New materials based on coordination compounds of metals with polyfunctional ligands as porous polymers, catalysts, biologically active substances and nanostructured compounds

Programme

Research project within the State Program financed by the National Agency for Research and Development of the Republic of Moldova

Strategic priority

V. Economic competitiveness and innovative technologies

Strategic direction

3. Materials, innovative technologies and products

Code
ANCD/20.80009.5007.04.
Duration
2020-2023
Institutions

Institute of Chemistry

Laboratories/Centers

Laboratory of Bioinorganic Chemistry and Nanocompzite

Project manager

Dr. habilitate, assoc. prof. Vasile LOZAN

Team:
Dr. DRUTA Vadim  Dr. DRAGANCEA Diana 
Dr. TAPCOV Victor   JOVMIR Tudor
Dr. CUZAN Olesea PUSCASU Boris
Dr. BALAN Iolanta  POPA Tatiana
Dr. MELNIC Silvia VODA Irina
Dr. SHOVA Sergiu  NEGUTA Elena
Dr. GORINCIOI Viorina DERIVOLCOV Ion
Abstract

The project 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 molecules, physiologically active substances, molecular magnets, specific catalysts for heterogeneous catalysis, nanostructured or highly porous materials. 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, Thermogravimetry, Chromato-Mass-spectrometry, Ciclovoltammperometry, study of sorbtion processes, etc.). This investigation will give the opportunity to: substantially clarify the role of the sinthesized complexes in the technological and biological processes; to publish and disseminate 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 implementation 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 for 2020-2023 years.

Results, activities

New porous coordination polymers of some 3d, s and lanthanide elements (52 compounds) were obtained based on ligands containing carboxylic groups and/or donor nitrogen atoms, with permanent porosity, hydrolytically and thermally stable. They can be used as potential sorbents for gas storage and as catalysts in heterogeneous acylation processes. The investigation of the luminescent properties of coordination polymers of lanthanides demon-strated that the compounds containing La3+, Nd3+ and Gd3+ possess only the emission associated with the organic ligand, and the polymers containing Eu3+ and Tb3+ show pure metal-centered radiation, while the polymer networks containing Dy3+ and Sm3+ exhibits dual metal- and ligand-centered luminescence.

The synthesis of polynuclear complex combinations of some 3d and s metals (21 compounds) based on ligands containing donor atoms S, C, O, N and Schiff bases was carried out. They possess enhanced antibacterial proper-ties against bacteria and fungi, inhibitory properties of fungal proliferation in biological processes and can serve as potential catalysts of redox processes or as molecular magnets.

Heteronuclear complex combinations of manganese(II), nickel(II) and cobalt(II) based on sebacic acid and o-phenanthroline, characterized by X-ray diffraction, possess ferromagnetic and antiferromagnetic properties.

Heteronuclear complex combinations of copper(II) based on salicylic acid characterized by X-ray diffraction possess enhanced antimicrobial properties to various pathogenic microorganisms

Nanoparticles based on small oxides synthesized from small trinuclear carboxylates characterized by electron microscopy, possess antimicrobial properties and have an increased biosynthetic influence on Trichoderma cultures.

Within the project, 14 scientific articles were published in prestigious journals with impact factors, 5 articles in national journals, category A, team members participated in 11 international and national scientific conferences (on-line) and published 9 abstracts, have obtained 11 patents and submitted 3 patent applications. At the invention salons, the patents were awarded with gold, silver, bronze medals and special prizes. A habilitation doctoral thesis and a doctoral thesis were support, 1 doctoral thesis is in progress.

 Scientific activities

Scientific seminar, December 18, 2020





 

 

A scientific seminar dedicated to the commemoration of the eminent scientist, Academician, Laureate of the State Prize in Science and Technology Constantin TURTA was organized, who on December 20, 2020, would have turned 80 years old.

