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Electronic structure of self-assembled peptide nucleic acid thin films

Publication ,  Journal Article
Wolak, MA; Balaeff, A; Gutmann, S; Helmrich, HJ; Vosloo, R; Beerbom, MM; Wierzbinski, E; Waldeck, DH; Bezer, S; Achim, C; Beratan, DN; Schlaf, R
Published in: Journal of Physical Chemistry C
September 1, 2011

The electronic structure of self-assembled monolayers (SAMs) of peptide nucleic acid (PNA) formed on Au substrates was investigated. Cys-appended PNA 7-mers of thymine (Cys-T7) were incubated on Au substrates in a nitrogen glovebox attached to a photoemission spectrometer. Ultraviolet and X-ray photoemission spectroscopy (UPS and XPS) measurements on the resulting SAMs revealed the hole injection barrier at the interface and the interface dipole. Electronic structure calculations based on molecular dynamics sampling of the PNA structure yielded the HOMO-LUMO gap and the electronic density of states for PNA. Combined with the UPS data, the theoretical calculation enabled estimation of the charge injection barriers at the interface, as well as the assignment of individual UP spectral features to specific molecular orbitals. Interestingly, the dipole moment of the PNA backbone is predicted to polarize PNA MOs, shifting the preferred HOMO localization toward the C-terminus of PNA. Control measurements on Cys-appended, abasic PNA backbone 7-mers (Cys-Bckb7) allowed the identification of the emissions related to the PNA backbone in the UP spectra. The orbital line-up at the interface between the Au substrate and the Cys-PNA indicates a significant interface dipole resulting in the alignment of the Au Fermi level near the center of the PNA HOMO-LUMO gap. This alignment causes large charge injection barriers for both holes and electrons, and thus impedes charge transfer from Au into the Cys-PNA SAM. © 2011 American Chemical Society.

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Published In

Journal of Physical Chemistry C

DOI

EISSN

1932-7455

ISSN

1932-7447

Publication Date

September 1, 2011

Volume

115

Issue

34

Start / End Page

17123 / 17135

Related Subject Headings

  • Physical Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 10 Technology
  • 09 Engineering
  • 03 Chemical Sciences
 

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Wolak, M. A., Balaeff, A., Gutmann, S., Helmrich, H. J., Vosloo, R., Beerbom, M. M., … Schlaf, R. (2011). Electronic structure of self-assembled peptide nucleic acid thin films. Journal of Physical Chemistry C, 115(34), 17123–17135. https://doi.org/10.1021/jp201602j
Wolak, M. A., A. Balaeff, S. Gutmann, H. J. Helmrich, R. Vosloo, M. M. Beerbom, E. Wierzbinski, et al. “Electronic structure of self-assembled peptide nucleic acid thin films.” Journal of Physical Chemistry C 115, no. 34 (September 1, 2011): 17123–35. https://doi.org/10.1021/jp201602j.
Wolak MA, Balaeff A, Gutmann S, Helmrich HJ, Vosloo R, Beerbom MM, et al. Electronic structure of self-assembled peptide nucleic acid thin films. Journal of Physical Chemistry C. 2011 Sep 1;115(34):17123–35.
Wolak, M. A., et al. “Electronic structure of self-assembled peptide nucleic acid thin films.” Journal of Physical Chemistry C, vol. 115, no. 34, Sept. 2011, pp. 17123–35. Scopus, doi:10.1021/jp201602j.
Wolak MA, Balaeff A, Gutmann S, Helmrich HJ, Vosloo R, Beerbom MM, Wierzbinski E, Waldeck DH, Bezer S, Achim C, Beratan DN, Schlaf R. Electronic structure of self-assembled peptide nucleic acid thin films. Journal of Physical Chemistry C. 2011 Sep 1;115(34):17123–17135.
Journal cover image

Published In

Journal of Physical Chemistry C

DOI

EISSN

1932-7455

ISSN

1932-7447

Publication Date

September 1, 2011

Volume

115

Issue

34

Start / End Page

17123 / 17135

Related Subject Headings

  • Physical Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 10 Technology
  • 09 Engineering
  • 03 Chemical Sciences