Synthesis and study of new materials based on coordination compounds with polyfunctional ligands and with useful properties in medicine, biology and technology ((SSMCCLP))

Strategic priority

V. Innovative technologies, sustainable energy, digitization

Strategic direction

Fundamental research in physics, chemistry, mathematics

Code
010602
Duration
2024-2027
Institutions

Institute of Chemistry of MSU
Faculty of Chemistry and Chemical Technology of MSU

Laboratories/Centers
  1. Laboratory of Bioinorganic Chemistry and Nanocomposite
  2. Laboratory of Coordination Chemistry
  3. Laboratory Advanced Materials  in Biopharmaceutics and Technics
Project manager

Dr. habilitate, assoc. prof. Vasile Lozan

Team:
Dr. DRUTA Vadim  Dr. hab., assoc. prof. BULHAC Ion Acad. GULEA Aurelian
Dr. CUZAN Olesea Dr. hab., prof. STEFIRTA Anastasia  Dr. GRAUR Vasilii
Dr. DRAGANCEA Diana  Dr. COCU Maria Dr. RUSNAC Roman
Dr. GORINCIOI Viorina  Dr. DANILESCU Olga  Dr. USATAIA Irina
JOVMIR Tudor Dr. LOZOVAN Vasile Dr. GRAUR Ianina
VODA Irina Dr. URECHE Dumitru  Dr. SÎRBU Angela
Dr. NEGUTA Elena CUBA Lidia Dr. ȚAPCOV Victor 
DERIVOLCOV Ion   Dr. BULIMESTRU Ion
    Dr. BÎRCĂ Maria
    Dr. POPA Nelea
    Dr. COTOVAIA Aliona
Abstract

The subprogramm is expected to develop optimal processes/methods for synthesis of about 10 to 15 new ligands containing O, S, N, P donor atoms and about 40-50 new coordination compounds of 3d- and 4f- transition metals and s-type metals with properties of potential adsorbents for small molecu-les, physiologically active substances, molecular magnets, specific catalysts for heterogeneous cata-lysis, nanostructured or highly porous materials. New coordination compounds of some 3d metals with N-(4-methoxyphenyl)-2-oxopropanamide, 1-(piperidin-1-yl)propane-1,2-dione, 1-(morpholin-4-yl)propane-1,2-dione, o/m/p-phthalic dialdehydes and 1-(azepan-1-yl)propane-1,2-dione 4-allyl/phenylthiosemicarbazones as potential antimicrobial, antifungal, antioxidant agents will be eaborated and studied. Coordination compounds of some 3d biometals with ligands containing thiosemicarbazones with different substituents in the 4N position: cyclohexyl, hexyl, tert-butyl /thiosemicarbazones of natural origin based on cinnamaldehyde and its derivatives with biological properties. The new coordination compounds will be characterized with adequate physical and physico-chemical methods of analyses (elemental analysis, X-ray , IR, NMR, RNG, ESR, UV-Vis, Magnetochemistry, Electronic microscopy, Ther-mogravimetry, Chro- mato-Mass-spectrometry, Ciclovoltammperometry, study of sorbtion proce-sses, etc.). This investigation will give the opportunity to: substantially clarify the role of the sinthe-sizedcomplexes in the fisiological, technological and biological processes; to publish and dissemi-nate the obtained scientific results in national and international journals; to present their at various scientific forums in the form of oral reports and posters; to recommend for certification and imple-mentation on the level from idea to implementation; to perform the intermediary and final reports of obtained results. Expected research are directly related to the strategic direction of the activity of science and innovation in Moldova, The National PROGRAM in the fields of research and innovation for the years 2024-2027.

Results, activities

Summary of the activity and results obtained in 2024

New porous coordination polymers of some s- and 3d-elements were obtained based on ligands containing carboxylic, triazole, pyrazole groups with nitrogen donor atoms, with permanent porosity, hydrolytically and thermally stable. They can be used as potential sorbents for gas storage and as catalysts in heterogeneous processes.

