Characterization of mismatched DNA hybridization via a redox-active diviologen bound in the PNA-DNA minor groove

Eli G. Hvastkovs, Daniel Buttry

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

Diviologen molecules of the general formula CH 3(CH 2) 11V 2+(CH 2) 11V 2+(CH 2) 11CH 3 (C 12VC 6VC 12, V 2+ = 4,4-bipyridinium or viologen) were employed to electrochemically assay DNA hybridization to PNA probes immobilized at Au electrodes. Immobilized 15-mer PNA probes were exposed to 25-mer DNA oligonucleotides containing either complementary or single base mismatched sequences. In the presence of complementary PNA-DNA hybrids, the y 2+/+ redox couple C 12VC 6VC 12 exhibited a unique double-wave cyclic voltammogram, with a formal potential shifted -100 mV from the E f in the presence of single base mismatched DNA hybrids or PNA probes alone. Integration of the CVs demonstrated that C 12VC 6VC 12 exhibited binding cooperativity to the complementary PNA-DNA hybrids and saturated at a ratio of 2:1 (C 12VC 6VC 12:hybrid). Reduced C 12VC 6VC 12 (V +) absorption spectra showed a significant λ max blue shift (22 nm) in the presence of complementary hybrids compared to the AmaK in the presence of PNA or mismatched DNA hybrids. Chronocoulometry was employed to assay surface populations and obtain thermodynamics for C 12VC 6VC 12 binding. These data are consistent with C 12VC 6VC 12 bound in the minor groove of complementary hybrids as face-to-face π-dimers. This approach to distinguishing complementary hybrids from mismatched hybrids is novel, with potential applications involving detection of DNA damage or single nucleotide polymorphism (SNP) analysis.

Original languageEnglish (US)
Pages (from-to)3839-3844
Number of pages6
JournalLangmuir
Volume25
Issue number6
DOIs
StatePublished - Mar 17 2009

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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