Surface-enhanced resonant Raman spectroscopy

SERS. A phenomenon that certainly involves the adsorbent-adsorbate interaction is that of surface-enhanced resonance Raman spectroscopy, or SERS. The basic observation is that for pyridine adsorbed on surface-roughened silver, there is an amazing enhancement of the resonance Raman intensity (see Refs. 124—128). More recent work has involved other adsorbates and colloidal... 

Plenary 3. Ronald E Hester et al, e-mail address reh York.ac.uk (SERS). Use of dioxane envelope to bring water insoluble cliromophores (chlorophylls) into contact with aqueous silver colloids for SERS enliancement. PSERRS— protected surface-enhanced resonance Raman spectroscopy . 

Hildebrandt P., Stockburger M., Surface-enhanced resonance Raman-spectroscopy of rhodamine-6G adsorbed on colloidal silver, J. Phys. Chem. 1984 88 5935-5944. 

Koglin E., Sequaris J.M., Interaction of proflavine with DNA studied by colloid surface enhanced resonance Raman-spectroscopy, J. Molecular Struct. 1986 141 405-409. 

P. Corio, S.D.M. Brown, A. Marucci, M.A. Pimenta, K. Kneipp, and G. Dresselhaus, M.S. Dresselhaus, Surface-enhanced resonant Raman spectroscopy of single-wall carbon nanotubes adsorbed on silver and gold surfaces. Phys. Rev. B 61, 13202—13211 (2000). 

The use of surface-enhanced resonance Raman spectroscopy (SERRS) as an identification tool in TLC and HPLC has been investigated in detail. The chemical structures and common names of anionic dyes employed as model compounds are depicted in Fig. 3.88. RP-HPLC separations were performed in an ODS column (100 X 3 mm i.d. particla size 5 pm). The flow rate was 0.7 ml/min and dyes were detected at 500 nm. A heated nitrogen flow (200°C, 3 bar) was employed for spraying the effluent and for evaporating the solvent. Silica and alumina TLC plates were applied as deposition substrates they were moved at a speed of 2 mm/min. Solvents A and B were ammonium acetate-acetic acid buffer (pH = 4.7) containing 25 mM tributylammonium nitrate (TBAN03) and methanol, respectively. The baseline separation of anionic dyes is illustrated in Fig. 3.89. It was established that the limits of identification of the deposited dyes were 10 - 20 ng corresponding to the injected concentrations of 5 - 10 /ig/ml. It was further stated that the combined HPLC-(TLC)-SERRS technique makes possible the safe identification of anionic dyes [150],... 

R.M. Seifar, M.A.F. Altelaar, RJ. Dijkstra, F. Ariese, U.A. Th. Brinkman and C. Gooijer, Surface-enhanced resonance Raman spectroscopy (SERRS) as an identification tool in column liquid chromatography. Anal. Chem., 72 (2000) 5718-5724. 

Ni F, Thomas L, Cotton TM. 1989. Surface-enhanced resonance Raman spectroscopy as an ancillary high-performance liquid chromatography detector for nitrophenol compounds. Anal Chem 61 888-894. 

Certain roughened surfaces (Ag or Au colloids) exhibit another nice intensification of the Raman effect of 103 to 106 by exciting surface plasmons in the colloid particles this is surface-enhanced Raman, first seen by Fleischmann54, and explained by van Duyne.55 Combining resonance and surface-enhanced effects in surface-enhanced resonance Raman spectroscopy (SERRS), the Raman intensity can increase by factors as large as 1012, so that solutions of concentration down to 10 12 M can be detected. 

Online coupling of surface-enhanced resonance Raman spectroscopy and IPC proved valuable for the identification of basic dyes [124]. Circular dichroism spectroscopy is an extraordinary technique for selective detection of compounds possessing optically active adsorption bands and was successfully coupled to IPC of steroids [125]. Table 12.4. summarizes the most important features and parameters to be compared when selecting a detection mode for an IPC application. 

Seifar, R.M. et al. At-line coupling of surface-enhanced resonance Raman spectroscopy and reversed-phase ion-pair chromatography. Ana/. Commun. 1999, 36, 273-276. 

Since the pioneering work by Cotton et al. on heme proteins (Cotton et al., 1980), surface enhanced resonance Raman spectroscopy (SERRS), Sec. 6.1, has been used to study a large variety of biomolecules, such as retinal proteins (Nabiev et al., 1985), flavoproteins (Coperland et al., 1984 Holt and Cotton, 1987), chlorophylls (Cotton and Van Duyne, 1982 Hildebrandt and Spiro, 1988), and oxyhemoglobins (de Groot and Hesters, 1987). The advantages of this technique include low sample concentration and fluorescence quenching. The main question is whether or not the native structure and function of the molecule is preserved on the metal surface. 

