Physico-chemical mechanisms of redox processes with electron transfer involved in vital, technological and environmental systems

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/20.80009.5007.27
Duration
2020-2023
Institutions
  1. Institute of Chemistry, Centre of Physical and Inorganic Chemistry, Laboratory of Physical and Quantum Chemistry
  2. State University of Moldova, Faculty of Chemistry and Chemical Technology
  3. Technical University of Moldova, Department of Oenology and Chemistry 
Project manager

Academician, dr. habilitate, professor Gheorghe DUCA

Team:

The team of the Institute of Chemistry

Cor. memb. GERU Ion Dr. ARSENE Ion
Dr. GORINCIOI Natalia   Dr. IALTICENCO Olga
Dr. habilitate COVALIOVA Olga   VICOL Crina
Dr. GORBACIOV Mihai HRAMCO Constantin
Dr. BARBA Alic SCALEȚCHI Valentina
Dr. ROMANCIUC Lidia MIDONI Irina
Dr. BALAN Iolanta BLAJA Piotr
Dr. ANGHEL Lilia PIATÎGHIN Serghei
Dr. habilitate ZINICOVSCAIA Inga BOLOCAN Natalia
Dr. GORINCIOI Elena  

     

Abstract

Chemical reactions with electron transfer between oxidants and reducing agents lay in the base of most important processes in living organisms and in the environment. These transformations involve complex processes and require detailed research on electronic structure, thermodynamics, kinetics and catalysis of redox reactions. Although up until now multiple studies have been conducted in this area, the problem is far from being resolved. In particular, the role of vibronic coupling in forming the electron transfer barrier and its possible manipulation is not explored. Not all pathways for the transformation of substances with reducing properties have been comprehensively studied, particularly those of the classes of enodiols, thiols, polyphenols and vitamins. In the same context, the problem of preventing negative effects caused by oxidants, such as damage to living cells, DNA, proteins and lipids remains unresolved.
The proposed study will contribute to solving the aforementioned problems as well as other related ones. In carrying out this project, the Institute of Chemistry in partnership with the State University of Moldova and the Technical University of Moldova will conduct interdisciplinary fundamental studies using a diverse range of chemical and physical methods, which will cover various fields of chemistry, in particular quantum chemistry, food and ecological chemistry, etc.

The following series of research will be carried out:

• Theoretical study of the mechanisms of charge transfer reactions using quantum-chemical calculations of electronic structure and vibronic theory;
• Model of the kinetics and thermodynamics of redox reactions, research the impact of reducing substances on the processes of self-purification of the aquatic environment and the photocatalytic oxidation of emerging pollutants;
• Synthesis and study of carbon quantum dots with antioxidant properties for application in biomedicine and the use of nuclear magnetic resonance spectroscopy for food quality control;
• Exploration of the action synergism of antioxidants, study of the lipid oxidation and establishing the associative interactions between antioxidants and lactoferin for the design of new functional and nutraceutical foods;
• Kinetic study of antioxidants action on the methanogenic  microorganisms activity in anaerobic fermentation of biochemical systems.

The envisaged research will contribute to the accumulation of new knowledge regarding the essence of the oxidation-reduction processes, reveal and theoretical justification of key mechanisms, discovery of new aspects of methods of controlling the redox reactions, all of which have a major interest for life and health, food products quality, as well as the state of the environment.
The intelligent management of the obtained results will stimulate the development of innovative targeted products, which will contribute to the economic development of the country. At the same time, the results will serve as basis for applying to international programs Horizon 2020, Horizon Europe 2027, COST, USNSF, NATO.
The results of the project will be the subject of discussion at seminars and scientific conferences, published in impact factor journals, incorporated into lectures for bachelors, masters and doctoral students, all the while contributing to the increase of the level of teaching and aspiration of young researchers in the development of their scientific career.