● The synthesis of polynuclear complex combinations of some 3d metals based on ligands con-taining S, C, O, N and Schiff base donor atoms was carried out. They possess enhanced antibac-terial properties against bacteria and fungi, inhibitory properties of fungal proliferation in biolo-gical processes and can serve as potential catalysts for redox processes or as molecular magnets.

● Synthesis methods of four new thiosemicarbazones with the abbreviation HL1-4 based on 4-allyl- and 4-phenylthiosemicarbazones N-(4-methoxyphenyl)-2-oxopropanamide and 1-(piperi-din-1-yl)propan-1,2-diones were developed. The molecular structure of which was confirmed by the help of spectral research methods (FTIR, NMR) and with of single crystal X-ray analysis.

●For the first time, 36 coordination compounds of Cu, Co, Fe, Ni, Zn were synthesized on the basis of HL1-4. In order to elucidate the composition, structure and physico-chemical properties of the synthesized compounds, modern research methods were applied. The biological proper-ties: antimicrobial, antifungal, antioxidant of the synthesized compounds were investigated.

●Phthalic acid dialdehydes upon condensation with monopyridinecarboxylic acid hydrazides form two types of chemical products: p- and m-dialdehydes with isonicotinic, nicotinic and picolinic acid hydrazides, in which two hydrazide molecules condense with one aldehyde group each, while in the case of o-dialdehyde, a hydrazide molecule of isonicotinic and nicotinic acids condenses with the two hydrazide nitrogen atoms, and the second molecule binds to the carbon atom of an aldehyde group.

●It has been found that the main emission intensity for luminophore coordinating agents is concentrated in the 450 nm region of the visible spectrum and they can be proposed as a useful material for obtaining blue lighting sources.

●In 2024, within the subprogramme, 2 monographs, 28 scientific articles were published in international, national journals, category A, B and various scientific collections. Team members participated in 14 international and national scientific conferences and published 46 abstracts, obtained 13 author patents. At the International Salons of Invention the patents were awarded with gold medals (30), silver medals (5), bronze medals (1) and 4 diplomas of excellence. 4 doctoral theses were defended.

Publications

National monographs

  1. GARBUZ, O., TODERAS, I., GULEA, A. Biological properties of some synthetic and natural compounds. Correlation of anticancer and antioxidant activities. Monograph. Tipografia Centrală. 271 p. Chisinau, 2024. ISBN 978-5-88554-387-3. https://www.bookchamber.md/carti-in-curs-de-aparitie-noiembrie-2024/
  2. GRAUR, V., GULEA, A. Novel biological agents based on metal complexes of N4-allylthiosemicarbazones and their derivatives. Monograph. Chișinău: CEP USM, 2024, 290 p. ISBN 978-9975-62-716-0. https://ichem.md/sites/default/files/2025-01/Monograph%20Graur%20Gulea%202024.pdf


