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  • 1
    In: Analyst, 2016, Vol.141(4), pp.1226-1232
    Description: Platinum-based drugs are commonly used in cancer treatment. The biological activity of a metallodrug is obviously closely related to its chemical and stereochemical characteristics. An overlooked aspect is the effect of the ligand to the electronic structure of the metal atom (coordinated atom). We report herein a Resonant X-ray Emission Spectroscopy (RXES) study on the chemical speciation of chiral platinum complexes in which diastereomers are distinguished on the basis of their metal electronic configuration. This demonstrates RXES high chemical speciation capabilities, a necessary property to further investigate the reactivity of the Pt atom towards nucleophiles or bionucleophiles, and an important complement the previously reported RXES abilities, namely that it can be employed for in situ studies at physiological concentrations.
    Keywords: Spectrometry, X-Ray Emission ; Antineoplastic Agents -- Chemistry ; Organoplatinum Compounds -- Chemistry;
    ISSN: 0003-2654
    E-ISSN: 1364-5528
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  • 2
    Language: English
    In: Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry, July 2015, Vol.20(5), pp.841-53
    Description: The structure-activity relationships of chiral 1,2-diaminophenylalkane platinum(II) anticancer derivatives are studied, including interactions with telomeric- and genomic-like DNA sequences, the pKa of their diaqua species, structural properties obtained from DFT calculations and resonant X-ray emission spectroscopy. The binding modes of the compounds to telomeric sequences were elucidated, showing no major differences with conventional cis-platinum(II) complexes like cisplatin, supporting that the cis-square planar geometry governs the binding of small Pt(II) complexes to G4 structures. Double-stranded DNA platination kinetics and acid-base constants of the diaqua species of the compounds were measured and compared, highlighting a strong steric dependence of the DNA-binding kinetics, but independent to stereoisomerism. Structural features of the compounds are discussed on the basis of dispersion-corrected DFT, showing that the most active series presents conformers for which the platinum atom is well devoid of steric hindrance. If reactivity indices derived from conceptual DFT do not show evidences for different reactivity between the compounds, RXES experiments provide new insight into the availability of platinum orbitals for binding to nucleophiles.
    Keywords: Antineoplastic Agents -- Chemistry ; DNA, Neoplasm -- Drug Effects ; Hydrocarbons, Chlorinated -- Pharmacology ; Organoplatinum Compounds -- Chemistry
    ISSN: 09498257
    E-ISSN: 1432-1327
    Source: MEDLINE/PubMed (U.S. National Library of Medicine)
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