Results, activities

2021

Scientific seminar,
September 07 - 09, 2021
(online)		 Scientific seminar (online):  “RECENT SCIENTIFIC ACHIEVEMENTS IN QUANTUM CHEMISTRY AND THEORY OF VIBRONIC EFFECTS IN MOLECULAR SYSTEMS”, with participation of Academician Isaac BERSUKER, Professor of Texas University, USA.
Two public lectures ant two oral scientific reports were presented.
The seminar was attended by about 40 researchers.
Program
The 7th International Conference "Ecological and Environmental Chemistry-2022", EEC-2022,
March 3-4, 2022 
(online)		 On March 3-4, 2022, in Chisinau, Republic of Moldova was held the 7th International Conference: "Ecological and Environmental Chemistry" (EEC-2022). 

The EEC-2022 Conference is part of a series of successful conferences organized in 1995, 2002, 2005, 2008, 2012 and 2017, supported by different international organizations such as UNESCO, CRDF/MRDA, CEI, NATO, ONRG, as well as the local R&D organizations.
The EEC-2022 Conference was an important international event that attracted more than 270 scientists, researchers, engineers, experts and students from 30 countries, specifically:  Armenia, Algeria, Azerbaijan, Belarus, Brazil, Canada, China, Czech Republic, Finland, France, Georgia, Hungary, Israel, Italy, Iraq, Kazakhstan, Moldova, Montenegro, Morocco, Poland, Romania, Russia, South Korea, Switzerland, Turkey, Vietnam, Ukraine, Uzbekistan and USA.

   Within the EEC-2022 Conference the following presentations were held:

  • The Academic Lecture, delivered by Academician, Professor Gheorghe Duca;
  • 8 Plenary Presentations provided by worldwide recognized scientists;
  • 80 Oral Presentations in the Five Parallel Sessions, presented by the experienced and young scientists from the above mentioned countries;
  • 165 Poster Presentations discussed on-line by the conference participants.


The two Volumes of the Abstract Book have been published, which include 260 Abstracts presented by participants of the EEC-2022 Conference.

Scientific seminar ”Landmarks on the time axis. Edition dedicated to the 85th birth anniversary of the correspondent member Ion GERU",
December 8, 2022

 The seminar was attended by about 40 persons.
Program
Scientific Webinar entitled  ”Spontaneous Symmetry Breaking and Jahn-Teller Effects, dedicated to the 95th birthday of Academician Isaac BERSUKER”, February 10, 2023 Program

2020

Project realization has contributed into elucidation of physical-chemical mechanisms of redox processes with electron transfer in vital, food, technological and environmental systems.  Theoretical studies demonstrated the antioxidant activity dependence of food unsaturated acids on particurities of their electron structure. Interactions of these acids with free radical DDPH proceeds through the intermediate complexes formation with partial charge transfer. Experimental research has shown that the combination of certain organic acids provides synergetic effect in active radicals dezactivation in agricultural products; stability of polysaccharides depends on medium acidity. Oxidation mechanism of lipids and other organic substances from vegetable oils, grapes and wine was revealed.  
Investigation of redox processes and radical auto-purification, as well as of advanced catalytic oxidation of emergent contaminants has allowed to determine their mechanisms and to reveal the thiolic substances role in formation of natural water quality. Research of the redox processes in waste waters using the Fenton reagent have demonstrated that antioxidants introduction in fermented biomass makes it possible to ensure their deodoration and detoxication.
Using the modified process, the 2-mm carbon quantum dots were synthesized, which are non-toxic and have potential of application as biosensors and chemical sensors, in catalysis and photocatalysis, for energy conversion, etc.   

Publications

Monographs

  1. DUCA, Gh.; VASEASHTA, A. Handbook of Research ”Emerging Developments and Environmental Impacts of Ecological Chemistry”. IGI Global, SUA., 2020. 649 p. ISBN13: 9781799812418, ISBN10: 1799812413, EISBN13: 9781799812432, doi: 10.4018/978-1-7998-1241-8.
     

