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Metallacarboranes as tunable redox potential electrochemical indicators for screening of gene mutation.

ABSTRACT: The substitution of hydrogen with chlorine in the metallacarborane [3,3-Fe(1,2-closo-C₂B₉H₁₁)₂]^- cluster modulates the formal potential of the Fe³⁺/Fe²⁺ redox couple, shifting it to a more positive value. Hence, very similar redox probes with a wide range of formal potentials, ranging from negative to positive values, are available. Thus, we have achieved the synthesis and studied the electrochemical behaviour of the sodium salt of [3,3-Fe(8,9,12-Cl₃-1,2-closo-C₂B₉H₈)₂]^- in aqueous media. This strategy allows tuning of the redox potential of the [3,3-Fe(1,2-closo-C₂B₉H₁₁)₂]^- framework with a minor change in its shape and dimensions. We also describe the interaction of the prepared [3,3-Fe(8,9,12-Cl₃-1,2-closo-C₂B₉H₈)₂]^- and the pristine [3,3-Fe(1,2-closo-C₂B₉H₁₁)₂]^- with DNA. These studies have been carried out not only with DNA in solution but also with DNA immobilized on screen-printed gold electrodes. The results obtained point to a strong interaction between the metallacarboranes and DNA, to a different extent with single stranded DNA (ssDNA) compared to double stranded DNA (dsDNA). This property makes them selective and wide-ranging potential electrochemical indicators of hybridization. The suitability of these new redox indicators for selective DNA biosensor development has been probed by the direct detection of two different mutations associated with cystic fibrosis in PCR amplicons extracted from blood cells.

SUBMITTER: Garcia-Mendiola T

PROVIDER: S-EPMC6022041 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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Metallacarboranes as tunable redox potential electrochemical indicators for screening of gene mutation.

García-Mendiola Tania T Bayon-Pizarro Victoria V Zaulet Adnana A Fuentes Isabel I Pariente Félix F Teixidor Francesc F Viñas Clara C Lorenzo Encarnación E

Chemical science 20160608 9

The substitution of hydrogen with chlorine in the metallacarborane [3,3-Fe(1,2-closo-C2B9H11)2]- cluster modulates the formal potential of the Fe3+/Fe2+ redox couple, shifting it to a more positive value. Hence, very similar redox probes with a wide range of formal potentials, ranging from negative to positive values, are available. Thus, we have achieved the synthesis and studied the electrochemical behaviour of ...[more]

PMID: 30034717

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Project description:Different synthetic methods have been developed to prepare eight new redox-active pincer-type ligands, H(X,Y), that have pyrazol-1-yl flanking donors attached to an ortho-position of each ring of a diarylamine anchor and that have different groups, X and Y, at the para-aryl positions. Together with four previously known H(X,Y) ligands, a series of 12 Ni(X,Y)2 complexes were prepared in high yields by a simple one-pot reaction. Six of the 12 derivatives were characterized by single-crystal X-ray diffraction, which showed tetragonally distorted hexacoordinate nickel(II) centers. The nickel(II) complexes exhibit two quasi-reversible one-electron oxidation waves in their cyclic voltammograms, with half-wave potentials that varied over a remarkable 700 mV range with the average of the Hammett ?(p) parameters of the para-aryl X, Y groups. The one- and two-electron oxidized derivatives [Ni(Me,Me)2](BF4)n (n = 1, 2) were prepared synthetically, were characterized by X-band EPR, electronic spectroscopy, and single-crystal X-ray diffraction (for n = 2), and were studied computationally by DFT methods. The dioxidized complex, [Ni(Me,Me)2](BF4)2, is an S = 2 species, with nickel(II) bound to two ligand radicals. The mono-oxidized complex [Ni(Me,Me)2](BF4), prepared by comproportionation, is best described as nickel(II) with one ligand centered radical. Neither the mono- nor the dioxidized derivative shows any substantial electronic coupling between the metal and their bound ligand radicals because of the orthogonal nature of their magnetic orbitals. On the other hand, weak electronic communication occurs between ligands in the mono-oxidized complex as evident from the intervalence charge transfer (IVCT) transition found in the near-IR absorption spectrum. Band shape analysis of the IVCT transition allowed comparisons of the strength of the electronic interaction with that in the related, previously known, Robin-Day class II mixed valence complex, [Ga(Me,Me)2](2+).

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Metallacarboranes as tunable redox potential electrochemical indicators for screening of gene mutation.

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Metallacarboranes as tunable redox potential electrochemical indicators for screening of gene mutation.

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