Open Access Original article

Thymine/adenine diblock-oligonucleotide monolayers and hybrid brushes on gold: a spectroscopic study

Caitlin Howell123*, Hicham Hamoudi24 and Michael Zharnikov2*

Author Affiliations

1 Institute of Toxicology and Genetics, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

2 Applied Physical Chemistry, University of Heidelberg, Im Neuenheimer Feld 253, 69120, Heidelberg, Germany

3 Present address: School of Engineering and Applied Sciences, Harvard University, 29 Oxford St, Cambridge, MA 02138, USA

4 Present address: International Center for Materials Nanoarchitectonics, Institute for Materials Science, Namiki 1-1, Tsukuba, Ibaraki, Japan

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Biointerphases 2013, 8:6  doi:10.1186/1559-4106-8-6

Published: 27 February 2013

Abstract

Background

The establishment of spectroscopic analysis techniques for complex, surface-bound biological systems is an important step toward the further application of these powerful experimental tools to new questions in biology and medicine.

Methods

We use a combination of the complementary spectroscopic techniques of X-ray photoelectron spectroscopy, Infrared reflection-absorption spectroscopy, and near-edge x-ray absorption fine structure spectroscopy to monitor the composition and molecular orientation in adenine/thymine diblock oligonucleotide films and their hybridized brushes on gold.

Results

We demonstrate that the surface-bound probe molecules, consisting of a binding adenine block, d(A), and a sensing thymine block, d(T), deviate from the ideal L-shape model due to the internal intra- and intermolecular hybridization. This effect becomes more pronounced with increasing length of the d(A) block. Nevertheless, these films were found to hybridize well with the complementary target d(A) strands, especially if they were treated in advance to reduce internal interaction between the molecules. In spite of the structural complexity of these films, the hybridization efficiency correlated well with the potential accessibility of the sensing d(T) blocks, defined by their lateral spacing.

Conclusions

These findings are a good demonstration of the strength of multi-technique spectroscopic analysis when applied to assemblies of biological molecules intrinsically prone to complex interactions.

Keywords:
ssDNA film; Diblock-oligonucleotide; HRXPS; NEXAFS; IRRAS