Chapters in monographs 

  1. Gorincioi, N.N.; Bersuker, I.B. Origin of puckering (buckling) of planar heterocycles and methods of its suppression. In: Heterocycles, Danielsen J.M.(ed.), Nova Science Publishers, Inc., 2020, p. 129-188. ISBN: 978-1-53617-804-3
  2. VASEASHTA, A.; DUCA, Gh,; CULIGHIN, E.; BOGDEVICI, O.; KHUDAVERDYAN, S. Smart and Connected Sensors Network for Water Contamination Monitoring and Situational Awareness. In book: Functional Nanostructures and Sensors for CBRN Defence and Environmental Safety and Security (NATO Science for Peace and Security Series C: Environmental Security), January 2020, pp 283-296. doi: http://doi.org/10.1007/978-94-024-1909-2_19.
  3. POVAR, I.; SPINU, O.; LUPASCU, T.; DUCA, Gh. Thermodynamic Stability of Natural Aqueous Systems. In: Handbook of Research ”Emerging Developments and Environmental Impacts of Ecological Chemistry”. IGI Global, SUA., 2020 pp 76-108, doi: 10.4018/978-1-7998-1241-8.ch004.
  4. DUCA, Gh.; MEREUTA, A.; TĂNĂSELIA, C.; LEVEI, E.; VELISCO, N. Assessment of Surface Water Pollution With Heavy Metals. In: Handbook of Research ”Emerging Developments and Environmental Impacts of Ecological Chemistry”. IGI Global, SUA., 2020, pp 212-228, doi: 10.4018/978-1-7998-1241-8.ch010.
  5. DUCA, Gh.; COVALIOV, V.; COVALIOVA, O. Intensive Biochemical Processes of Wastewater Treatment With High Caloricity Biogas Production. In: Handbook of Research ”Emerging Developments and Environmental Impacts of Ecological Chemistry”. IGI Global, SUA., 2020, pp 291-306, doi: 10.4018/978-1-7998-1241-8.ch013.
  6. GLADCHI V., BUNDUCHI E., ROMANCIUC L. Ecological Chemistry of Natural Waters. In: ”Emerging Developments and Environmental Impacts of Ecological Chemistry” de către Editura IGI Global, SUA, Co-editor Acad. Gh.Duca. https://www.igi-global.com/book/handbook-research-emerging-developments-environmental/231905., pp.197-211.

