Metal cation-induced deformation of DNA self-assembled monolayers on silicon: vibrational sum frequency generation spectroscopy.
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 (Mg(2+) > Ca(2+) > K(+) approximately 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.
Asanuma
Hidehiko
H
Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6, Canada.
Noguchi
Hidenori
H
Uosaki
Kohei
K
Yu
Hua-Zhong
HZ
D002412:Cations / Q000737:chemistry; D015342:DNA Probes / Q000737:chemistry*; D009690:Nucleic Acid Conformation; D012825:Silicon / Q000737:chemistry*; D013057:Spectrum Analysis; D013499:Surface Properties; D014732:Vibration
D002412:Cations; D015342:DNA Probes; D012825:Silicon