Tags

Type your tag names separated by a space and hit enter

Quantitative structure-activity relationship for the oxidation of aromatic organic contaminants in water by TAML/H2O2.
Water Res. 2018 09 01; 140:354-363.WR

Abstract

Tetra-amido macrocyclic ligand (TAML) activator is a functional analog of peroxidase enzymes, which activates hydrogen peroxide (H2O2) to form high valence iron-oxo complexes that selectively degrade persistent aromatic organic contaminants (ACs) in water. Here, we develop quantitative structure-activity relationship (QSAR) models based on measured pseudo first-order kinetic rate coefficients (kobs) of 29 ACs (e.g., phenols and pharmaceuticals) oxidized by TAML/H2O2 at neutral and basic pH values to gain mechanistic insight on the selectivity and pH dependence of TAML/H2O2 systems. These QSAR models infer that electron donating ability (EHOMO) is the most important AC characteristic for TAML/H2O2 oxidation, pointing to a rate-limiting single-electron transfer (SET) mechanism. Oxidation rates at pH 7 also depend on AC reactive indices such as fmin- and qH+, which respectively represent propensity for electrophilic attack and the most positive net atomic charge on hydrogen atoms. At pH 10, TAML/H2O2 is more reactive towards ACs with a lower hydrogen to carbon atoms ratio (#H:C), suggesting the significance of hydrogen atom abstraction. In addition, lnkobs of 14 monosubstituted phenols is negatively correlated with Hammett constants (σ) and exhibits similar sensitivity to substituent effects as horseradish peroxidase. Although accurately predicting degradation rates of specific ACs in complex wastewater matrices could be difficult, these QSAR models are statistically robust and help predict both relative degradability and reaction mechanism for TAML/H2O2-based treatment processes.

Links

Publisher Full Text (DOI)

Authors+Show Affiliations

Su H
School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Yu C
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Zhou Y
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Gong L
School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China.
Li Q
Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005, United States.
Alvarez PJJ
Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005, United States.
Long M
School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China; Key Laboratory for Thin Film and Microfabrication Technology (Ministry of Education), Shanghai Jiao Tong University, Shanghai 200240, China. Electronic address: long_mc@sjtu.edu.cn.

MeSH

CarbonHydrocarbons, AromaticHydrogen PeroxideHydrogen-Ion ConcentrationKineticsLigandsOxidation-ReductionQuantitative Structure-Activity RelationshipStatic ElectricityWastewaterWaterWater Pollutants, Chemical

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

29751317

Citation

Su, Hanrui, et al. "Quantitative Structure-activity Relationship for the Oxidation of Aromatic Organic Contaminants in Water By TAML/H2O2." Water Research, vol. 140, 2018, pp. 354-363.
Su H, Yu C, Zhou Y, et al. Quantitative structure-activity relationship for the oxidation of aromatic organic contaminants in water by TAML/H2O2. Water Res. 2018;140:354-363.
Su, H., Yu, C., Zhou, Y., Gong, L., Li, Q., Alvarez, P. J. J., & Long, M. (2018). Quantitative structure-activity relationship for the oxidation of aromatic organic contaminants in water by TAML/H2O2. Water Research, 140, 354-363. https://doi.org/10.1016/j.watres.2018.04.062
Su H, et al. Quantitative Structure-activity Relationship for the Oxidation of Aromatic Organic Contaminants in Water By TAML/H2O2. Water Res. 2018 09 1;140:354-363. PubMed PMID: 29751317.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Quantitative structure-activity relationship for the oxidation of aromatic organic contaminants in water by TAML/H2O2. AU - Su,Hanrui, AU - Yu,Chunyang, AU - Zhou,Yongfeng, AU - Gong,Lidong, AU - Li,Qilin, AU - Alvarez,Pedro J J, AU - Long,Mingce, Y1 - 2018/05/02/ PY - 2018/01/30/received PY - 2018/04/23/revised PY - 2018/04/27/accepted PY - 2018/5/12/pubmed PY - 2018/10/9/medline PY - 2018/5/12/entrez KW - Aromatic organic contaminants KW - Oxidation KW - Quantitative structure–activity relationship KW - TAML SP - 354 EP - 363 JF - Water research JO - Water Res VL - 140 N2 - Tetra-amido macrocyclic ligand (TAML) activator is a functional analog of peroxidase enzymes, which activates hydrogen peroxide (H2O2) to form high valence iron-oxo complexes that selectively degrade persistent aromatic organic contaminants (ACs) in water. Here, we develop quantitative structure-activity relationship (QSAR) models based on measured pseudo first-order kinetic rate coefficients (kobs) of 29 ACs (e.g., phenols and pharmaceuticals) oxidized by TAML/H2O2 at neutral and basic pH values to gain mechanistic insight on the selectivity and pH dependence of TAML/H2O2 systems. These QSAR models infer that electron donating ability (EHOMO) is the most important AC characteristic for TAML/H2O2 oxidation, pointing to a rate-limiting single-electron transfer (SET) mechanism. Oxidation rates at pH 7 also depend on AC reactive indices such as fmin- and qH+, which respectively represent propensity for electrophilic attack and the most positive net atomic charge on hydrogen atoms. At pH 10, TAML/H2O2 is more reactive towards ACs with a lower hydrogen to carbon atoms ratio (#H:C), suggesting the significance of hydrogen atom abstraction. In addition, lnkobs of 14 monosubstituted phenols is negatively correlated with Hammett constants (σ) and exhibits similar sensitivity to substituent effects as horseradish peroxidase. Although accurately predicting degradation rates of specific ACs in complex wastewater matrices could be difficult, these QSAR models are statistically robust and help predict both relative degradability and reaction mechanism for TAML/H2O2-based treatment processes. SN - 1879-2448 UR - https://www.unboundmedicine.com/medline/citation/29751317/Quantitative_structure_activity_relationship_for_the_oxidation_of_aromatic_organic_contaminants_in_water_by_TAML/H2O2_ DB - PRIME DP - Unbound Medicine ER -