Single-molecule surface-enhanced Raman spectroscopy of nonresonant molecules.

Single-molecule surface-enhanced Raman scattering (SERS) detection of nonresonant molecules is demonstrated experimentally using the bianalyte SERS method. To this end, bianalyte SERS is performed at 633 nm excitation using the nonresonant molecule 1,2-di-(4-pyridyl)-ethylene (BPE) in combination with a benzotriazole derivative as a partner. The results are then extended to the even more challenging case of a small nonresonant molecule, adenine, using an isotopically substituted adenine as bianalyte SERS partners. In addition, SERS cross sections of single-molecule events are quantified, thus providing estimates of the enhancement factors needed to see them. It turns out that an enhancement factor on the order of approximately 5 x 10(9) was sufficient for single-molecule detection of BPE, while maximum enhancement factors of approximately 5 x 10(10) were observed in extreme cases. In the case of adenine, single-molecule detection was only possible in the rare cases with enhancement factors of approximately 10(11). This study constitutes a quantitative fundamental test into the lowest detection limits (in terms of differential cross sections) for single-molecule SERS.

[1]  M. Käll,et al.  Direct Observation of Heterogeneous Photochemistry on Aggregated Ag Nanocrystals Using Raman Spectroscopy: The Case of Photoinduced Degradation of Aromatic Amino Acids , 2004 .

[2]  M. Moskovits.  Surface selection rules , 1982 .

[3]  Influence of photostability on single-molecule surface enhanced Raman scattering enhancement factors. , 2009, Analytical chemistry.

[4]  P. Etchegoin,et al.  Statistics of single-molecule surface enhanced Raman scattering signals: fluctuation analysis with multiple analyte techniques. , 2007, Analytical chemistry.

[5]  P. Etchegoin,et al.  Enhancement factor distribution around a single surface-enhanced Raman scattering hot spot and its relation to single molecule detection. , 2006, The Journal of chemical physics.

[6]  Dana D. Dlott,et al.  Measurement of the Distribution of Site Enhancements in Surface-Enhanced Raman Scattering , 2008, Science.

[7]  P. Etchegoin,et al.  Polarization-dependent effects in surface-enhanced Raman scattering (SERS). , 2006, Physical chemistry chemical physics : PCCP.

[8]  N. Pieczonka,et al.  Single molecule analysis by surfaced-enhanced Raman scattering. , 2008, Chemical Society reviews.

[9]  Katrin F. Domke,et al.  Enhanced Raman spectroscopy: Single molecules or carbon? , 2007 .

[10]  D. Meisel,et al.  Adsorption and surface-enhanced Raman of dyes on silver and gold sols , 1982 .

[11]  Andreas Otto,et al.  What is observed in single molecule SERS, and why? , 2002 .

[12]  B. Burkett,et al.  Bi-analyte SERS with isotopically edited dyes. , 2008, Physical chemistry chemical physics : PCCP.

[13]  A. Kudelski,et al.  SERS on carbon chain segments: monitoring locally surface chemistry , 2000 .

[14]  J. C. Jones,et al.  Synthesis of novel monoazo benzotriazole dyes specifically for surface enhanced resonance Raman scattering , 1998 .

[15]  M. Ishikawa,et al.  Surface-Enhanced Raman Scattering of Single Adenine Molecules on Silver Colloidal Particles. , 2001 .

[16]  P. Etchegoin,et al.  Phenomenological local field enhancement factor distributions around electromagnetic hot spots. , 2009, The Journal of chemical physics.

[17]  R. Aroca.  Surface-Enhanced Vibrational Spectroscopy: Aroca/Surface-Enhanced Vibrational Spectroscopy , 2007 .

[18]  P. Etchegoin,et al.  Sub-wavelength localization of hot-spots in SERS , 2004 .

[19]  R. V. Van Duyne,et al.  A frequency domain existence proof of single-molecule surface-enhanced Raman spectroscopy. , 2007, Journal of the American Chemical Society.

[20]  Eric C Le Ru,et al.  Investigation of particle shape and size effects in SERS using T-matrix calculations. , 2009, Physical chemistry chemical physics : PCCP.

[21]  Franz R. Aussenegg,et al.  Optimized surface-enhanced Raman scattering on gold nanoparticle arrays , 2003 .

[22]  R. Aroca,et al.  Distinguishing individual vibrational fingerprints: single-molecule surface-enhanced resonance raman scattering from one-to-one binary mixtures in Langmuir-Blodgett monolayers. , 2007, Analytical chemistry.

[23]  Katsuhiro Ajito,et al.  Observation of a small number of molecules at a metal nanogap arrayed on a solid surface using surface-enhanced Raman scattering. , 2007, Journal of the American Chemical Society.

[24]  Xu,et al.  Electromagnetic contributions to single-molecule sensitivity in surface-enhanced raman scattering , 2000, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[25]  D. Bergman,et al.  Self-similar chain of metal nanospheres as efficient nanolens , 2003, InternationalQuantum Electronics Conference, 2004. (IQEC)..

[26]  Pablo G. Etchegoin,et al.  Surface Enhanced Raman Scattering Enhancement Factors: A Comprehensive Study , 2007 .

[27]  R. G. Freeman,et al.  Size selection of colloidal gold aggregates by filtration: effect on surface‐enhanced Raman scattering intensities , 1999 .

[28]  P. Etchegoin,et al.  Proof of single-molecule sensitivity in surface enhanced Raman scattering (SERS) by means of a two-analyte technique. , 2006, The journal of physical chemistry. B.

[29]  Katrin F. Domke,et al.  Comment on “Scanning-probe Raman spectroscopy with single-molecule sensitivity” , 2007 .

[30]  P. Etchegoin,et al.  Statistics of single molecule SERS signals: is there a Poisson distribution of intensities? , 2007, Physical chemistry chemical physics : PCCP.

[31]  R. Maher,et al.  Vibrational pumping in surface enhanced Raman scattering (SERS). , 2008, Chemical Society reviews.

[32]  P. Etchegoin,et al.  Advanced aspects of electromagnetic SERS enhancement factors at a hot spot , 2008 .

[33]  P. Etchegoin,et al.  Single-molecule vibrational pumping in SERS. , 2009, Physical chemistry chemical physics : PCCP.

[34]  Hongxing Xu,et al.  Surface-enhanced Raman scattering and fluorescence near metal nanoparticles , 2005 .

[35]  Ramasamy Manoharan,et al.  Detection and identification of a single DNA base molecule using surface-enhanced Raman scattering (SERS) , 1998 .

[36]  P G Etchegoin,et al.  A perspective on single molecule SERS: current status and future challenges. , 2008, Physical chemistry chemical physics : PCCP.