Academician Constantin Turta is the founder of the Scientific School in the field of Bioorganic Chemistry in the Republic of Moldova and of the research directorate in the field of using Mössbauer spectroscopy in chemistry.   
Publications

Articles in international journals

  1. BEJAN, D.;, BAHRIN, L.-G.; SHOVA, S.; MARANGOCI, N.L.; KOKCAM-DEMIR, U.;LOZAN, V.; JANIAK, C. New microporous lanthanide organic frameworks. Synthesis,structure, luminescence, sorption, and catalytic acylation of 2-naphthol. Molecules. 2020,25, 3055; doi:10.3390/molecules25133055 (IF 3.267)
  2. CUZAN-MUNTEANU, O.; SIRBU, D.; GIORGI, M.; SHOVA, S.; GIBSON, E.A.; RÉGLIER, M.; ORIO, M.; MARTINS, L.M.D.R.S.; BENNISTON, A.C. Neutral Lipophilic Palladium(II) Complexes and their Applications in Electrocatalytic Hydrogen Production and C‐C Coupling Reactions. European Journal of Inorganic Chemistry. 2020,10, 813-822. ISSN 1099-0682. doi: 10.1002/ejic.201901283 (IF: 2.578).
  3.  LOZAN V.; MAKHLOUFI G.; DRUTA V.; BOUROSH P.; KRAVTSOV V.; MARANGOCI N.; HEERING C.; JANIAK Ch. Synthesis and structure of zinc(II) and cobalt(II) coordination polymers involving the elongated 2’, 3’, 5’, 6’ tetramethylterphenyl-4, 4”-dicarboxylate ligand. Inorgcanica Chimica Acta, 2020, 506, 119500. doi.org/10.1016/j.ica.2020.119500 (IF: 2,433).
  4. BRATANOVICI, B.-I.; NICOLESCU, A.; SHOVA, S.; DASCĂLU, I.-A.;ARDELEANU, R.; LOZAN, V.; ROMAN, Gh. Design and synthesis of novel ditopic ligands with a pyrazole ring in the central unit. Research on Chemical Intermediates. 2020, 46, 1587–1611. (I.F. 2,064) https://doi.org/10.1007/s11164-019-04052-3.
  5. BAHRIN, L.-G.; BEJAN. D.; SHOVA, S.; GDANIEC, M.; FRONC, M.; LOZAN, V.; JANIAK, C. Alkali- and alkaline-earth metal–organic networks based on a tetra(4-Carboxy-phenyl) bimesitylene-linker, Polyhedron, 2019, 173, 114128, https://doi.org/10.1016/j.poly.2019.114128 (I.F. 2.343)
  6. DASCĂLU, I.-A., MIKHALYOVA, E., SHOVA, S., BRATANOVICI, B.I., ARDELEANU, R., MARANGOCI, N.L., LOZAN, V., ROMAN, G. Synthesis, crystal structure and luminescent properties of isoreticular lanthanide–organic frameworks based on a tetramethyl-substituted terphenyldicarboxylic acid. In: Polyhedron, 2021, nr. 194. ISSN 0277-5387, DOI:10.1016/j.poly.2020.114929 (IF = 2.88)
  7. BRATANOVICI, B.-I., SHOVA, S., LOZAN, V., DASCALU, I.-A., ARDELEANU, R., ROMAN, G. 1-(4-Carboxyphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid – A versatile ligand for the preparation of coordination polymers and mononuclear complexes. In: Polyhedron, v.200, 15 May 2021, https://doi.org/10.1016/j.poly.2021.115115. (IF = 2.88)
  8. CUBA, L.; GORINCIOI, E.; DRAGANCEA, D.; SHOVA, S.; BOUROSH, P. Noncovalent Interactions in the Architectures with Substituted Salicylaldehyde Semicarbazones. In: Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya. 2021, nr. 7(47), pp.488-501, DOI: 10.1134/S1070328421070034 (IF = 1,168)
  9. DRAGANCEA, D., NOVITKI, Gh., MADALAN, A.M., ANDRUH, M. New cyanido-bridged heterometallic 3d-4f 1D coordination polymers: Synthesis, crystal structures and magnetic properties. In: Magnetochemistry. 2021, nr. 5(7), pp. 1-14. ISSN 2312-7481, DOI:10.3390/magnetochemistry7050057. (IF = 2,193)
  10. GULEA, A., GRAUR, V.О., ULCHINA, I., BOUROSH, P., SMAGLII, V., GARBUZ, O., TSAPKOV, V.I. Synthesis, Structure, and Biological Activity of Mixed-Ligand Amine-Containing Copper(II) Coordination Compounds with 2-(2-Hydroxybenzylidene)-N-(prop-2-en-1-yl)hydrazinecarbothioamide. In: Russian Journal of General Chemistry. 2021, nr. 1(91), pp. 98-107. ISSN 1070-3632, DOI: 10.1134/S1070363221010114. (IF = 0,81)
  11. ARAUZO, A., BARTOLOME, B., LUZON, J., ALONSO-GUTIÉRREZ, P., VLAD, A., CAZACU, M., ZALTARIOV, M.-F., SHOVA, S., BARTOLOME, J., TURTA, C. In: Molecules. Basel, Switzerland. 2021, nr. 18(26), pp. 1-26. , DOI: 10.3390/molecules26185626. (IF = 4,411)
  12. TSYMBAL, L.V., ANDRIICHUK, I.L., LOZAN, V., SHOVA, S., LAMPEKA, Y.D. Synthesis and crystal structure of diaqua(1,4,8,11-tetraazacyclotetradecane) zinc(II) bis(hydrogen-4-phosphonato-biphenyl-40-carboxylato)(1,4,8,11-tetraazacyclotetradecane) zinc(II). In: Acta Cryst. 2022. E78, 625–628.https://doi.org/10.1107/S2056989022004534.
  13. CUZAN,O.; SHOVA, S.; NOVITCHI, G.; LOZAN, V. Synthesis, characterization and magnetochemical study of cobalt, nickel and manganese coordination polymers, Inorganica Chimica Acta, 2023, 553, pp. 121526. ISSN 0020-1693, DOI: 10.1016/j.ica.2023.121526 (IF: 3.118)
  14. TERENTI, N.; MELNIC, E.; FRUTH, V.; NEDELKO, N.; ALESHKEVYCH, P.;  LEWINSKA, S.; SLAWSKA-WANIEWSKA, A.; KRAVTSOV, V.Ch.; LAZARESCU, A.; LOZAN, V. Synthesis and microstructure of BaMnO3 oxide obtained from coordination precursor. Journal of Solid State Chemistry V.324, August 2023, 124108  https://doi.org/10.1016/j.jssc.2023.124108 (IF: 3,656)


