Interactions of praseodymium and neodymium with nucleosides and nucleotides: absorption difference and comparative absorption spectral study.

The interactions of praseodymium(III) and neodymium(III) with nucleosides and nucleotides have been studied in different stoichiometry in water and water-DMF mixtures by employing absorption difference and comparative absorption spectrophotometry. The 4f-4f bands were analysed by linear curve analysis followed by gaussian curve analysis, and various spectral parameters were computed, using partial and multiple regression method. The magnitude of changes in both energy interaction and intensity were used to explore the degree of outer and inner sphere coordination, incidence of covalency and the extent of metal 4f-orbital involvement in chemical bonding. Crystalline complexes of the type [Ln(nucleotide)2(H2O)2]- (where nucleotide--GMP or IMP) were characterized by IR, 1H NMR, 31P NMR data. These studies indicated that the binding of the nucleotide is through phosphate oxygen in a bidentate manner and the complexes undergo substantial ionisation in aqueous medium, thereby supporting the observed weak 4f-4f bands and lower values for nephelauxetic effect (1-beta), bonding (b) and covalency (delta) parameters derived from coulombic and spin orbit interaction parameters.

Interaction of some fluorinated nucleic acid components with praseodymium: an absorption spectral approach.

Absorption difference and comparative absorption spectrophotometric studies on praseodymium(III) and fluorouracil, fluorocytosine, fluoroadenine, fluorothymine, fluorouridine, fluorocytidine, fluoroadenosine and fluorothymidine systems at pH approximately 5.5 and in different stoichiometries in 80% DMF medium have been carried out. Magnitudes of spectral parameters, viz. Coulombic (Fk), spin-orbit (zeta 4f), nephelauxetic (beta), bonding (b), intensity (T lambda Judd-Ofelt), and oscillator strength (P) and their variation have provided information on the binding mode of these biomolecules in terms of outer and inner sphere complexation, degree of covalency and extent of 4f orbital involvement. Preliminary ultrasonic studies have indicated that these biomolecules behave as structure breakers, hence weak ligands in aqueous medium, while strengthening water structure in semi-nonaqueous medium. The analysis of the isolated solid complexes has suggested octa- and nona-coordination for praseodymium(III) in fluorinated nucleic bases and fluorinated nucleoside complexes.