{"title":"水介质中羟基自由基与喹啉草醚和喹乙醇除草剂反应的动力学和机理的理论研究","authors":"Hari P. Upadhyaya","doi":"10.1002/qua.27430","DOIUrl":null,"url":null,"abstract":"<p>The kinetic and mechanistic studies for the reaction of hydroxyl radical with two quinoline based herbicides, namely, quinclorac and quinmerac has been performed using various computational methods in aqueous media. Geometry optimizations were performed using Density Functional Theory (DFT) methods including water as the solvent. Local reactivity parameters of these herbicides towards the <sup>•</sup>OH radical are predicted using condensed Fukui function. Single point energies of various species were calculated using double hybrid method, namely, B2PLYP–D for better accuracy. The pK<sub>a</sub> values for these acid based herbicides allow them to exist in deprotonated form in aqueous condition. Hence, the calculations are also performed for the deprotonated or the anionic form apart from the neutral species. Individual rate coefficients for <sup>•</sup>OH radical addition reaction with each carbon atoms were evaluated using conventional transition state theory using one–dimensional tunneling corrections. The solvent effect on reaction is implemented through Collins–Kimball formulations. Both the approaches, namely, the Fukui index and individual rate constant determination confirms that the most reactive site for the <sup>•</sup>OH radical addition in these two herbicide is the carbon atom attached to the <span></span>COOH group. The total rate constant for the <sup>•</sup>OH radical reaction with both neutral and anionic forms of these two herbicides are relatively high and equal to its diffusion-limit value. Evaluation of the ecotoxicities of the parent herbicides and their OH adducts is estimated using the structure–activity relationship concept.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"124 11","pages":""},"PeriodicalIF":2.3000,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.27430","citationCount":"0","resultStr":"{\"title\":\"Theoretical studies on the kinetics and mechanism of hydroxyl radical reaction with quinclorac and quinmerac herbicides in aqueous media\",\"authors\":\"Hari P. Upadhyaya\",\"doi\":\"10.1002/qua.27430\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The kinetic and mechanistic studies for the reaction of hydroxyl radical with two quinoline based herbicides, namely, quinclorac and quinmerac has been performed using various computational methods in aqueous media. Geometry optimizations were performed using Density Functional Theory (DFT) methods including water as the solvent. Local reactivity parameters of these herbicides towards the <sup>•</sup>OH radical are predicted using condensed Fukui function. Single point energies of various species were calculated using double hybrid method, namely, B2PLYP–D for better accuracy. The pK<sub>a</sub> values for these acid based herbicides allow them to exist in deprotonated form in aqueous condition. Hence, the calculations are also performed for the deprotonated or the anionic form apart from the neutral species. Individual rate coefficients for <sup>•</sup>OH radical addition reaction with each carbon atoms were evaluated using conventional transition state theory using one–dimensional tunneling corrections. The solvent effect on reaction is implemented through Collins–Kimball formulations. Both the approaches, namely, the Fukui index and individual rate constant determination confirms that the most reactive site for the <sup>•</sup>OH radical addition in these two herbicide is the carbon atom attached to the <span></span>COOH group. The total rate constant for the <sup>•</sup>OH radical reaction with both neutral and anionic forms of these two herbicides are relatively high and equal to its diffusion-limit value. Evaluation of the ecotoxicities of the parent herbicides and their OH adducts is estimated using the structure–activity relationship concept.</p>\",\"PeriodicalId\":182,\"journal\":{\"name\":\"International Journal of Quantum Chemistry\",\"volume\":\"124 11\",\"pages\":\"\"},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2024-06-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.27430\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Quantum Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/qua.27430\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Quantum Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/qua.27430","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Theoretical studies on the kinetics and mechanism of hydroxyl radical reaction with quinclorac and quinmerac herbicides in aqueous media
The kinetic and mechanistic studies for the reaction of hydroxyl radical with two quinoline based herbicides, namely, quinclorac and quinmerac has been performed using various computational methods in aqueous media. Geometry optimizations were performed using Density Functional Theory (DFT) methods including water as the solvent. Local reactivity parameters of these herbicides towards the •OH radical are predicted using condensed Fukui function. Single point energies of various species were calculated using double hybrid method, namely, B2PLYP–D for better accuracy. The pKa values for these acid based herbicides allow them to exist in deprotonated form in aqueous condition. Hence, the calculations are also performed for the deprotonated or the anionic form apart from the neutral species. Individual rate coefficients for •OH radical addition reaction with each carbon atoms were evaluated using conventional transition state theory using one–dimensional tunneling corrections. The solvent effect on reaction is implemented through Collins–Kimball formulations. Both the approaches, namely, the Fukui index and individual rate constant determination confirms that the most reactive site for the •OH radical addition in these two herbicide is the carbon atom attached to the COOH group. The total rate constant for the •OH radical reaction with both neutral and anionic forms of these two herbicides are relatively high and equal to its diffusion-limit value. Evaluation of the ecotoxicities of the parent herbicides and their OH adducts is estimated using the structure–activity relationship concept.
期刊介绍:
Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.