Degradation Mechanisms of 4,7-Dihydroxycoumarin Derivatives in Advanced Oxidation Processes: Experimental and Kinetic DFT Study

Žiko Milanović, Dušan Dimić (), Erik Klein, Monika Biela, Vladimír Lukeš, Milan Žižić, Edina Avdović, Drago Bešlo, Radiša Vojinović, Jasmina Dimitrić Marković and Zoran Marković ()
Additional contact information
Žiko Milanović: Department of Science, Institute for Information Technologies, University of Kragujevac, Jovana Cvijića bb, 34000 Kragujevac, Serbia
Dušan Dimić: Faculty of Physical Chemistry, University of Belgrade, 12−16 Studentski Trg, 11000 Belgrade, Serbia
Erik Klein: Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37 Bratislava, Slovakia
Monika Biela: Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37 Bratislava, Slovakia
Vladimír Lukeš: Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37 Bratislava, Slovakia
Milan Žižić: Life Sciences Department, Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade, Serbia
Edina Avdović: Department of Science, Institute for Information Technologies, University of Kragujevac, Jovana Cvijića bb, 34000 Kragujevac, Serbia
Drago Bešlo: Department of Agroecology and Environmental Protection, Faculty of Agrobiotechnical Sciences Osijek, University Josip Juraj Strossmayer Osijek, Vladimir Prelog 1, 31000 Osijek, Croatia
Radiša Vojinović: Faculty of Medical Sciences, University of Kragujevac, Svetozara Markovića 69, 34000 Kragujevc, Serbia
Jasmina Dimitrić Marković: Faculty of Physical Chemistry, University of Belgrade, 12−16 Studentski Trg, 11000 Belgrade, Serbia
Zoran Marković: Department of Science, Institute for Information Technologies, University of Kragujevac, Jovana Cvijića bb, 34000 Kragujevac, Serbia

IJERPH, 2023, vol. 20, issue 3, 1-19

Abstract: Coumarins represent a broad class of compounds with pronounced pharmacological properties and therapeutic potential. The pursuit of the commercialization of these compounds requires the establishment of controlled and highly efficient degradation processes, such as advanced oxidation processes (AOPs). Application of this methodology necessitates a comprehensive understanding of the degradation mechanisms of these compounds. For this reason, possible reaction routes between HO • and recently synthesized aminophenol 4,7-dihydroxycoumarin derivatives, as model systems, were examined using electron paramagnetic resonance (EPR) spectroscopy and a quantum mechanical approach (a QM-ORSA methodology) based on density functional theory (DFT). The EPR results indicated that all compounds had significantly reduced amounts of HO • radicals present in the reaction system under physiological conditions. The kinetic DFT study showed that all investigated compounds reacted with HO • via HAT/PCET and SPLET mechanisms. The estimated overall rate constants ( k overall ) correlated with the EPR results satisfactorily. Unlike HO • radicals, the newly formed radicals did not show (or showed negligible) activity towards biomolecule models representing biological targets. Inactivation of the formed radical species through the synergistic action of O 2 /NO x or the subsequent reaction with HO • was thermodynamically favored. The ecotoxicity assessment of the starting compounds and oxidation products, formed in multistage reactions with O 2 /NO x and HO • , indicated that the formed products showed lower acute and chronic toxicity effects on aquatic organisms than the starting compounds, which is a prerequisite for the application of AOPs procedures in the degradation of compounds.

Keywords: 4,7-dihydroxycoumarin; DFT; EPR; AOPs; radical scavenging; hydroxyl radical; QM?ORSA (search for similar items in EconPapers)
JEL-codes: I I1 I3 Q Q5 (search for similar items in EconPapers)
Date: 2023
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