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Synthesis and characterization of complexes based on the fragment [Mo2O2S2]2+ for applications in biology


Author: Cebotari Diana
Degree:doctor of chemistry
Speciality: 02.00.01 - Inorganic chemistry
Year:2023
Scientific advisers: Aurelian Gulea
doctor habilitat, professor, Moldova State University
Floquet Sébastien
profesor universitar, Universitatea Paris-Saclay
Institution: Moldova State University

Status

The thesis was presented on the 22 November, 2022
Approved by NCAA on the 24 February, 2023

Abstract

Adobe PDF document1.08 Mb / in romanian
Adobe PDF document1.05 Mb / in english

Thesis

CZU 544.142.3:[546.77+547.497](043)

Adobe PDF document 15.40 Mb / in romanian
220 pages


Keywords

molybdenum, coordination compounds, mono- or bis-thiosemicarbazone, biological properties

Summary

Thesis structure: introduction, 5 chapters, general conclusions and recommendations, 99 bibliographic references, 10 annexes, 141 pages of basic text, 92 figures, 40 tables. The obtained results are published in 10 scientific papers.

The aim and objectives of the thesis: to find the synthesis conditions, to determine the composition, the structure, the biological and physico-chemical properties of the compounds combining the fragment [Mo2O2S2]2+ and various ligands of tiosemicarbazone-type; analysis of the structure-activity correlation; synthesis and characterization of the more voluminous mono-thiosemicarbazones and symmetrical bis-thiosemicarbazones; synthesis of compounds based on [Mo2O2S2]2+ with ligands of thiosemicarbazone; use of different strategies in order to isolate isomerically pure complexes; characterization of thiosemicarbazones and synthesized compounds by applying modern physical methods of research: FT-IR, EDX, MALDI-TOF, ESI-MS, 1H, DOSY, 1H{15N} HMBC NMR analysis, elemental analysis and X-ray diffraction; study of the biological properties: antimicrobial, antifungal and antioxidative properties of the synthesized compounds; investigating of the influence of the nature of the central atom on biological activity by replacing the molybdenum cluster with the copper atom.

The scientific novelty and originality: synthesis of 20 new complexes based on the fragment [MoV2O2S2]2+ and ligands of mono-thiosemicarbazone or bis-tiosemicarbazone and 15 new compounds of CuII based on phenol bis-tiosemicarbazones; isolation of pure isomeric MoV complexes. Application of more modern physical methods for the characterization of thiosemicarbazones and coordination compounds. Obtaining for the first time of MoV compounds based on bis-thiossemobazones and studying their biological properties. Investigation of the structure-activity correlation, taking into account the nature of the ligand and the nature of the central atom.

The solved scientific problem: the optimal conditions for the synthesis of bis-tiosemicarbazones were found and 3 different families of coordination compounds were synthesized on the basis of the fragment [MoV2O2S2]2+. The use of flexible or rigid bis-tiosemicarbazones has contributed to the isolation of pure isomeric compounds.

Theoretical significance and applicative value: the thesis contributes to the extension of scientific information on the study and characterization of physical and biological properties of coordination compounds based on [MoV2O2S2]2+ with different thiosemicarbazones or bis-thiosemicarbazones ligands. The antimicrobial, antifungal and antioxidant activities of free ligands and compounds were tested, studying the structure-activity correlation, which is influenced by the nature of the ligand and that of the central atom.

The applicability of the work: the expansion of the arsenal of biologically active compounds to fungi of the C. albicans species. Advanced study of compounds based on MoV and bis-thiosemicarbazones in electrocatalysis and design of artificial enzymes. The results of the research can be included in the standard courses at the bachelor's or master's cycle at the State University of Moldova.