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The FPMD simulations are performed within the spin-polarized density functional theory using a gradient-corrected exchange-correlation functional and norm-conserving pseudopotentials (see ref 14). The wave functions are expanded at the Γ-point of the Brillouin zone on a plane-wave basis set up to an energy cutoff of 60 Ry. All the simulations are performed in a cubic cell with edge length 18 Å, using periodic boundary conditions. The reported gas-phase bond energy values are calculated for each Pt dimer as the absolute value of the difference in total energy between the fully relaxed dimer structure and the same system after increasing the Pt-Pt distance to 12 Å and relaxing the other atomic positions. In the case of charged cells, we correct the total energy of the system according to the methods described in ref 17, and the convergence of the computed values is checked with particular care.
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We do not expect qualitative differences in the investigated dimer formation reactions if the Pt(II) ions are bound to guanine or to other nucleotides (such as, e.g., adenine) because of their chemical similarity.
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4 (Fluka, Switzerland), which was previously aged for at least 24 h. The complex-to-nucleotide ratio was kept at 65:1. The metallization of the DNA molecules was accomplished at 27°C by addition of a 10 mM solution of DMAB (Fluka) in stoichiometric excess with respect to the amount of Pt(II) complexes. For the UV-vis and SFM studies; a 20 μg/mL solution of DNA from salmon testes (SIGMA-Aldrich, Germany) was used instead of λ-DNA.
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Indeed, preliminary experiments that will be reported in a forthcoming work show that the kinetics of metal formation in the presence of activated DNA accelerates if we increase the (CG) content of the DNA sequence. This suggests the possibility of combining the selectively heterogeneous metal cluster nucleation described in this work with a base-specific Pt(II) binding to DNA molecules of predefined sequence. Although how to do this is far from obvious at the current stage, it is interesting to notice that this would amount to a space-resolved metallization technique in which the metal structure is grown preferentially on a predefined portion of a biological template.
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