Anelchyk G. Luminescent determination of hydroxyl and carboxyl 1,4-benzodiazepines and some carboxylic acids using lanthanide complexes

The thesis is devoted to search of new analytical forms based on terbium (III) and europium (III) complexes with 3-substituted 1,4-benzodiazepines (BD) (hydroxyl- and carboxyl-) and some NSAIDs (ketoprofen, ketorolac, flurbiprofen, naproxen and indomethacin) to determine ligands using sensitized luminescence of lanthanide ions. Spectrophotometric and protolytic characteristics of reagents and conditions of their complex formation with ions of Eu(III) and Tb(III) were determined. It has been established, that the maximum intensity of the luminescence of complexes is observed in aqueous solutions. Only in case of cinazepam (L1) the formation of ternary complexes Tb(III)-L1-TOРO = 1:1:2 and 1:2:1 has been found as the result of studing the influence of the donor-active substances and surfactants on the emission of complexes. In case of 3-hydroxy 1,4-benzodiazepines the donor-active substances practically do not influence on the Ilum of their lanthanide complexes, but in the presence of anionic surfactants (AS) the ternary complexes Tb(III)-L2-11- AS = 1:1:2 and Tb(III)-L2-11- AS = 1:2:1 (in excess of reagent) have been formed. In the case of NSAIDs the synergistic effect, which is realized in the combined action of the two components (TOРO and Triton X-100) and characterized by the fact that the summary effect exceed the action of each component separately, have been established. The observed synergism has been explained by the formation of ternary complexes Ln(III) -NSAID-TOРO = 1:1:2 and 1:2:1 in the micelle medium. The complexation of 1,4-benzodiazepines, carboxyl- (cinazepam) and a hydroxylcontaining (L2-11), with lanthanide ions has been observed in the first time. The principle difference between these two groups of reagents during the formation of ternary complexes has been established . Highly sensitive, simple and express methods for determination of a number of drugs and biologically active substances with the limits of determination from 0.015 to 1.33 mg/ml has been developed on the base of the new analytical forms - ternary complexes Ln(III)-BD(NSAIDs)-AS (TOРO). Key words: ternary complexes, terbium, europium, sensitized luminescence, biologically active substances, 3-substituted 1,4-benzodiazepines, non-steroidal anti-inflammatory drugs.