    Articles in international journals
  7. DUCA, Gh., TRAVIN, S., VASEASHTA, A., GLADCHI, V., KOZLOV, Yu. Global warming – pro and contrary interpretations using modelling and analysis of two cities. In: Int. J. Global Warming, vol. 24, No. 2, 2021, pp. 108-130. DOI: 10.1504/IJGW.2021.115894
  8. DUCA, GH., BOLOCAN, N. Understanding the chemical reactivity of dihydroxyfumaric acid and its derivatives trough conceptual DFT. In: Revista de Chimie, 2021(4), 72, 162-174. https://doi.org/10.37358/RC.21.4.8465  (IF:  1,351)
  9. ДУКА, Г., БЛОНСКИ, В., ГЛАДКИ, В., ТРАВИН, С. Фотохимические превращения  тиолов на примере цистеина и их влияние на формирование редокс-состояния природных вод. В: Экологическая химия. 2021, 30(2); pp. 94–100. https://chemjournals.thesa.ru/eco/a/30_2/p93.pdf  (IF: 0,395)
  10. CIOCARLAN, A., HRISTOZOVA, G., ARICU, A., DRAGALIN, I., ZINICOVSCAIA, I., YUSHIN, N., GROZDOV, D., POPESCU, V. Determination of the elemental composition of aromatic plants cultivated industrially in the republic of moldova using neutron activation analysis. In: Agronomy. 2021, nr. 5(11), pp. 1-20. ISSN 2073-4395, DOI: https://doi.org/10.3390/agronomy11051011  https://ibn.idsi.md/ro/vizualizare_articol/132488 (IF:  3,64)
  11. GORBACHEV, M.YU., GORINCHOY, N.N., ARSENE, I. Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study. In: International Journal of Organic Chemistry, 2021, 11(1), pp. 1-13. DOI: https://doi.org/10.4236/ijoc.2021.111001 (IF: 0,58)
  12. SUBOTIN, Iu., DRUŢĂ, R., POPOVICI, V., COVACI, E., STURZA, R. Kinetic of ferced oxidation of grape seeds, walnuts and corn germs oils in the presence of antioxidants. In: Food and Nutrition Sciences, in print. https://www.scirp.org/journal/ paperinformation (IF: 1,04)
  13. VICOL, C., CIMPOIU, C., DUCA, G. Investigation of synergic/anti-synergic interactions of dihydroxifumaric acid and ascorbic acis with DPPH. In: Studia Universitatis Babeș-Bolyai Chemia. 2021, 66 (2), p. 49-58. DOI: 10.24193/subbchem.2021.2.04  (IF: 0,48)
  14. ZINICOVSCAIA, I., HRAMCO, C., CHALIGAVA, O., YUSHIN, N.,  GROZDOV, D., VERGEL, K.,  DUCA, Gh. Accumulation of potentially toxic elements in mosses collected in the Republic of Moldova. In: Plants. 2021, nr. 3(10), pp. 1-13. ISSN 2223-7747, DOI: 10.3390/plants10030471   https://ibn.idsi.md/ro/vizualizare_articol/126134 (IF: 2,762)
  15. ZINICOVSCAIA, I. et.al. Removal of metals from synthetic and real galvanic nickel-containing effluents by Saccharomyces cerevisiae. In: Chemistry and Ecology. 2021, nr. 1(37), pp. 83-103. ISSN 0275-7540. DOI: 10.1080/02757540.2020.1817404 https://ibn.idsi.md/ro/vizualizare_articol/126614 (IF:1,93)
  16. ZINICOVSCAIA, I., IVLIEVA, A., PETRITSKAYA, E., ROGATKIN, D., YUSHIN, N., GROZDOV, D., VERGEL, K., MAMULOVÁ-KUTLÁKOVÁ, K. Assessment of TiO2 Nanoparticles Accumulation in Organs and Their Effect on Cognitive Abilities of Mice. In: Physics of Particles and Nuclei Letters. 2021, nr. 3(18), pp. 378-384. ISSN 1547-4771. DOI: 10.1134/S1547477121030146  https://ibn.idsi.md/ro/vizualizare_articol/133995
  17. STURZA, R., DRUŢĂ, R., COVACI, E., DUCA, Gh., SUBOTIN I. Mecanisms of sunflower oil transforming into forces thermal oxidation processes. In: Journal of Engineering Science, vol. XXVII, no.3, 2020. https://doi.org/10.5281/zenodo.3949716
  18. DUCA, Gh.; TRAVIN, S.O. Reactions’ Mechanisms and Applications of Hydrogen Peroxide. American Journal of Physical Chemistry. 2020, 9(2). ISSN: 2327-2430 (Print); ISSN: 2327-2449 (Online). pp. 36-44. doi:10.11648/j.ajpc.20200902.13.
  19. DUCA, Gh.; COVALIOV, V.; COVALIOVA, O. Production, Structure and Photocatalytic Properties of Nanotubular TiO2. Environmental Engineering and Management Journal. 2020, 19(1), p. 1-10. – ISSN: 582-9596.

 GORBACIOV, M.Yu., GORINCHOY, N.N., ARSENE, I. Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study. International Journal of Organic Chemistry, 2021, vol. 11, No. 1, pp. 1-13. https://doi.org/10.4236/ijoc.2021.111001.

