Towards chemical analysis of nanostructures in biofilms II: tip-enhanced Raman spectroscopy of alginates

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Author(s) Schmid, Thomas, Messmer, Andreas, Yeo, Boon-Siang, Zhang, Weihua, Zenobi, Renato
Publication Type Journal Items, Publication Status: Published
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Title Towards chemical analysis of nanostructures in biofilms II: tip-enhanced Raman spectroscopy of alginates
Author(s) Schmid, Thomas
Messmer, Andreas
Yeo, Boon-Siang
Zhang, Weihua
Zenobi, Renato
Journal or Series Title Analytical and bioanalytical chemistry
Volume Number 391
Issue Number 5
Start Page 1907
End Page 1916
ISSN 1618-2642
Publisher Springer
Publication Place Berlin
Publication Date 2008-07
Keyword(s) Alginate
Biological samples
Tip-enhanced Raman spectroscopy (TERS)
Atomic force microscopy (AFM)
Abstract This study examines the feasibility of using tip-enhanced Raman spectroscopy (TERS) for label-free chemical characterization of nanostructures in biological systems. For this purpose, a well-defined model system consisting of calcium alginate fibers is studied. In a companion paper, calcium alginate fibers and their network structures were shown to be a good model for the extracellular polysaccharides of biofilms at the nanoscale. TERS analysis of biological macromolecules, such as alginates, is complicated by heterogeneity in their sequence, molecular weight, and conformations, their small Raman cross-section, and the large number of functional groups, which can chemically interact with the silver surface of the tip and cause significant band shifts. Due to these effects, Raman frequencies in TERS spectra of biopolymers do not necessarily resemble band positions in the normal Raman spectrum of the bulk material, as is the case for less complex samples (e.g., dye molecules) studied so far. Additionally, analyte decomposition due to laser heating can have a significant influence, and carbon contamination signals can sometimes even overwhelm the weak analyte signals. Based on the investigation of alginates, strategies for spectra correction, choice of appropriate reference samples, and data interpretation are presented. With this approach, characteristic frequency ranges and specific marker bands can be found for biological macromolecules that can be employed for their identification in complex environments.
DOI 10.1007/s00216-008-2101-1
Additional Notes Received 23 December 2007, Revised 20 March 2008, Accepted 25 March 2008, Published online 23 April 2008
Document Type Article
Publication Status Published
Language English
NEBIS System Number 004239219
Source Database ID WOS-000256908200044
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  author = "Schmid, Thomas and Messmer, Andreas and Yeo, Boon-Siang and Zhang, Weihua and Zenobi, Renato",
  title = "{T}owards chemical analysis of nanostructures in biofilms {I}{I}: tip-enhanced {R}aman spectroscopy of alginates",
  journal = "Analytical and bioanalytical chemistry",
  year = 2008,
  volume = "391",
  number = "5",
  pages = "1907--1916",
  month = jul,

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