Articles in Web of Science and SCOPUS journals

  1. ARAUZO, A., BARTOLOMÈ, E., LUZÓN, J., MELNIC, S., SHOVA, S.,BARTOLOMÈ, J.Low-Temperature Magnetism of Ln2Ba (Ln = Nd, Er, Ho) Furoate-Based Polymeric Chains: Slow Relaxation, Magnetic Anisotropy and Interactions. In: Low Temperature Physics, 2024, vol. 50, pp. 452–466. https://doi.org/10.1063/10.0026058 https://www.scimagojr.com/journalsearch.php?q=13789&tip=sid. (IF. 1,1)
  2. CEBOTARI, D., CALANCEA, S., GARBUZ, O., BALAN, G., MARROT, J., SHOVA, S., GUÉRINEAU, V., TOUBOUL, D., TSAPKOV, V., GULEA, A., FLOQUET, S.. Synthesis, structure and biological properties of a series of dicopper (bis-thiosemicarbazone) complexes. In: New Journal of Chemistry, 2024, 48(26), 12043-12053. https://doi.org/10.1039/D4NJ003s42J https://www.scimagojr.com/journalsearch.php?q=24824&tip=sid. (IF: 2,7)
  3. CHUMAKOV, Y., GRAUR, V., GRAUR, I., TSAPKOV, V., GARBUZ, O., GULEA, A. Insights into Antiradical Behavior: Crystal Structures and DFT Analysis of 2-Formylpyridine N4-Allylthiosemicarbazone Salts. In: Acta Chimica Slovenica. 2024, 71, 609-618. ISSN 1318-0207. https://doi.org/10.17344/acsi.2024.8728  https://www.scimagojr.com/journalsearch.php?q=22658&tip=sid&clean=0. (IF: 1,2)  
  4. COCU, M.A., BOUROSH, P. N., KRAVTSOV, V. K., DANILESCU, O. S., BULHAC, I. I. Mononuclear Nickel(II) and Copper(II) Coordination Compounds with Ligands Based on Acetyl(benzoyl)acetone S-Methylisothiosemicarbazones and 8-Quinolinecarboxaldehyde. Synthesis and Crystal Structure. In: Russian Journal of Coordination Chemistry, 2024, Vol. 50, No. 3, pp. 217–225. https://doi.org/10.1134/S1070328423601267 https://www.scimagojr.com/journalsearch.php?q=21523&tip=sid&clean=0. (IF: 1,9)
  5. DANILESCU, O., BOUROSH, P., BULHAC, I., SHOVA, S., KRAVTSOV, V.CH., CARABA, M. N., CARABA, I.V., POPESCU, R., CRISAN, M., HAIDU, D., KULIKOVA, O., COSTRIUCOVA, N.V., PETUHOV, O., CROITOR, L. Laminated dihydrazone Zn(II) coordination polymer with prospects for sensory and multifunctional biomedical applications. In: Polyhedron, 2024, vol. 258, pp. 117039 https://doi.org/10.1016/j.poly.2024.117039  https://www.scimagojr.com/journalsearch.php?q=25303&tip=sid.   (FI: 3,05).
  6. GORINCHOY, V., CUZAN, O., SHOVA, S., LOZAN, V. Synthesis and structural studies of heterometallic{[FeCa2(Sal)2(SalH)3(DMA)2(CH3OH)2]}n salicylate complex. In: Chemistry Journal of Moldova, General, Industrial and Ecological Chemistry, 2024, vol. 19, No. 1, pp. 62-68. DOI: https://doi.org/10.19261/cjm.2024.1168 https://www.scimagojr.com/journalsearch.php?q=21100773812&tip=sid&clean=0. (Categoria A)
  7. GRAUR, I., GRAUR, V., CADIN, M., GARBUZ, O., BOUROSH, P., MELNIC, E., LOZAN-TIRSU, C., BALAN, G., TSAPKOV, V., FALA, V., GULEA, A. Synthesis and Characterization of Copper(II) and Nickel(II) Complexes with 3-(Morpholin-4-yl)propane-2,3-dione 4-Allylthiosemicarbazone Exploring the Antibacterial, Antifungal and Antiradical Properties. In: Molecules, 2024, 29(16), 3903. https://doi.org/10.3390/molecules29163903 https://www.scimagojr.com/journalsearch.php?q=26370&tip=sid. (IF: 4,2)
