Correlation of molecular orientation and packing density in a dsDNA self-assembled monolayer observable with surface-enhanced Raman spectroscopy

J Am Chem Soc. 2008 Oct 29;130(43):14040-1. doi: 10.1021/ja804367c. Epub 2008 Oct 4.

Abstract

Observations of two spectrally distinct ring breathing modes of guanine and adenine in the surface-enhanced Raman spectrum (SERS) of a dsDNA self-assembled monolayer on an Au nanoshell SERS substrate provide information concerning the orientation of its constituent molecules. The two modes vary with DNA concentration in a highly systematic manner, consistent with studies suggesting DNA molecules tend toward a more horizontal orientation at low-surface concentrations and a more vertical conformation at high concentrations. The introduction of small molecular spacers coadsorbed onto the Au nanoshell surface to "raise" the DNA molecules yields a SERS spectrum consistent with a more upright molecular orientation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adenine / chemistry
  • DNA / chemistry*
  • Gold / chemistry*
  • Guanine / chemistry
  • Metal Nanoparticles / chemistry*
  • Models, Molecular
  • Nucleic Acid Conformation*
  • Reference Standards
  • Spectrum Analysis, Raman / methods*
  • Spectrum Analysis, Raman / standards
  • Sulfhydryl Compounds / chemistry
  • Surface Properties

Substances

  • Sulfhydryl Compounds
  • Guanine
  • Gold
  • DNA
  • Adenine