Aqueous degradation of 6-APA by hydroxyl radical: a theoretical study

Aydogdu, Seyda; Hatipoğlu, Arzu

doi:10.1007/s00894-023-05636-y

Cited by 4 publications

(2 citation statements)

References 44 publications

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“…Secondly, GaussView 5.0.8 software was used to draw the structures of reactants and products in the primary degradation pathways of 16 commercial FQs. Finally, based on density functional theory at the M062X/6-31G(d) basis set level [ 21 ], the Gaussian software was used to calculate the ease of primary degradation reactions of 16 FQ molecules in AOPs (characterized by the bond dissociation energy (kJ/mol) in the advanced oxidation degradation pathway). The lower the bond dissociation energy value, the easier the internal chemical bonds of the FQ molecules break, indicating higher degradability of the FQ molecules in the AOPs [ 22 ].…”

Section: Methodsmentioning

confidence: 99%

Identification and Mechanistic Analysis of Toxic Degradation Products in the Advanced Oxidation Pathways of Fluoroquinolone Antibiotics

Sun,

Wang,

et al. 2024

Toxics

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The degradation of fluoroquinolones (FQs) via advanced oxidation processes (AOPs) is a promising avenue, yet the complete mineralization of certain FQ molecules remains elusive, raising concerns about the formation of toxic by-products. This study delineates five primary AOP degradation pathways for 16 commercially available FQ molecules, inferred from existing literature. Density functional theory (DFT) was employed to calculate the bond dissociation energies within these pathways to elucidate the correlation between bond strength and molecular architecture. Subsequently, Comparative Molecular Similarity Index Analysis (CoMSIA) models were constructed for various degradation reactions, including piperazine ring cleavage, defluorination, hydroxylation, and piperazine ring hydroxylation. Three-dimensional contour maps generated from these models provide a deeper understanding of the interplay between FQ molecular structure and bond dissociation energy. Furthermore, toxicity predictions for 16 FQ molecules and their advanced oxidation intermediates, conducted using VEGA 1.2.3 software, indicate that degradation products from pathways P2 and P5 pose a heightened health risk relative to their parent compounds. Furthermore, the application of the Multwfn program to compute the Fukui function for FQ molecules discerns the disparity in degradation propensities, highlighting that N atoms with higher f0 values can augment the likelihood of piperazine ring cleavage. HOMO-LUMO distribution diagrams further confirm that methoxy substitution at the 1-position leads to a dilution of HOMOs on the piperazine ring and an increased energy gap for free radical reactions, diminishing the reactivity with hydroxyl radicals. This study elucidates the pivotal role of structural characteristics in FQ antibiotics for their degradation efficiency within AOPs and unveils the underlying mechanisms of bond dissociation energy disparities. The toxicity parameter predictions for FQ molecules and their intermediates offer unique perspectives and theoretical underpinnings for mitigating the use of high-risk FQs and for devising targeted degradation strategies to circumvent the generation of toxic intermediates in AOPs through molecular structure optimization.

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Section: Methodsmentioning

confidence: 99%

Identification and Mechanistic Analysis of Toxic Degradation Products in the Advanced Oxidation Pathways of Fluoroquinolone Antibiotics

Sun,

Wang,

et al. 2024

Toxics

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show abstract

“…37 Nevertheless, many studies focused on As(III) removal efficiencies or coupling of •OH production and As(III) oxidation. [38][39][40] However, the effects of the dynamic interaction of solid phase Fe(II) and As(III) with DO on As removal remain unclear.…”

Section: Introductionmentioning

confidence: 99%