  8. PARSHUTIN, V. V., KOVAL, A. V., GORINCHOY, V. V.,LOZAN, V. I. Effect of Heteronuclear Salicylate Complex {[FeSr2(SalH)2(Sal)2(NO3)(DMA)4]}n on Corrosion of Steel St. 3 in Water.ISSN 1068-3755, In: Surface Engineering and Applied Electrochemistry, 2024, vol. 60, No. 1, pp. 109–121. https://doi.org/10.3103/S1068375524010137  https://www.scimagojr.com/journalsearch.php?q=11700154397&tip=sid. (IF: 1,1)
  9. RUSNAC, Roman, GARBUZ, Olga, KRAVTSOV, Victor, MELNIC, Elena, ISTRATI, Dorin, TSAPKOV, Victor, POIRIER, Donald, GULEA, Aurelian. Novel Copper(II) Coordination Compounds Containing Pyridine Derivatives of N4-methoxyphenyl-Thiosemicarbazones with Selective Anticancer Activity. In: Molecules, 2024. https://scholar.google.com/citations?view_op=view_citation&hl=ro&user=ONi_tMIAAAAJ&sortby=pubdate&citation_for_view=ONi_tMIAAAAJ:SjuI4pbJlxcC   https://www.scimagojr.com/journalsearch.php?q=26370&tip=sid. (IF: 4,2)
  10. TERENTI, N., LAZARESCU, A., SHOVA, S., BOUROSH, P., NEDELKO, N.,SLAWSKA-WANIEWSKA, A., ZARICIUC, E., LOZAN, V.Synthesis, X-ray and antibacterial activity of new copper(II)thiosemicarbazone complexes derived from4-formyl-3-hydroxy-2-naphthoic acid. In: Inorganica Chimica Acta, 571 (2024) 122216. https://doi.org/10.1016/j.ica.2024.122216. https://www.scimagojr.com/journalsearch.php?tip=sid&q=25270.  (IF: 2,7)
  11. TERENTI, N.; NEDELKO, N.; MELNIC, E.; PREDA, S., FRUTH, V.; LATUCH, J., KRAVTSOV, V.Ch.; SLAWSKA-WANIEWSKA, A.; LAZARESCU, A.; LOZAN, V. Heterometallic Co–Sr 2,3-pyridinedicarboxylate complex and its relatedperovskite oxide: Synthesis, structural characterization and magnetic properties. In: Journal of Solid State Chemistry, vol. 331, March 2024, 124538. https://doi.org/10.1016/j.jssc.2023.124538 (IF: 3,656). https://www.scimagojr.com/journalsearch.php?q=26972&tip=sid. (IF: 3,2)
  12. URECHE, D.; BULHAC, I.; BOUROSH, P. Mono- and binuclear coordination compounds of Ni(II) and Mn(II) with dioximic and dicarboxylic ligands. In: Chemistry Journal of Moldova, 2024. https://doi.org/10.19261/cjm.2024.1212  http://cjm.ichem.md/sites/default/files/article_files/U.P.-ChemJMold_10.19261cjm.2024.1212-Ureche.pdf. https://www.scimagojr.com/journalsearch.php?q=21100773812&tip=sid&clean=0. (Categoria A)
  13. VERLAN, V., CULEAC, I., GHNEA, V., BORDIAN, O., ZUBAREVA, V., BULHAC,, I., COJOCARU, I., ENACHESCU, M. Photoluminescence and thermo-stability of polymer composite nanomaterial [Eu(μ2–OC2H5)(btfa)(NO3)(phen)] 2phen)/PEPC. In: Romanian Reports in Physics, 76, 509, 2024. https://doi.org/10.59277/RomRepPhys.2024.76.509. https://rrp.nipne.ro/2024/AN76509.pdf.  https://www.scimagojr.com/journalsearch.php?q=10800153309&tip=sid&clean=0. (IF: 2,1)


