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

Publisher: MDPI Country of Publication: Switzerland NLM ID: 101238455 Publication Model: Electronic Cited Medium: Internet ISSN: 1660-4601 (Electronic) Linking ISSN: 16604601 NLM ISO Abbreviation: Int J Environ Res Public Health Subsets: MEDLINE

Original Publication: Basel : MDPI, c2004-

Hydroxyl Radical* ; Water Pollutants, Chemical*/analysis; Oxidation-Reduction ; Aquatic Organisms ; Kinetics

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 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.

Sci Total Environ. 2019 Oct 1;685:729-740. (PMID: 31234135)
J Chem Phys. 2005 Oct 15;123(15):154101. (PMID: 16252936)
Environ Pollut. 2012 Jun;165:182-92. (PMID: 22285063)
Comput Biol Chem. 2020 Feb;84:107170. (PMID: 31810852)
Cutan Ocul Toxicol. 2007;26(1):1-13. (PMID: 17464744)
Int J Mol Sci. 2021 Dec 09;22(24):. (PMID: 34948070)
Sci Rep. 2015 Aug 28;5:13544. (PMID: 26315062)
J Chem Theory Comput. 2005 Jan;1(1):70-7. (PMID: 26641117)
Chemosphere. 2008 May;71(10):1986-95. (PMID: 18262586)
J Ethnopharmacol. 2000 Nov;73(1-2):299-305. (PMID: 11025169)
J Phys Chem A. 2019 Aug 29;123(34):7499-7506. (PMID: 31385701)
Food Chem. 2019 Apr 25;278:469-475. (PMID: 30583398)
Bioorg Med Chem Lett. 2019 Jul 15;29(14):1749-1755. (PMID: 31104994)
ALTEX. 2001;18(2):147-8. (PMID: 11378689)
Spectrochim Acta A Mol Biomol Spectrosc. 2019 Jan 5;206:421-429. (PMID: 30172238)
Eur J Med Chem. 2019 Nov 1;181:111587. (PMID: 31404864)
Br J Clin Pharmacol. 2001 May;51(5):429-35. (PMID: 11422000)
Heliyon. 2020 Jan 27;6(1):e03217. (PMID: 32042967)
J Comput Chem. 2014 Oct 30;35(28):2019-26. (PMID: 25142611)
Curr Pharm Des. 2004;10(30):3813-33. (PMID: 15579073)
Environ Sci Pollut Res Int. 2014;21(11):7194-203. (PMID: 24622989)
Int J Environ Res Public Health. 2019 Dec 25;17(1):. (PMID: 31881722)
Free Radic Biol Med. 2009 Apr 15;46(8):1049-57. (PMID: 19185609)
Antioxidants (Basel). 2021 Aug 18;10(8):. (PMID: 34439551)
J Comput Chem. 2013 Oct 30;34(28):2430-45. (PMID: 23939817)
Free Radic Biol Med. 2002 Feb 1;32(3):228-32. (PMID: 11827748)
Appl Environ Microbiol. 2017 Jun 16;83(13):. (PMID: 28432098)
RSC Adv. 2020 Nov 27;10(71):43262-43272. (PMID: 35519718)
Eur J Biochem. 2000 Sep;267(18):5687-92. (PMID: 10971578)
Chem Res Toxicol. 2017 Jun 19;30(6):1286-1301. (PMID: 28475314)
Environ Sci Process Impacts. 2014 May;16(6):1182-203. (PMID: 24549240)
Eur J Med Chem. 2015 Aug 28;101:476-95. (PMID: 26188907)
Phys Chem Chem Phys. 2011 Apr 21;13(15):7178-88. (PMID: 21409256)
Br J Pharmacol Chemother. 1963 Feb;20(1):29-35. (PMID: 19108174)
J Phys Chem B. 2018 Jun 14;122(23):6198-6214. (PMID: 29771524)
Int J Mol Sci. 2022 Jan 01;23(1):. (PMID: 35008914)

Keywords: 4,7-dihydroxycoumarin; AOPs; DFT; EPR; QM−ORSA; hydroxyl radical; radical scavenging

3352-57-6 (Hydroxyl Radical)
0 (Water Pollutants, Chemical)

Date Created: 20230211 Date Completed: 20230214 Latest Revision: 20230318

20250114

PMC9916318

10.3390/ijerph20032046

36767412