Tuning of Oxidation Potential of Ferrocene for Ratiometric Redox Labeling and Coding of Nucleotides and DNA

0520856 - ÚOCHB 2021 RIV DE eng J - Journal Article
Simonova, Anna - Magriñá, I. - Sýkorová, Veronika - Pohl, Radek - Ortiz, M. - Havran, Luděk - Fojta, Miroslav - O'Sullivan, C. K. - Hocek, Michal
Tuning of Oxidation Potential of Ferrocene for Ratiometric Redox Labeling and Coding of Nucleotides and DNA.
Chemistry - A European Journal. Roč. 26, č. 6 (2020), s. 1286-1291. ISSN 0947-6539. E-ISSN 1521-3765
R&D Projects: GA MŠMT(CZ) EF16_019/0000729
Grant - others:AV ČR(CZ) AP1501
Program: Akademická prémie - Praemium Academiae
Institutional support: RVO:61388963 ; RVO:68081707
Keywords : DNA * electrochemistry * ferrocenes * nucleobases * redox labelling
OECD category: Organic chemistry
Impact factor: 5.236, year: 2020
Method of publishing: Open access
https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.201904700

Three sets of 7-deazaadenine and cytosine nucleosides and nucleoside triphosphates bearing either unsubstituted ferrocene, octamethylferrocene and ferrocenecarboxamide linked through an alkyne tether to position 7 or 5, respectively, were designed and synthesized. The modified dNFcXTPs were good substrates for KOD XL DNA polymerase in primer extension and were used for enzymatic synthesis of redox-labelled DNA probes. Square-wave voltammetry showed that the octamethylferrocene oxidation potential was shifted to lower values, whilst the ferrocenecarboxamide was shifted to higher potentials, as compared to ferrocene. Tailed PEX products containing different ratios of Fc-labelled A (dAFc) and FcPa-labelled C (dCFcPa) were synthesized and hybridized with capture oligonucleotides immobilized on gold electrodes to study the electrochemistry of the redoxlabelled DNA. Clearly distinguishable, fully orthogonal and ratiometric peaks were observed for the dAFc and dCFcPa bases in DNA, demonstrating their potential for use in redox coding of nucleobases and for the direct electrochemical measurement of the relative ratio of nucleobases in an unknown sequence of DNA.
Permanent Link: http://hdl.handle.net/11104/0305515