Articles in international journals 

  1. GARBUZ, O., GRAUR, V., GRAUR, I., RAILEAN, N., TODERAS, I., PAHONTU, E., CEBAN, I., JINGA, V., ISTRATI, D., CEBAN, E., GULEA, A. Biological Activity of Copper(II) Complex (2-((2-(Prop-2-En-1- Ylcarbamothioyl) Hydrazinylidene)Methyl)-Phenolato)-ChloroCopper(II)         Monohydrate. In: Journal of Cancer Science and Clinical Therapeutics, 2024, 8 pp. 287-294. ISSN: 2637- 5079. https://www.doi.org/10.26502/jcsct.5079251
  2. NEDBALIUC, Boris; CIOBANU, Eugeniu; GRIGORCEA, Sofia; URECHE, Dumitru; COROPCEANU, Eduard; BRÎNZĂ. Lilia. [CaL3][Co(NCS)4] – potential agent for enhancing the productivity of Chlorella Vulgaris Beijer. microalga. In: Acta et commentationes. Științe Exacte și ale Naturii. 2024, nr. 17(1), pp. 74-80. DOI: https://doi.org/10.36120/2587-3644.v17i1.74-80.
  3. ȘTEFÎRȚĂ, A.; BULHAC, I.; BRÎNZĂ, L.; COCU, M.; ZUBAREVA, V. Physiological particularities of maize plants and the effect of some antioxidants under conditions of moderate drought. In: Journal of Applied Life Sciences and Environment, 2024. Vol. 57. Issue 1 (197), pp. 1-17. https://doi.org/10.46909/alse-571121
  4. URECHE, Dumitru; BULHAC, Ion; BOUROSH, Pavlina. New (o-phenylenediaminglyoximato)-(o-phenylenediaminglyoxime)zinc(II) chloride. Synthesis and crystal structure. In: Acta et commentationes. Științe Exacte și ale Naturii. 2024, nr. 17(1), pp 32-41. DOI: https://doi.org/10.36120/2587-3644.v17i1.32-41


