement mechanism for the scattering. Dye-coded nanoparticles that do not undergo hybridization experience no enhancement and hence do not give surface enhanced resonance Raman scattering. This is due to the massive difference in enhancement from nanoparticle assemblies compared with individual nanoparticles. The electromagnetic enhancement is the dominant effect and, coupled with an understanding of the surface chemistry, allows surface enhanced resonance Raman scattering nanosensors to be designed based on a natural biological recognition process.     

Properties of polypropylene nanocomposites containing silver nanoparticles

Silver/polypropylene (PP) nanocomposites containing silver nanoparticles smaller than 10 nm were prepared using a new synthetic method. AgNO3 crystals were dissolved into hydrophilic domain of polyoxyethylene maleate-based surfactant (PEOM), which gives self-assembly nano-structures. The AgNO3 in the nano-domains of PEOM was reduced by NaBH4 to form nanoparticles. The colloidal solutions with silver nanoparticles were diluted with ethanol and were mixed with PP pellets. Silver nanocomposites were prepared by extrusion compounding process after drying the pellets. Contents of silver nanoparticles dispersed within PP resin were changed from 100 to 1000 ppm. Formation of silver nanoparticles within PP was confirmed by UV-Vis spectroscopy and TEM. Size and distribution of dispersed silver nanoparticles were also measured by TEM. Silver/PP nanocomposites films showed not only improved thermal stability but also increased mechanical properties compared to neat PP film. Tensile properties of PP nanocomposites were largely improved compared with neat PP resin, and elongation increased also by 175% for the nanocomposites containing 1000 ppm silver nanoparticles.     

Moving nanoparticles with Raman scattering

We show how to change optically the distance between two protein-linked gold nanoparticles by Raman-induced motion of the linker protein. Rayleigh scattering spectroscopy of the coupled-particle plasmon allows us to compare the inter-nanoparticle distance of individual protein-linked gold nanoparticle dimers before and after surface-enhanced Raman scattering (SERS). We find that low-intensity (50 microW/microm2) laser light in resonance with the nanoparticle-dimer plasmon provokes a change of the inter-nanoparticle distance on the order of 0.5 nm whenever SERS from the proteins connecting the nanoparticles can be observed.     

Ag nanoparticles coated SWCNT with surface enhanced Raman scattering (SERS) signals

We report here a simple method to fabricate the silver nanoparticles (AgNPs) coated DNA-SWCNTs that give SERS signals. Dynamic light scattering (DLS), atomic force microscopy (AFM), and high resolution transmission electron microscopy (HRTEM) suggested the products are dispersive and soluble in aqueous solution. The Raman scattering spectra show AgNPs coated SWCNTs have enhanced the Raman signal when compared with pure SWCNT. From the radial breathing mode (RBM) of the Raman spectra, we can disclose that this DNA-SWCNT has unique chirality, which implies that it could be a good nanoprobe for cell marking.     

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.     

Effect of oxidation on surface-enhanced Raman scattering activity of silver nanoparticles: a quantitative correlation

We quantitatively studied, using X-ray photoelectron spectroscopy (XPS), oxidation of substrate-immobilized silver nanoparticles (Ag NPs) in a wide range of conditions, including exposure to ambient air and controlled ozone environment under UV irradiation, and we correlated the degree of silver oxidation with surface-enhanced Raman scattering (SERS) enhancement factors (EFs). The SERS activity of pristine and oxidized Ag NPs was assessed by use of trans-1,2-bis(4-pyridyl)ethylene (BPE) and sodium thiocynate as model analytes at the excitation wavelength of 532 nm. Our study showed that the exposure of Ag NPs to parts per million (ppm) level concentrations of ozone led to the formation of Ag(2)O and orders of magnitude reduction in SERS EFs. Such an adverse effect was also notable upon exposure of Ag NPs under ambient conditions where ozone existed at parts per billion (ppb) level. The correlated XPS and SERS studies suggested that formation of just a submonolayer of Ag(2)O was sufficient to decrease markedly the SERS EF of Ag NPs. In addition, studies of changes in plasmon absorption bands pointed to the chemical enhancement as a major reason for deterioration of SERS signals when substrates were pre-exposed to ambient air, and to a combination of changes in chemical and electromagnetic enhancements in the case of substrate pre-exposure to elevated ozone concentrations. Finally, we also found UV irradiation and ozone had a synergistic effect on silver oxidation and thus a detrimental effect on SERS enhancement of Ag NPs and that such oxidation effects were analyte-dependent, as a result of inherent differences in chemical enhancements and molecular binding affinities for various analytes.