Direct Experimental Observation of the Effect of the Base Pairing on the Oxidation Potential of Guanine

Caruso, Tonino; Carotenuto, Maurizio; Vasca, Ermanno; Peluso, Andrea

doi:10.1021/ja055130s

Cited by 57 publications

(96 citation statements)

References 22 publications

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“…4 is adapted from Xiang et al 9 . Materials characterization (Supplementary Sections 9-11) and conductance measurements (Supplementary Sections [12][13][14] are described in the Supplementary Information. The measured resistance oscillations are, indeed, found to be enhanced in the reversed sequences (quantitative analysis is given below), as predicted by the V/V 2 coherent (odd length)/incoherent (even length) semi-quantitative argument described above.…”

Section: Resultsmentioning

confidence: 99%

Engineering nanometre-scale coherence in soft matter

et al. 2016

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Electronic delocalization in redox-active polymers may be disrupted by the heterogeneity of the environment that surrounds each monomer. When the differences in monomer redox-potential induced by the environment are small (as compared with the monomer-monomer electronic interactions), delocalization persists. Here we show that guanine (G) runs in double-stranded DNA support delocalization over 4-5 guanine bases. The weak interaction between delocalized G blocks on opposite DNA strands is known to support partially coherent long-range charge transport. The molecular-resolution model developed here finds that the coherence among these G blocks follows an even-odd orbital-symmetry rule and predicts that weakening the interaction between G blocks exaggerates the resistance oscillations. These findings indicate how sequence can be exploited to change the balance between coherent and incoherent transport. The predictions are tested and confirmed using break-junction experiments. Thus, tailored orbital symmetry and structural fluctuations may be used to produce coherent transport with a length scale of multiple nanometres in soft-matter assemblies, a length scale comparable to that of small proteins.

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Section: Resultsmentioning

confidence: 99%

Engineering nanometre-scale coherence in soft matter

et al. 2016

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“…[35][36][37][38] The electron-and hole-transfer phenomena of different systems can be understood by the investigation of the electron affinity and ionization potential of molecules. [35][36][37][38][39][40][41] The computed vertical electron affinity (EA v ) and vertical ionization potential (IP v ) of guanine, the GC base pair, and G-Au n and GC-Au n complexes are shown in Table 2. It is evident from the data shown in this Table that guanine and the GC base pair have negative electron affinities, although it is less negative for the GC base pair than for guanine.…”

Section: Bsse-corrected and -Uncorrected (In Parenthesis) Interactionmentioning

confidence: 99%

DFT Investigation of the Interaction of Gold Nanoclusters with Nucleic Acid Base Guanine and the Watson−Crick Guanine-Cytosine Base Pair

et al. 2009

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The interaction of gold nanoclusters (Au n , n ) 2, 4, 6, 8, 10, 12) with nucleic acid purine base guanine (G) and the Watson-Crick guanine-cytosine (GC) base pair through the major groove site (N7 site of guanine) of DNA was investigated theoretically. Geometries of complexes were optimized at the density functional theory (DFT) level employing the hybrid B3LYP functional. The 6-31G(d) basis set was used for all atoms except gold, for which the LANL2DZ effective core potential (ECP) was used. Natural population analysis was performed to determine NBO charges. The vertical first ionization potential and electron affinity of guanine and the guanine-cytosine base pair and their complexes with gold nanoclusters were also analyzed. It was revealed that gold clusters interact more strongly with the GC base pair than with isolated guanine. It was found that consequent to the binding of gold nanoclusters a substantial amount of electronic charge was transferred from guanine (or the guanine-cytosine base pair) to the gold clusters. Furthermore, the amount of the electronic charge transferred to the gold cluster was found to be larger for GC-Au n complexes than that in the G-Au n complexes. The vertical ionization potential, electron affinity, and biological significance of the interaction of gold nanoclusters with nucleic acid building blocks have also been discussed.

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“…Several reports show that the widely used B3LYP functional is capable of predicting reliable ionization energies, for aromatic systems, even for difficult cases such as the oxidation of DNA nucleobases, nucleosides and oligonucleotides in solution [11][12][13][14][15][16][17][18]. However B3LYP was found to underestimate oxidation free energies of triphenylamine-based dipolar chromophores for dye-sensitized solar cells, while meta functionals furnished more accurate results [19].…”

Section: Introductionmentioning

confidence: 99%

“…1, all of them undergo single electron oxidation. Most of them are donoracceptor (DA) conjugate chromophores such as the tricyanofuran amine 12 which exhibits non linear optical activity [20][21][22], amino oligoenes 1-5 [23], coumarine and perylene dyes (13,16) used so far as sensitizers for dye sensitized solar cells (DSSC) [24,25].…”

Section: Introductionmentioning

confidence: 99%