Articles in national journals

  1. GORINCHOY, V. Synthesis and structural caracterization of the tetranuclear iron(III)cluster with salicylic acid. : Chemistry Journal of Moldova, 2020, vol. 15, nr. 2, pp.62–68.  ISSN 1857–1727. Disponibil: http://dx.doi.org/10.19261/cjm.2020.758. (Categoria A).
  2. GORINCHOY, V., CUZAN, O., MELNIC, S., PETUHOV, O., SHOVA, S. Synthesis and characterisation of new {Fe2CrO} heterotrinuclear iron-chromium clusters. In: Chemistry Journal of Moldova, 2021, v.16, Nr.2. p. 66-75.
  3. VODA, I. A new 2D coordination polymer based on zinc(II), 1,2,3-benzenetricarboxylic acid and 4,4ʹ-bis(imidazol-1-ylmethyl)biphenyl: synthesis and crystal structure” Chemistry Journal of Moldova http://doi.org/10.19261/cjm.2022.1021.
  4. ПАРШУТИН, В. В., КОВАЛЬ, А. В., ГОРИНЧОЙ, В. В., ЛОЗАН, В. И. Влияние гетероядерного салицилатного комплекса {[FeSr2(SalH)2(Sal)2(NO3)(DМА)4]}n на коррозию стали Ст. 3 в воде, In: Электронная обработка материалов. 2023, v. 59, pp. 47-59. https://doi.org/10.52577/eom.2023.59.1.47


