Plasmonic platforms of self-assembled silver nanostructures in application to fluorescence.

Fluorescence intensity changes were investigated theoretically and experimentally using self-assembled colloidal structures on silver semitransparent mirrors. Using a simplified quasi-static model and finite element method, we demonstrate that near-field interactions of metallic nanostructures with a continuous metallic surface create conditions that produce enormously enhanced surface plasmon resonances. The results were used to explain the observed enhancements and determine the optimal conditions for the experiment. The theoretical parts of the studies are supported with reports on detailed emission intensity changes which provided multiple fluorescence hot spots with 2-3 orders of enhancements. We study two kinds of the fluorophores: dye molecules and fluorescent nanospheres characterized with similar spectral emission regions. Using a lifetime-resolved fluorescence/reflection confocal microscopy technique, we find that the largest rate for enhancement (~1000-fold) comes from localized areas of silver nanostructures.

[1]  Javier Aizpurua,et al.  Metallic nanoparticle arrays: a common substrate for both surface-enhanced Raman scattering and surface-enhanced infrared absorption. , 2008, ACS nano.

[2]  R. Silbey,et al.  Molecular Fluorescence and Energy Transfer Near Interfaces , 2007 .

[3]  Michele Follen,et al.  Real-time vital optical imaging of precancer using anti-epidermal growth factor receptor antibodies conjugated to gold nanoparticles. , 2003, Cancer research.

[4]  Zygmunt Gryczynski,et al.  Effects of fluorophore-to-silver distance on the emission of cyanine-dye-labeled oligonucleotides. , 2003, Analytical biochemistry.

[5]  Leon Hirsch,et al.  Gold nanoshell bioconjugates for molecular imaging in living cells. , 2005, Optics letters.

[6]  J. Lakowicz.  Principles of fluorescence spectroscopy , 1983 .

[7]  A. V. Alekseeva,et al.  Preparation and optical scattering characterization of gold nanorods and their application to a dot-immunogold assay. , 2005, Applied optics.

[8]  Harry A. Atwater.  The promise of plasmonics. , 2007 .

[9]  R. V. Van Duyne,et al.  Probing the structure of single-molecule surface-enhanced Raman scattering hot spots. , 2008, Journal of the American Chemical Society.

[10]  Zygmunt Gryczynski,et al.  Enhanced fluorescent immunoassays on silver fractal-like structures. , 2008, Analytical chemistry.

[11]  George C. Schatz,et al.  A nanoscale optical biosensor: The long range distance dependence of the localized surface plasmon resonance of noble metal nanoparticles , 2004 .

[12]  A. V. Alekseeva,et al.  Can the light scattering depolarization ratio of small particles be greater than 1/3? , 2005, The journal of physical chemistry. B.

[13]  Louis E. Brus,et al.  Drying-mediated self-assembly of nanoparticles , 2003, Nature.

[14]  J. Enderlein,et al.  Tuning the fluorescence emission spectra of a single molecule with a variable optical subwavelength metal microcavity. , 2009, Physical review letters.

[15]  Zygmunt Gryczynski,et al.  Metal-enhanced fluorescence immunoassays using total internal reflection and silver island-coated surfaces. , 2004, Analytical biochemistry.

[16]  Marco Finazzi,et al.  Near-field second-harmonic generation in single gold nanoparticles , 2008 .

[17]  J. Lakowicz,et al.  One‐ and two‐photon induced fluorescence of Pacific Blue‐labeled human serum albumin deposited on different core size silver colloids , 2006, Biopolymers.

[18]  E. Goldys,et al.  Plasmon-enhanced fluorescence near metallic nanostructures: biochemical applications , 2007 .

[19]  Jörg Enderlein,et al.  Spectral properties of a fluorescing molecule within a spherical metallic nanocavityPresented at the LANMAT 2001 Conference on the Interaction of Laser Radiation with Matter at Nanoscopic Scales: From Single Molecule Spectroscopy to Materials Processing, Venice, 3–6 October, 2001. , 2002 .

[20]  J. Lakowicz,et al.  Waveguide-modulated surface plasmon-coupled emission of Nile blue in poly(vinyl alcohol) thin films. , 2006, Thin solid films.

