Faculty of Chemistry, Biology and Biotechnology, Department of Biophysical Chemistry and Nanobiotechnologies
Free radical and radical chain oxidation with molecular oxygen. Antioxidants and bioantioxidants

The composition of the scientific group: Head of the Project: Doctor of Chemistry, Professor Oleksandr Shendrik; Principal investigator: Doctor of Chemistry, senior researcher Olha Kushch; Investigators: senior lecturer Oleksandr Tsyapalo, head of the educational and research laboratory Olha Zosenko, head of the educational laboratory Hanna Starkova, graduate student Iryna Hordeyeva

General information about the research group implementing the project

The team has been working on the problem for over 40 years. The funds to finance research are raised through grants from the national budget provided by the National Academy of Sciences and the Ministry of Education and Science of Ukraine. The results were published in more than 100 research papers, including 60 papers in peer-reviewed journals (Scopus, WoS), and three monographs. 4 patents were obtained, 6 PhD theses were defended.


Short description of the project

The research aims to:

  • solve the fundamental problem of the reactivity of particles in radical-chain reactions between organic substances and molecular oxygen;
  • develop the mechanisms of substrate activation;
  • find effective catalytic systems to increase the efficiency and selectivity during oxidative processing of hydrocarbons;
  • develop simple and cheap ways of initiation and inhibition;
  • create new catalytic systems.

The most significant results achieved

The results of basic research accumulated by the group allowed the researchers to start realizing several applied projects as laboratory models. Implementing these into practice requires organizational, material and financial resources. The most interesting proposals are listed below.

6.1. New thiazole derivatives demonstrating antioxidant and antimicrobial activities (Fig. 1).

Fig.1. New thiazole derivatives with antioxidant and antimicrobial properties

Protected by the patent:

  1. 4-(1,3-thiazol-4-yl)benzene-1,2-diols exhibiting anti-radical and antibacterial properties: utility model patent of Ukraine 87109: IPC C07D 277/02, A61P 17/18, A61P 31/04. Odaryuk V., Kanibolotska L., Burakov M., Shendryk O., Odaryuk I., Poddubna O., Lebedieva N., Kanibolotskyi O.; applicant and patent holder – Donetsk National University, L.M. Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry of the NAS of Ukraine. – u201308588; declared 08.07.2013; published 27.01.2014, Bull. No. 2 (in Ukrainian).

Publications:

  1. Synthesis and study of the antioxidant activity of 3,4-dihydroxyphenylthiazoles / A.M. Shendrik, N.I.Burakov, A.L. Kanibolotsky, V.V. Odaryuk, L.V. Kanibolotska, I.D. Odaryuk // Journal of Organic and Pharmaceutical Chemistry. – 2011. – Vol. 9, issue 4 (36) – P. 61-64.

Application areas

Drug development. Pharmacy.

6.2 A fundamentally new chemiluminescent method for determining the quality of raw materials for tea products and packaged teas available in wholesale and retail trade

The assessment is performed based on intensity and nature of the ultra-weak chemiluminescent glow using the original technique, where calculations are made using a 4-parameter equation (see Fig. 2):

1/t (Vi) = 3.42*10-3 + 1.36*I1 + 2.27*10-1*I2 + 1.24*10-2*t1 + 3.74*10-3 t2

Fig. 2. The principle for determining the quality of tea

The results were obtained using the original supersensitive chemiluminescent (CL) device (Fig. 3).

Fig. 3. Supersensitive CL device

To continue this research we need to make a CL device or purchase its commercial counterpart.

The method is patented. Lebedkova O., Kanibolotska L., Shendryk O. Method for chemiluminescent determination of polyphenolic compounds of aqueous tea extracts. Patent of Ukraine No. 75488 dated December 10, 2012.


Application area

Production and sales of tea products.

6.3 Bicatalytic oxidoreductase-based systems to be used for “green” free radical oxidation and polymerization processes

The project was launched in 2016. It aims to develop new ecological radical processes of oxidative modification of natural and synthetic substances using enzyme-organic catalysts and “green” oxidants – molecular oxygen and hydrogen peroxide (see Fig. 4). The systems under study will be tested during the oxidation of substrates derived from renewable vegetable raw materials (lignin model compounds, terpenes, furan derivatives) in order to obtain valuable oxygen-containing compounds and realize complex oxidative degradation of wastewater pollutants such as natural and synthetic dyes, antibiotics, pesticides.

Fig. 4. Schematic diagram for creation of self-reproducing cyclic biocatalytic laccase-based systems.

The efficiency of the system was confirmed experimentally. The results are published (see Fig. 5).

Fig. 5. Results on decolorization of synthetic dyes were published in the journal: Chemistryselect 2019, 4, 3905-3913.


Application area

New environmental and resource-regenerating sustainable biotechnological processes


Available equipment

The research is carried out using the methods of gas chromatography-mass spectrometry and high-performance liquid chromatography-mass spectrometry, NMR, IR-Fourier and UV-VIS spectroscopy, quantum chemical calculations. There are UV-VIS spectrophotometers and an atomic absorption spectrometer (see Fig. 6) available at the faculty. Quantum chemical calculations are performed using open-source GAMESS-US. It is installed on the computing cluster, located on the University’s server. Access to other equipment is provided by the L.M. Lytvynenko Institute of Physical-Organic Chemistry and Coal Chemistry of the NASU and Vinnytsia Research Experimental Forensic Center of the Ministry of Internal Affairs of Ukraine.

Fig. 6. UV-VIS spectrophotometer Specord S50 and atomic absorption spectrometer AAS Vario 6, manufactured by Analytikjena, Germany.


Important publications

Publications by Oleksandr Shendryk, the head of scientific school, are shown on fig.7 – 39 articles in Scopus, 62 – in WoS, 96 – in Google Scholar.

Fig. 7. O. Shendryk’s profiles in international scientometric databases

Scopus author profile: https://www.scopus.com/authid/detail.uri?authorId=6603500198

ORCID: https://orcid.org/0000-0002-5518-1019


Contacts:

Oleksandr Shendryk

Tel. +(38)-097-716-0331, E-mail: o.shendrik@donnu.edu.ua