Document Type

Article

Publication Date

2017

DOI

10.1039/c6sc03445d

Publication Title

Chemical Science

Volume

8

Issue

2

Pages

1269-1281

Abstract

Physicochemical properties of coordination compounds can be exploited for molecular recognition of biomolecules. The inherent π-π stacking properties of [Pt(chelate)(N-donor)]2+([PtN4]) complexes were modulated by systematic variation of the chelate (diethylenetriamine and substituted derivatives) and N-donor (nucleobase or nucleoside) in the formally substitution-inert PtN4 coordination sphere. Approaches to target the HIV nucleocapsid protein HIVNCp7 are summarized building on (i) assessment of stacking interactions with simple tryptophan or tryptophan derivatives to (ii) the tryptophan-containing C-terminal zinc finger and (iii) to the full two-zinc finger peptide and its interactions with RNA and DNA. The xanthosine nucleoside was identified as having significantly enhanced stacking capability over guanosine. Correlation of the LUMO energies of the modified nucleobases with the DFT π-stacking energies shows that frontier orbital energies of the individual monomers can be used as a first estimate of the π-stacking strength to Trp. Cellular accumulation studies showed no significant correlation with lipophilicity of the compounds, but all compounds had very low cytotoxicity suggesting the potential for antiviral selectivity. The conceptual similarities between nucleobase alkylation and platination validates the design of formally substitution-inert coordination complexes as weak Lewis acid electrophiles for selective peptide targeting.

Comments

Open Access Article. Published on 06 October 2016.

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

Original Publication Citation

Tsotsoros, S. D., Lutz, P. B., Daniel, A. G., Peterson, E. J., de Paiva, R. E. F., Rivera, E., . . . Farrell, N. P. (2017). Enhancement of the physicochemical properties of Pt(dien)(nucleobase) (2+) for HIVNCp7 targeting. Chemical Science, 8(2), 1269-1281. doi:10.1039/c6sc03445d

ORCID

0000-0002-3490-576X (Bayse)

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