Metal cation-induced deformation of DNA self-assembled monolayers on silicon: Vibrational sum frequency generation spectroscopy

被引：0
|
作者：
Asanuma, Hidehiko [1 ]
Noguchi, Hidenori [2 ]
Uosaki, Kohei [2 ]
Yu, Hua-Zhong [1 ]
机构：
[1] Department of Chemistry, Simon Fraser University, Burnaby, BC V5A 1S6, Canada
[2] Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0180, Japan
来源：
Journal of the American Chemical Society | 2008年 / 130卷 / 25期
关键词：
Nucleic acids possess charged phosphate groups in their backbones; which require counterions to reduce the repulsive Coulombic interactions between the strands. Herein we report how different mono-and divalent metal cations influence the molecular orientations of DNA molecules on silicon surfaces upon immobilization and hybridization. Our sum frequency generation (SFG) spectroscopy studies demonstrated that the degree of conformational variation of DNA self-assembled monolayers on silicon depends on the type of metal cations present. The molecular orientation change of immobilized single-stranded oligonucleotides correlates with DNA-cation affinity (Mg2+ > Ca2+ > K+ ∼ Na+): metal cations with the strongest affinity disrupt the structure of the underlying linker monolayer the most. Upon hybridization the trend is reversed; which is attributed to the greater ability of divalent cations to mask the negative charges on the DNA backbone. These findings provide useful information for the construction of more sensitive DNA biosensors; particularly the optimization of on-chip hybridization performance. © 2008 American Chemical Society;
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页码：8016 / 8022
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