[21]  F. Schleifenbaum,et al.  Microcavity-controlled single-molecule fluorescence. , 2005, Chemphyschem : a European journal of chemical physics and physical chemistry.

[22]  Jian Zhang,et al.  Silver-enhanced fluorescence emission of single quantum dot nanocomposites. , 2009, Chemical Communications.

[23]  Ignacy Gryczynski,et al.  Metal-enhanced fluorescence: an emerging tool in biotechnology. , 2005, Current opinion in biotechnology.

[24]  Jian Zhang,et al.  Dye-labeled silver nanoshell-bright particle. , 2006, The journal of physical chemistry. B.

[25]  S. d'Auria,et al.  Carbon nanotube-based biosensors , 2008 .

[26]  E. Fort,et al.  Surface enhanced fluorescence , 2008 .

[27]  Bodo Fuhrmann,et al.  Surface-enhanced fluorescence from metal sculptured thin films with application to biosensing in water , 2009 .

[28]  Xiaohua Huang,et al.  Surface plasmon resonance scattering and absorption of anti-EGFR antibody conjugated gold nanoparticles in cancer diagnostics: applications in oral cancer. , 2005, Nano letters.

[29]  K. Sokolov,et al.  Enhancement of molecular fluorescence near the surface of colloidal metal films. , 1998, Analytical chemistry.

[30]  Nader Engheta,et al.  Circuits with Light at Nanoscales: Optical Nanocircuits Inspired by Metamaterials , 2007, Science.

[31]  George C. Schatz,et al.  Gold nanoparticle dimer plasmonics: finite element method calculations of the electromagnetic enhancement to surface-enhanced Raman spectroscopy , 2009, Analytical and bioanalytical chemistry.

[32]  Sulabha K. Kulkarni,et al.  Plasmon-assisted photonics at the nanoscale , 2007 .

[33]  I. Gryczynski,et al.  Monolayers of silver nanoparticles decrease photobleaching: application to muscle myofibrils. , 2008, Biophysical journal.

[34]  Anand Gole,et al.  Surface-enhanced Raman spectroscopy of self-assembled monolayers: sandwich architecture and nanoparticle shape dependence. , 2005, Analytical chemistry.

[35]  I. Gryczynski,et al.  Interference of surface plasmon resonances causes enhanced depolarized light scattering from metal nanoparticles. , 2007, Chemical physics letters.

[36]  Bodo Fuhrmann,et al.  Comparative study of enhanced fluorescence from nano sculptured thin films , 2008, NanoScience + Engineering.

[37]  M. Moskovits.  Surface-enhanced spectroscopy , 1985 .

[38]  I. Gryczynski,et al.  Fluorescence Quenching/Enhancement Surface Assays: Signal Manipulation Using Silver-coated Gold Nanoparticles. , 2008, Chemical physics letters.

[39]  W. P. Hall,et al.  A Localized Surface Plasmon Resonance Biosensor: First Steps toward an Assay for Alzheimer's Disease , 2004 .

[40]  E. Ozbay.  Plasmonics: Merging Photonics and Electronics at Nanoscale Dimensions , 2006, Science.

[41]  James Pond,et al.  Aluminum nanoparticles as substrates for metal-enhanced fluorescence in the ultraviolet for the label-free detection of biomolecules. , 2009, Analytical chemistry.

[42]  Zygmunt Gryczynski,et al.  Fluorescence amplification by electrochemically deposited silver nanowires with fractal architecture. , 2007, Journal of the American Chemical Society.

[43]  W Mandecki,et al.  Metal Enhanced Fluorescence on Silicon Wafer Substrates. , 2008, Chemical physics letters.

[44]  J. Storhoff,et al.  Selective colorimetric detection of polynucleotides based on the distance-dependent optical properties of gold nanoparticles. , 1997, Science.

[45]  L. Brus,et al.  Evidence for Spinodal Phase Separation in Two-Dimensional Nanocrystal Self-Assembly , 2000 .

[46]  Michael S. Feld,et al.  SURFACE-ENHANCED RAMAN SCATTERING : A NEW TOOL FOR BIOMEDICAL SPECTROSCOPY , 1999 .

[47]  M. T. Neves-Petersen,et al.  Long wavelength depolarized light scattering from silver nanoparticles , 2007 .