Articles in national journals 

  1. GRAUR, I., MAXIM, M., GRAUR, V. О., TSAPKOV, V. I., GULEA, A., GARBUZ, O. Exploring the antioxidant activity of 1-(piperidin-1-yl) propane-1, 2-dione 4-phenylthiosemicarbazone and 3d metal coordination compounds with this ligand. In: Studia Universitatis Moldaviae (Seria Ştiinţe Reale şi ale Naturii), 2024, 171(1), 239-246. DOI: https://doi.org/10.59295/sum1(171)2024_28
  2. PÎNTEA, A., CIURSIN, A., RUSNAC, R., GULEA, A. (2024). Combinații coordinative ale Cu(II) în baza N-hexil-2-[(piridin-2-il) metiliden] hidrazine-1-carbotioamidei: proiectare, sinteză, evaluarea proprietăților antimicrobiene și antifungice. In: Revista științifică a Universtității de Stat din Moldova, (1), 171. https://doi.org/10.59295/sum1(171)2024_21  https://doi.org/10.59295/sum1(171)2024_21 


Patents

  1. BULHAC, Ion, URECHE, Dumitru, CILOCI, Alexandra, BOUROȘ, Pavlina, TIURINA, Janeta, LABLIUC, Svetlana. Tetra(izitiocianat)cobalt(II) de tris(dimetilpiridin-2,6-dicarboxilat)strontium cu proprietăți de stimulator al activității lipolitice la tulpina de fungi Rhizopus arrhizus CNMN FD 03. Brevet de invenție MD 4831 C8 din 2024.04.30. https://www.db.agepi.md/Inventions/details/a%202021%200037
  2. BULHAC, Ion; URECHE, Dumitru; CILOCI, Alexandra; COCU, Maria; CLAPCO, Steliana; LABLIUC, Svetlana. Tetra(izotiocianat)cobaltat(II) de tris(dietil piridin-2,6-dicarboxilat)calciu cu proprietăţi de stimulator al activităţii lipolitice la tulpina de fungi Rhizopus arrhizus CNMN FD 03. Brevet de invenție MD 4870 B1 din 31.05.2024. https://www.db.agepi.md/Inventions/details/a%202022%200004
  3. DANILESCU, O., BULHAC, I., COCU, M., BOUROȘ, P., CILOCI, A., CLAPCO, S., LABLIUC, S., MATROI, A. Perclorat de 2,6-diacetilpiridin-bis(picolinoilhidrazon)-bis(aqua)fier(III)–hidrat(1/2,5) cu proprietăți de stimulator al sintezei lipazelor exocelulare pentru tulpina de fungi Rhizopus arrhizus CNMN FD 03. Brevet de invenție MD 4874 din 30.06.2024. https://db.agepi.md/Inventions/details/a%202022%200005
  4. DANILESCU, O., BULHAC, I., CROITOR, L., BOUROȘ, P., KULICOVA, O. Nitrat de 2,6-diacetilpiridin-bis(picolinoilhidrazon)-(aqua)(nitrato)cadmiu(II)–monohidrat cu proprietăți fotoluminescente. Brevet de invenție MD 4884 din 24.08.31. https://db.agepi.md/Inventions/details/a%202022%200015
  5. GARBUZ O., GRAUR V., ȚAPCOV V., TODERAȘ I., GULEA A. Clorură de tris[N-(prop-2-en-1-il)hidrazincarbotioamid]cobalt(III), care posedă proprietăți de stimulator al statutului antioxidant total al hemolimfei albinelor Apis mellifera  și larvelor acestora. Brevet de invenție MD 4905. 2024 din 2024.10.31.  https://www.db.agepi.md/Inventions/details/a%202023%200014/LinkTitluAcc
  6. GULEA A., ȚAPCOV V., POIRIER D., LOZAN V. Utilizarea di(m-S)-bis{cloro-[N-(fenil)-N’-(piridin-2-il-metiliden)carbamohidrazonotioat][4-amino-N-(1,3-tia-zol-2-il)benzensulfonamid]cupru} dihidrat în calitate de inhibitor al activității enzimei 17b-HSD Tipul 1. Brevet de invenție MD 4903 din 2024.10.31.  https://www.db.agepi.md/Inventions/details/a%202023%200022/LinkTitluAcc
  7. GULEA Aurelian; CEBOTARI Diana; FLOQUET Sébastien; ŢAPCOV Victor; BĂLAN Greta; LOZAN-TÎRŞU C. (m2-Bromo)-{m2-2,2'-[(5-terţ-butil-2-oxido-1,3-fenilen)dimetaniliden]bis(N-metilhidrazin-1-carbotioamido)}-di-cupru(II), care manifestă activitate antimicotică faţă de Candida albicans. Brevet de invenție MD 4886 din 2024.09.30. https://www.db.agepi.md/Inventions/details/a%202022%200041/LinkTitluElib
  8. GULEA Aurelian; RUSNAC Roman; ŢAPCOV Victor; BĂLAN Greta; LOZAN-TÎRŞU Carolina; CEBAN Emil. Hidratul de bis{N-ciclohexil-N'-[(piridin-2-il)metiliden]carbamohidrazontioato}nichel, care manifestă activitate bacteriostatică faţă de bacteriile din specia Streptococcus pneumoniae. Brevet de invenție MD 4883 din 2024.08.31. https://www.db.agepi.md/Inventions/details/a%202022%200028/LinkTitluElib
  9. GULEA, A.; ȚAPCOV, V.; ISTRATI, D.; POIRIER, D. Utilizarea di(m-S)-bis{cloro-[N-(2,4-dimetilfenil)-N’-(piridin-2-ilmetiliden)carbamohidrazonotioat]cupru} tetrahidrat în calitate de inhibitor al proliferării celulelor HepG2 ale cancerului la ficat. Brevet de invenție  MD 4899 din 2024.08.31. https://www.db.agepi.md/Inventions/details/a%202023%200021/LinkTitluAcc
  10. LOZAN, Vasile; PARŞUTIN, Vladimir; COVALI, Alexandr; JOVMIR, Tudor. Procedeu de protecţie a oţelului de coroziune în apă. Brevet de invenție  MD 1726 Z din 2024.06.30. https://www.db.agepi.md/Inventions/details/s%202022%200093/LinkTitluElib
  11. LOZAN, Vasile, PARŞUTIN, Vladimir, PARAMONOV, Anatolii, COVALI, Alexandr. Procedeu de protecţie a oţelului de coroziune în apă. Brevet de invenție MD 1764 Y  din 2024.07.31. https://www.db.agepi.md/Inventions/details/s%202023%200057/LinkTitluAcc
  12. LOZAN, Vasile, PARŞUTIN, Vladimir, PARAMONOV, Anatolii, COVALI, Alexandr. Procedeu de protecţie a oţelului de coroziune în apă. Brevet de invenție MD 1746 Y din 2024.10.31. https://www.db.agepi.md/Inventions/details/s%202023%200056/LinkTitluElib
  13. LOZAN, Vasile, PARŞUTIN, Vladimir, COVALI, Alexandr, GORINCIOI, Viorina. Procedeu de protecţie a oţelului de coroziune în apă. Brevet de invenție MD 1754 Y din 2024.05.31. https://www.db.agepi.md/Inventions/details/s%202023%200058/LinkTitluAcc