Yegorova A. Use of sensitized luminescence of lanthanide ions for determination of bioactive substanses

Dissertation is devoted to search of new possibilities of the use of sensibilized luminescence of lanthanide ions (SLL) in their binary- and ternary complexes offered as analytical forms for direct and indirect determination of bioactive substances, molecules or ions which are able either to sensibilize or to quench central ion emission. The new class of organic reagents is introduced into the fluorescent analysis - oxyquinoline carboxylic acid amides derivatives, which are able to form complexes with lanthanides (Ln) in the water medium (without use of organic solvents, surfactants and synergetic agents) possessing high luminescent characteristics. Relationship between the structure of ligands and the quantum yield (Ф) of luminescence and lifetime of the excited state of europium (III) and terbium (III) complexes was established through 2D-QSРR models. Рriority influence on the Ф and lifetime of electrostatic and Van-der-Waals interactions, topology and lipophilicity of the ligands was established. The conditions of formation and luminescent properties of Ln(III) complexes with some medicinal preparations (MP) offered as sensitizers of central ion emission were investigated. New analytical forms for determination of tetracycline, fluoroquinoline and cephalosporine antibiotics, hydroxyl- and carboxylsubstituted 1,4-benzodiazepines, non-steroidal anti-inflammatory drugs were proposed. For medicinal preparations applied in the form of salts of organic bases, which cations do not interact with Ln(ІІІ), but the anions of these salts either enhance or decrease the luminescence of coordination unsaturated complexes Ln(ІІІ):sensitizer = 1 : 1. Comletely new possibility for the determination of namely these MP by influence of their anions was established. It has been shown that SLL quenching by some medicinal preparations do not interact with Ln(ІІІ) caused by reaction between quencher and ligand-sensitizer. It has been established that the terbium (III) ions form complexes with carboxylated crown ethers, luminescence of which is quenched in result of formation of mixed-metal complexes Tb(III) - Na+ -4-carboxybenzo-15-crown-5 and Tb(III) - K+ -4-carboxybenzo-18-crown-6. On the basis of new analytical forms the methods for direct and indirect luminescent determination of different MP in dosage forms and also some bioactive substances in bioliquids and model solutions: ATP, DNA, proteins (BSA, IgG, HSA and hemoglobin), glucose, alkaline phosphatase, hydrogen peroxide were developed. Use of efficient enhancement solutions based on the studied Ln(ІІІ) complexes in the immunofluorescence analysis was proposed. Keywords: complex compounds, lanthanides, sensibilized luminescence, biologically active substances.