Understanding tip-enhanced Raman spectra of biological molecules

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Author(s) Blum, Carolin, Schmid, Thomas, Opilik, Lothar, Weidmann, Simon, Fagerer, Stephan R., Zenobi, Renato
Publication Type Journal Items, Publication Status: Published
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Title Understanding tip-enhanced Raman spectra of biological molecules
Subtitle A combined Raman, SERS and TERS study
Author(s) Blum, Carolin
Schmid, Thomas
Opilik, Lothar
Weidmann, Simon
Fagerer, Stephan R.
Zenobi, Renato
Journal or Series Title Journal of Raman Spectroscopy
Volume Number 43
Issue Number 12
Start Page 1895
End Page 1904
ISSN 0377-0486
Publisher Wiley
Publication Place Chichester
Publication Date 2012-12
Keyword(s) Tip-enhanced Raman spectroscopy (TERS)
Surface-enhanced Raman spectroscopy (SERS);
Biological molecules;
Interpretation of spectra
Abstract Although conventional Raman, surface-enhanced Raman (SERS) and tip-enhanced Raman spectroscopy (TERS) have been known for a long time, a direct, thorough comparison of these three methods has never been carried out. In this paper, spectra that were obtained by conventional Raman, SERS (on gold and silver substrates) and TERS (in ‘gap mode’ with silver tips and gold substrates) are compared to learn from their differences and similarities. Because the investigation of biological samples by TERS has recently become a hot topic, this work focuses on biologically relevant substances. Starting from the TER spectra of bovine serum albumin as an example for a protein, the dipeptides Phe–Phe and Tyr–Tyr and the tripeptide Tyr–Tyr–Tyr were investigated. The major findings were as follows. (1) We show that the widely used assumption that spectral bands do not shift when comparing SER, TER and conventional Raman spectra (except due to binding to the metal surface in SERS or TERS) is valid. However, band intensity ratios can differ significantly between these three methods. (2) Marker bands can be assigned, which should allow one to identify and localize proteins in complex biological environments in future investigations. From our results, general guidelines for the interpretation of TER spectra are proposed.
DOI 10.1002/jrs.4099
Additional Notes Published online 22 June 2012
Document Type Article
Publication Status Published
Language English
Assigned Organisational Unit(s) 03430
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NEBIS System Number 000027994
Source Database ID FORM-1358156484
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  author = "Blum, Carolin and Schmid, Thomas and Opilik, Lothar and Weidmann, Simon and Fagerer, Stephan R. and Zenobi, Renato",
  title = "{U}nderstanding tip-enhanced {R}aman spectra of biological molecules: {A} combined {R}aman, {S}{E}{R}{S} and {T}{E}{R}{S} study",
  journal = "Journal of Raman Spectroscopy",
  year = 2012,
  volume = "43",
  number = "12",
  pages = "1895--1904",
  month = dec,

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