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Extent of intramolecular pi stacks in aqueous solution in mixed-ligand copper(II) complexes formed by heteroaromatic amines and 1-[2-(Phosphonomethoxy)ethyl]cytosine (PMEC), a relative of antivirally active acyclic nucleotide analogues (Part 72)[1, 2]
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Blindauer, Claudia A., Sigel, Astrid, Operschall, Bert P., Holý, Antonín and Sigel, Helmut (2013) Extent of intramolecular pi stacks in aqueous solution in mixed-ligand copper(II) complexes formed by heteroaromatic amines and 1-[2-(Phosphonomethoxy)ethyl]cytosine (PMEC), a relative of antivirally active acyclic nucleotide analogues (Part 72)[1, 2]. Zeitschrift fuer anorganische und allgemeine Chemie, Volume 639 (Number 8-9). pp. 1661-1673. doi:10.1002/zaac.201300095 ISSN 0044-2313.
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Official URL: http://dx.doi.org/10.1002/zaac.201300095
Abstract
Stability constants of the ternary Cu(Arm)(H;PMEC)(+) and Cu(Arm)(PMEC) complexes were measured by potentiometric pH titrations and compared with those of Cu(Arm)(H;PMEA)(+) and Cu(Arm)(PMEA) {PMEA(2-)} and related species. The basicity of the terminal phosphonate group is similar in PMEC2- and PMEA(2-). Stability-constant comparisons reveal, that in the monoprotonated ternary u(Arm)(H;PMEC)(+) complexes H+ is at the phosphonate group, that the ether oxygen atom of the -CH2-O-CH2-P(O)(2)(-) (OH) residue participates, next to the P(O)(2)(-)(OH) group, in Cu(Arm)(2+) coordination. The Cu(Arm)(PMEC) complexes are considerably more stable than the corresponding Cu(Arm)(R-PO3) species. The stability enhancements are mainly attributed to intramolecular stacks and to the formation of five-membered chelates involving the ether oxygen atom of the -CH2-O-CH2-P(O)(3)(2-) residue of PMEC2-. Analysis of the intramolecular equilibria reveals that ca. 10% of the isomeric ternary complexes exist with Cu(Arm)(2+) solely coordinated to the phosphonate group, ca. 25% as a five-membered chelate involving the ether oxygen, and ca. 65% with an intramolecular pi-pi stack between the pyrimidine moiety of PMEC2- and the rings of Bpy or Phen. It seems feasible that the reduced stacking intensity of PMEC2- and a different hydrogen bonding, leads to a different orientation of the cytosine (compared to adenine) in the active site of the nucleic acid polymerases, resulting in a reduced antiviral activity of PMEC compared to PMEA.
Item Type: | Journal Article | ||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Journal or Publication Title: | Zeitschrift fuer anorganische und allgemeine Chemie | ||||
Publisher: | Wiley - V C H Verlag GmbH & Co. KGaA | ||||
ISSN: | 0044-2313 | ||||
Official Date: | 2013 | ||||
Dates: |
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Volume: | Volume 639 | ||||
Number: | Number 8-9 | ||||
Page Range: | pp. 1661-1673 | ||||
DOI: | 10.1002/zaac.201300095 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access |
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