Silica-void-gold nanoparticles: temporally stable surface-enhanced Raman scattering substrates.

Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA.
Journal of the American Chemical Society (Impact Factor: 11.44). 11/2008; 130(43):14273-9. DOI: 10.1021/ja8059039
Source: PubMed

ABSTRACT Reproducible detection of a target molecule is demonstrated using temporally stable solution-phase silica-void-gold nanoparticles and surface-enhanced Raman scattering (SERS). These composite nanostructures are homogeneous (diameter = 45 +/- 4 nm) and entrap single 13 nm gold nanoparticle cores inside porous silica membranes which prevent electromagnetic coupling and aggregation between adjacent nanoparticles. The optical properties of the gold nanoparticle cores and structural changes of the composite nanostructures are characterized using extinction spectroscopy and transmission electron microscopy, respectively, and both techniques are used to monitor the formation of the silica membrane. The resulting nanostructures exhibit temporally stable optical properties in the presence of salt and 2-naphthalenethiol. Similar SERS spectral features are observed when 2-naphthalenethiol is incubated with both bare and membrane-encapsulated gold nanoparticles. Disappearance of the S-H Raman vibrational band centered at 2566 cm(-1) with the composite nanoparticles indicates that the target molecule is binding directly to the metal surface. Furthermore, these nanostructures exhibit reproducible SERS signals for at least a 2 h period. This first demonstration of utilizing solution-phase silica-void-gold nanoparticles as reproducible SERS substrates will allow for future fundamental studies in understanding the mechanisms of SERS using solution-phase nanostructures as well as for applications that involve the direct and reproducible detection of biological and environmental molecules.

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    Bulletin- Korean Chemical Society 11/2011; 32(11). · 0.84 Impact Factor
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    ABSTRACT: Powdered nanocomposite materials composed of SBA-15 mesoporous silica and different types of Au nanoparticles within the mesoporous channel pores (Au/SBA-15) are shown to serve as robust and efficient substrates for surface-enhanced Raman spectroscopy (SERS). Using the Au/SBA-15 samples as SERS substrates and 4-mercaptopyridine (4-Mpy) as SERS reporter molecule, SERS enhancement factors as high as 105 are obtained. The degree of SERS enhancement is found to depend on the size of the Au nanoparticles as well as the synthetic procedures employed to synthesize the Au/SBA-15 materials. The high SERS enhancement given by the Au/SBA-15 as compared to any other powered SERS substrates appears to be the result of the formation of SERS “hot spots” due to the side-by-side alignment of Au nanoparticles within the cylindrical channel pores of the SBA-15 mesoporous silica host. Because of their powdered forms, longevity, simple sample preparation procedures, easily tunable surface, and high SERS enhancement factors, Au/SBA-15 can also be expected to serve as simple and convenient-to-use substrates for SERS-based analysis of various analytes, besides 4-Mpy. Furthermore, this work demonstrates the synthesis of supported “naked” Au nanoparticles and their use as SERS substrate directly and without any further chemical modification.
    The Journal of Physical Chemistry C 10/2011; 115(46):22810–22817. · 4.84 Impact Factor
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    ABSTRACT: Control over the composition, shape, size, stability, and local dielectric environment of solution-phase metallic substrates is vital to consistent surface-enhanced Raman scattering (SERS) signals. Because of their inherent instability, solution-phase nanoparticles can undergo uncontrolled aggregation when target molecules are added. Here, we demonstrate that both molecular surface coverage of the Raman active molecule, 2-naphthalenethiol (2-NT), and nanoparticle concentration are critical parameters for obtaining reproducible SERS signals using solution-phase gold nanoparticles. Both gold nanoparticle and 2-naphthalenethiol concentrations are varied, and the extinction of the nanoparticle substrate and the SERS intensity of the target molecule are monitored as a function of time. These results indicate that extinction and SERS spectral intensities increase predictably below full monolayer surface coverage. When excess molecules are added, uncontrolled and irreproducible nanoparticle aggregation leads to optimal overlap between the plasmonic properties of the nanoparticles and the SERS excitation wavelength. Importantly, this is the first report which correlates solution-phase nanoparticle concentration and stability to molecular surface coverage for simultaneous localized surface plasmon resonance (LSPR) and SERS spectroscopic measurements. As a result, these data should facilitate the experimental design and use of solution-phase SERS substrates for more predictable molecular detection.
    The Journal of Physical Chemistry C 09/2011; 115(38):18511–18517. · 4.84 Impact Factor


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