TY  - JOUR
AU  - Milanović, Žiko
AU  - Dimić, Dušan
AU  - Klein, Erik
AU  - Biela, Monika
AU  - Lukeš, Vladimir
AU  - Žižić, Milan
AU  - Avdović, Edina
AU  - Bešlo, Drago
AU  - Vojinović, Radiša
AU  - Dimitrić-Marković, Jasmina
AU  - Marković, Zoran
PY  - 2023
UR  - http://rimsi.imsi.bg.ac.rs/handle/123456789/2111
AB  - 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 (koverall) 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 O2/NOx or the subsequent reaction with HO• was thermodynamically favored. The ecotoxicity assessment of the starting compounds and oxidation products, formed in multistage reactions with O2/NOx 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.
PB  - MDPI, Basel, Switzerland
T2  - International Jornal of Environmental Research and Public Health
T1  - Derivatives in Advanced Oxidation Processes: Experimental and Kinetic DFT Stud
EP  - 2064
SP  - 2046
VL  - 20
DO  - 10.3390/ijerph20032046
ER  - 

@article{
author = "Milanović, Žiko and Dimić, Dušan and Klein, Erik and Biela, Monika and Lukeš, Vladimir and Žižić, Milan and Avdović, Edina and Bešlo, Drago and Vojinović, Radiša and Dimitrić-Marković, Jasmina and Marković, Zoran",
year = "2023",
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 (koverall) 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 O2/NOx or the subsequent reaction with HO• was thermodynamically favored. The ecotoxicity assessment of the starting compounds and oxidation products, formed in multistage reactions with O2/NOx 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.",
publisher = "MDPI, Basel, Switzerland",
journal = "International Jornal of Environmental Research and Public Health",
title = "Derivatives in Advanced Oxidation Processes: Experimental and Kinetic DFT Stud",
pages = "2064-2046",
volume = "20",
doi = "10.3390/ijerph20032046"
}

Milanović, Ž., Dimić, D., Klein, E., Biela, M., Lukeš, V., Žižić, M., Avdović, E., Bešlo, D., Vojinović, R., Dimitrić-Marković, J.,& Marković, Z.. (2023). Derivatives in Advanced Oxidation Processes: Experimental and Kinetic DFT Stud. in International Jornal of Environmental Research and Public Health
MDPI, Basel, Switzerland., 20, 2046-2064.
https://doi.org/10.3390/ijerph20032046

Milanović Ž, Dimić D, Klein E, Biela M, Lukeš V, Žižić M, Avdović E, Bešlo D, Vojinović R, Dimitrić-Marković J, Marković Z. Derivatives in Advanced Oxidation Processes: Experimental and Kinetic DFT Stud. in International Jornal of Environmental Research and Public Health. 2023;20:2046-2064.
doi:10.3390/ijerph20032046 .

Milanović, Žiko, Dimić, Dušan, Klein, Erik, Biela, Monika, Lukeš, Vladimir, Žižić, Milan, Avdović, Edina, Bešlo, Drago, Vojinović, Radiša, Dimitrić-Marković, Jasmina, Marković, Zoran, "Derivatives in Advanced Oxidation Processes: Experimental and Kinetic DFT Stud" in International Jornal of Environmental Research and Public Health, 20 (2023):2046-2064,
https://doi.org/10.3390/ijerph20032046 . .