Dehalogenation of persistent halogenated organic compounds: A review of computational studies and quantitative structure–property relationships

Luo, Jing; Hu, Jiwei; Wei, Xionghui; Li, Lingyun

doi:10.1016/j.chemosphere.2015.02.013

Cited by 43 publications

(19 citation statements)

References 181 publications

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“…In the recent years, theoretical investigations have been extensively performed to provide important information about reaction pathways [15][16][17][18]. DFT-based reactivity descriptors, such as Fukui functions and local softness, [19] were widely used to predict the most probable reactive sites without actual calculations of the corresponding potential energy surface [20,21].…”

Section: Introductionmentioning

confidence: 99%

Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study

Dostanić

Lončarević

Zlatar

et al. 2016

Journal of Hazardous Materials

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A series of arylazo pyridone dyes was synthesized by changing the type of the substituent group in the diazo moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The structural and electronic properties of the investigated dyes was calculated at the M062X/6-31+G(d,p) level of theory. The observed good linear correlations between atomic charges and Hammett σp constants provided a basis to discuss the transmission of electronic substituent effects through a dye framework. The reactivity of synthesized dyes was tested through their decolorization efficiency in TiO2 photocatalytic system (Degussa P-25). Quantitative structure-activity relationship analysis revealed a strong correlation between reactivity of investigated dyes and Hammett substituent constants. The reaction was facilitated by electron-withdrawing groups, and retarded by electron-donating ones. Quantum mechanical calculations was used in order to describe the mechanism of the photocatalytic oxidation reactions of investigated dyes and interpret their reactivities within the framework of the Density Functional Theory (DFT). According to DFT based reactivity descriptors, i.e. Fukui functions and local softness, the active site moves from azo nitrogen atom linked to benzene ring to pyridone carbon atom linked to azo bond, going from dyes with electron-donating groups to dyes with electron-withdrawing groups.

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Section: Introductionmentioning

confidence: 99%

Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study

Dostanić

Lončarević

Zlatar

et al. 2016

Journal of Hazardous Materials

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“…The earlier studies have confirmed that the structural parameters for PBDE congeners calculated at the B3LYP/6-31+G(d) level are reliable [ 22 , 42 , 45 ]. Average absolute errors between the calculated values and experimental values of bond length for the neutral persistent halogenated organic compounds (HOCs) are less than 0.04 Å [ 25 ]. Zhao et al reported that the C–Br bond lengths from B3LYP/6-31+G(d) are 0.01 Å greater than the experimental values [ 42 ].…”

Section: Resultsmentioning

confidence: 99%

“…PBDE congeners are conformationally flexible, thus the conversion of stable conformers can occur readily with low energy barriers [ 25 ]. The ideal way to identify the true energy minimum is to calculate the potential energy surface (PES), because the interconversion of the stable conformers for PBDEs can occur with low energy barriers [ 25 , 27 ]. The relationships between the total energy and the C–Br bond lengths of the anionic species for BDE-5, BDE-22, BDE-47 were analyzed using the PES, as shown in Figures S1–S3 .…”

Section: Resultsmentioning

confidence: 99%

“…Many researchers simulated structures and studied the properties of PBDEs using quantum chemical methods [ 21 , 22 , 23 , 24 , 25 ]. Most of their theoretical results are consistent with the experimental data.…”

Section: Introductionmentioning

confidence: 99%

“…The previous studies reported that the results of DFT models are better than those of semiempirical methods [ 27 ]. In comparison with the X-ray crystal structure, the observed order of precision was DFT > PM3 = AM1 > MNDO for 2,3,7,8-TCDD [ 25 , 28 ].…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers

Shi

et al. 2016

IJMS

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The B3LYP/6-311+G(d)-SDD method, which considers the relativistic effect of bromine, was adopted for the calculations of the selected polybrominated diphenyl ethers (PBDEs) in the present study, in which the B3LYP/6-311+G(d) method was also applied. The calculated values and experimental data for structural parameters of the selected PBDEs were compared to find the suitable theoretical methods for their structural optimization. The results show that the B3LYP/6-311+G(d) method can give the better results (with the root mean square errors (RMSEs) of 0.0268 for the C–Br bond and 0.0161 for the C–O bond) than the B3LYP/6-311+G(d)-SDD method. Then, the B3LYP/6-311+G(d) method was applied to predict the structures for the other selected PBDEs (both neutral and anionic species). The lowest unoccupied molecular orbital (LUMO) and the electron affinity are of a close relationship. The electron affinities (vertical electron affinity and adiabatic electron affinity) were discussed to study their electron capture abilities. To better estimate the conversion of configuration for PBDEs, the configuration transition states for BDE-5, BDE-22 and BDE-47 were calculated at the B3LYP/ 6-311+G(d) level in both gas phase and solution. The possible debromination pathway for BDE-22 were also studied, which have bromine substituents on two phenyl rings and the bromine on meta-position prefers to depart from the phenyl ring. The reaction profile of the electron-induced reductive debromination for BDE-22 were also shown in order to study its degradation mechanism.

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Quantitative Structure-Activity Modelling of Toxic Compounds

Satpathy¹

2018

Environmental Chemistry for a Sustainable World

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Dehalogenation of persistent halogenated organic compounds: A review of computational studies and quantitative structure–property relationships

Cited by 43 publications

References 181 publications

Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study

Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study

Theoretical Studies on Structures, Properties and Dominant Debromination Pathways for Selected Polybrominated Diphenyl Ethers

Quantitative Structure-Activity Modelling of Toxic Compounds

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