Articles in national journals:

  1. GORINCHOY, N.;  BALAN, I.; POLINGER, V.; BERSUKER, I.B. Pseudo Jahn-Teller origin of the proton-transfer energy barrier in the hydrogen-bonded [FHF]- system. Chemistry Journal of Moldova, 2021, 16(1), pp. 115-120. DOI: http://dx.doi.org/10.19261/cjm.2021.834
  2. LIS, A., GLADCHI, V., DUCA, Gh., TRAVIN, S. Sensitized photolysis of thioglycolic acid in aquatic environment. In: Chemistry Journal of Moldova. 2021, nr. 1(16), pp. 46-59. ISSN 1857-1727, DOI: 10.19261/cjm.2021.796. https://ibn.idsi.md/ro/vizualizare_articol/134252
  3. КОВАЛЕВА, О., КОВАЛЕВ, В. Фотокаталитическое обеззараживание патогенных бактериальных систем в водной среде.  In: Intellectus. 2021, Nr.3-4, pp.  ISSN 1810-7079.   http://www.agepi.md/ro/intellectus
  4. SANDU, M., TĂRÎŢĂ, A., GLADCHI, V., DRAGALINA, G. Conţinutul amoniacului neionizat în apele din râul Prut şi din afluenţii lui de stânga. In: Studia Universitatis Moldaviae, 2021, nr.1(141) Seria “Științe reale și ale naturii” ISSN 1814-3237 ISSN online 1857-498X, p.137-145.
  5. MOCANU, L., GONŢA, M., MATVEEVICI, V., DUCA, Gh., PORUBIN-SCHIMBĂTOR, V. Îndepărtarea cefalexinei din soluții apoase utilizând procesul fotocatalitic Fenton. In: Revista de Ştiinţă, Inovare, Cultură şi Artă „Akademos”. 2021, nr. 2(61), pp. 53-60. ISSN 1857-0461, DOI: 10.52673/18570461.21.2-61.03 
  6. КОВАЛЕВ, В.; КОВАЛЕВА, О. Биохимическая трансформация сероводорода и пути дезодорирования сточных вод. Studia Universitatis Moldaviae. Ser. “Şt. reale şi ale naturii”. 2020, Nr.6 (136), pp. 177-185. ISSN1814 3237, online 1857 498X, DOI: http://doi.org./10.5281/zenodo.4431823


Patents 

  1. COVALIOVA, O.; COVALIOV, V.; UNGUREANU, D.; COPTIUG, E. Instalaţie de decontaminare a toxinelor organice şi bacteriilor din mediul acvatic. Patent MD 4738. Publ. 2021.01.31, BOPI 1/2021   
  2. COVALIOV, V.; COVALIOVA, O.; UNGUREANU, D. Instalaţie de obţinere a biogazului. Patent MD 4744. Publ. 2021.02.28, BOPI 2/2021
  3. COVALIOV, Victor; SACHEVICI, Veaceslav; COVALIOVA, Olga; RUSNAC, Arcadie; POLESCHUK, Gheorgy. Procedeu de deodorizare a deşeurilor organice. Patent MD 4750, 2021-10-31. http://www.db.agepi.md/inventions/    
  4. COVALIOV, Victor, COVALIOVA, Olga, NENNO, Vladimir, UNGUREANU, Dumitru, CIOBANU, Natalia, Dispozitiv pentru arderea fără fum a combustibilului gazos cu conţinut redus de metan. Brevet MD 4766. 2021-08-31. http://www.db.agepi.md/inventions/
  5. COVALIOV, Victor, COVALIOVA, Olga, NENNO, Vladimir, DUCA, Gheorghe, Procedeu de obţinere a biogazului. Patent MD 4767. 2021-09-30. http://www.db.agepi.md/inventions/
  6. COVALIOV, V.; SACHEVICI, V.; COVALIOVA, O.; RUSNAC, A.; POLESCHUK, Gh.  Procedeu de deodorizare a deseurilor organice. Positive decision no. 9705  from 2021.01.22