A1 Journal article – refereed
Palladacyclic Conjugate Group Promotes Hybridization of Short Oligonucleotides

List of Authors: Madhuri Hande, Sajal Maity, Tuomas Lönnberg
Publisher: MDPI
Publication year: 2018
Journal: International Journal of Molecular Sciences
Journal acronym: INT J MOL SCI
Volume number: 19
Issue number: 6
Number of pages: 11
ISSN: 1422-0067
eISSN: 1422-0067

Short oligonucleotides with cyclopalladated benzylamine moieties at their 5-termini have been prepared to test the possibility of conferring palladacyclic anticancer agents sequence-selectivity by conjugation with a guiding oligonucleotide. Hybridization of these oligonucleotides with natural counterparts was studied by UV and CD (circular dichroism) melting experiments in the absence and presence of a competing ligand (2-mercaptoethanol). Cyclopalladated benzylamine proved to be strongly stabilizing relative to unmetalated benzylamine and modestly stabilizing relative to an extra A center dot T base pair. The stabilization was largely abolished in the presence of 2-mercaptoethanol, suggesting direct coordination of Pd(II) to a nucleobase of the complementary strand. In all cases, fidelity of Watson-Crick base pairing between the two strands was retained. Hybridization of the cyclopalladated oligonucleotides was characterized by relatively large negative enthalpy and entropy, consistent with stabilizing Pd(II) coordination partially offset by the entropic penalty of imposing conformational constraints on the flexible diethylene glycol linker between the oligonucleotide and the palladacyclic moiety.

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Last updated on 2019-30-07 at 17:30