MacAskill A, Crawford D, Graham D, Faulds K (2009) DNA sequence detection using surface-enhanced resonance Raman spectroscopy in a homogeneous multiplexed assay. Anal Chem 81 8134-8140... 

Fundamental questions related to the electronic configuration of the open or colored forms and the number and structures of the photomerocyanine isomers are considered on the basis of the results of continuous-wave (stationary) and time-resolved (picosecond, nanosecond, and millisecond) Raman experiments. For spironaphthoxazine photochromic compounds, the Raman spectra may be attributed to the TTC (trans-trans-cis) isomer having a dominant quinoidal electronic configuration. Surface-enhanced resonance Raman spectroscopy (SERRS) is demonstrated as a new analytical method for the study of the photodegradation process in solution for nitro-BIPS derivatives. The development of this method could lead to the identification of the photoproducts in thin polymer films or sol-gel matrices and ultimately to control of degradation. 

Trace detection and analysis of species at pico- to femtomolar concentrations using surface-enhanced resonance Raman spectroscopy (SERRS). 

Besides the methods given in Table 6-1 and Table 6-2, several others are available to determine dinitrophenols in biological and environmental samples. Immunoassay methods with sensitivities comparable to those of the conventional methods given in Tables 6-1 and 6-2 are noteworthy (Bush and Rechnitz 1987 Huang et al. 1992 Kusterbeck et al. 1990 Wannlund and DeLuca 1982). However, methods based on antibody sorption have not yet been validated on samples derived from environmental and biological sources, so it is not clear what methods of clean-up are necessary prior to quantitation of dinitrophenols. Some of the other detection methods with superior sensitivities that can determine dinitrophenols are surface-enhanced resonance Raman spectroscopy (Ni et al. 

Murgida, D,H. and Hildebrandt, P. (2004) Electron-transfer processes of cytochrome c at interfaces. New insights by surface-enhanced resonance Raman spectroscopy. Accounts of Chemical Research, 37, 854-861. 

SERS and Surface-Enhanced Resonant Raman Spectroscopy 273... 

A further resonant contribution to the enhancement is possible when the molecule has an electronic transition in resonance, or dose to resonance, with the exciting laser so that one obtains surface-enhanced resonant Raman scattering or surface-enhanced resonant Raman spectroscopy (SERRS). In these circumstances the resonant enhancement typically contributes an additional factor of between 100 and 1000 to the intensity of the signal and this makes SERRS a particularly attractive approach for analytical apphcations because of its extremely high sensitivity. 

Hildebrandt, P. and Stockburger, M. (1986) Surface-enhanced resonance Raman spectroscopy of cytochrome c at room and low temperatures. Journal (f Physical Chemistry, 90, 6017-6024. 

Lecomte, S., Wackerbarth, H., Soulimane, T., Buse, G., and Hildebrandt, P. (1998) Time-resolved surface-enhanced resonance Raman spectroscopy for smdying electron-transfer dynamics of heme proteins. Journal of the American Chemical Society, 120, 7381-7382. 

R.LC. (2009) Electron transfer kinetics of cytochrome c probed by bme-resolved surface-enhanced resonance Raman spectroscopy. Journal of Physical Chemistry B, 113, 2492-2497. 

H., and Lecomte, S. (2007) Kinetics of the electron transfer reaction of cytochrome c(552) adsorbed on biomimetic electrode studied by time-resolved surface-enhanced resonance Raman spectroscopy and electrochemistry. European Biophysics Journal, 36,1039-1048. 

Jiang, X., Wang, Y.L, Qu, X.H., and Dong, S.L (2006) Surface-enhanced resonance Raman spectroscopy and spectroscopy study of redox-induced conformational equilibrium of cytochrome c adsorbed on DNA-modified metal electrode. Biosensors Bioelectronics, 22,49-55. 

Holt, R.E. and Cotton, T.M. (1987) Free flavin interference in surface enhanced resonance Raman-spectroscopy of glucose oxidase. Journal of the American Chemical Society, 109,1841-1845. 

Developments in Raman spectroscopy, with applications for colorants, have included resonance Raman, surface enhanced Raman spectroscopy (SERS), surface enhanced resonance Raman spectroscopy (SERRS) and near-infrared Fourier transform Raman spectroscopy (NIR-FT-Raman), with the latter technique discussed in the next section. 

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