Patents

  1. LUPAŞCU, L.; JOVMIR, T.; POPA, T.; LOZAN, V. Aplicare a 2,6-bis(S-metilizotiosemicarbazidometiliden) -4-metilfenolato- tricloro- dicupru hidrat în calitate de remediu contra bacteriilor fitopatogene. Brevet de invenție MD 4663. 2019-12-31.
  2. JOVMIR, T.; BURDUNIUC, O.; POPA, T.; DRUŢĂ, V.; GULEA, A.; LOZAN, V. Compus hidrosolubil 2,6- bis (S-metilizotiosemicarbazidometiliden)-4-metilfenolato-tricloro- dicupru- hidrat pentru utilizare în calitate de remediu antimicotic. Brevet de invenție MD 4696, B1.2019.04.04, BOPI 5/2020, p. 67.
  3. JOVMIR, T.; BĂLAN, G.; POPA, T.; DRUŢĂ, V.; GULEA, A.; LOZAN, V. Compus hidrosolubil 2,6- bis(S-metilizotiosemicarbazidometiliden)-4-metilfenolato-tricloro- dicupru-hidrat pentru utilizare în calitate de remediu farmaceutic selectiv contra bacteriilor Gram-pozitive. Brevet de invenție MD 4687 B1, 2019.04.04, BOPI nr. 04/2020, p. 41.
  4. GORINCHOY, V.; LOZAN, V.; BURDUNIUC, O.; BALAN, G.; TSAPCOV, V.; GULEA A. Utilizarea tetrasalicilatului de bariu-cupru în calitate de inhibitor al proliferării fungilor din specia Cryptococcus Neoformans. BOPI nr.9/2020, 4712 B1 (2020.09.30).
  5. JOVMIR, T., BĂLAN, G., POPA, T., DRUȚĂ, V., GULEA, A., LOZAN V.  Compus hidrosolubil 2,6-bis(S-metilizotiosemicarbazidometilen)-4-metilfenolato-tricloro-dicupru hidrat în calitate de remediu farmaceutic selectiv contra bacteriilor Gram-pozitive. Brevet de invenție MD4687 C1, data eliberării 2021.01.31.
  6. JOVMIR, T.,BURDUNIUC, O.,POPA, T., DRUȚĂ, V., GULEA, A., LOZAN, V. MD4696 C1, Compus hidrosolubil 2,6-bis(S- metilizotiosemicarbazidometi-len)-4-metilfenolato-tricloro-dicupru hidrat în calitate de remediu antimicotic.  Brevet de invenție MD4696 C1, data eliberării 2021.02.28.
  7. LOZAN V., JOVMIR T.; PARȘUTIN Vl., COVALI Al. Procedeu de protecția a oțelului de coroziune în apă. Brevet de invenție MD1615 Y; Data publicării: 2021-04-30.
  8. LOZAN, V., PARȘUTIN, Vl., COVALI, Al., JOVMIR, T. Procedeu de protecție a oțelurilor contra coroziunii în apă. Brevet de invenție MD1534 Z; data eliberării 2021.12.31.
  9. GULEA, A., GRAUR, V., ȚAPCOV, V., BĂLAN, G., LOZAN, V.  Utilizarea  cloro-{N-prop-2-en-1-il-N'-[1-(piridin-2-il)etilidencarbamohidrazontioato}cupru în calitate de inhibitor al proliferării bacteriilor din specia Acinetobacter baumannii.  Brevet de invenție MD nr. 4810. Publicat BOPI. Nr. 6/2022. P. 50
  10. LOZAN, V., PARSHUTIN, Vl., COVALI, Al., JOVMIR, T. Procedeu de protecție a oțelului de coroziune în apă.  Brevet de invenție, MD 1726 Y 2023.11.30. BOPI nr.11/2023.
  11. GULEA, A., GRAUR, V., BALAN, G., ȚAPCOV, V., TODERAȘ, I., LOZAN, V. Nitrato- (N-(prop-2-en-1-il)-N,-(1-(piridin-2-il)-etiliden)carbamohidrazontio) cupru, care manifestă activitate antimicrobiană față de bacteriile din specia Streptococcus pneumoniae. Brevet de inventie, MD4842 C1 2023.01.31 BOPI nr.1/2023.