International Research Fellowship Program: Using Computational Chemistry to Assess Reactivity of Contaminants in Surface Waters

国际研究奖学金计划：利用计算化学评估地表水中污染物的反应性

• 批准号: 0852999
• 负责人: Jennifer Guerard
• 金额: $ 13.75万
• 依托单位: Guerard Jennifer
• 依托单位国家: 美国
• 项目类别: Fellowship Award
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-01-01 至 2011-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0852999&HistoricalAwards=false
• 关键词: International; Research; Fellowship; Program; Using

0852999GuerardThe International Research Fellowship Program enables U.S. scientists and engineers to conduct nine to twenty-four months of research abroad. The program's awards provide opportunities for joint research, and the use of unique or complementary facilities, expertise and experimental conditions abroad.This award will support a twenty-four-month research fellowship by Dr. Jennifer J. Guerard to work with Dr. Silvio Canonica at the Swiss Federal Institute of Aquatic Science and Technology and with Dr. J. Samuel Arey at Ecole Polytech Federale in Switzerland.Organic contaminants in natural waters have the potential to be degraded by a variety of reaction pathways. Assessment of the fate and impact of these contaminants often hinges heavily on quantification of the principal degradation processes responsible for their removal or transformation into other compounds. It is increasingly understood that light-induced processes play a significant and complicated role in the degradation of many aquatic contaminants. This project will use state of the art computational methods to predict the single electron oxidation potentials and reaction kinetics of compounds that can undergo electron transfer upon photo excitation to the triplet excited state (sulfonamides and phenylurea herbicides) and analogues for dissolved organic matter (electron-rich phenols and substituted anilines), a heterogeneous substance ubiquitous in all natural surface waters. A novel computational approach will calculate free energy of ionization in water solutions to provide reliable computation of aqueous one-electron oxidation free energies of organic contaminants to within 1-2 kcal/mol error. The Rehm-Weller model will be applied to describe the kinetics of oxidation by triplet-excited DOM. These model developments will allow us to better assess the significance of 3DOM* for the environmental degradation of a wider range of target pollutants in aquatic systems.

0852999 Guerard国际研究奖学金计划使美国科学家和工程师能够在国外进行9到24个月的研究。 该计划的奖项提供了联合研究的机会，以及使用独特或互补的设施，专业知识和国外的实验条件。这个奖项将支持一个二十四-Jennifer J.盖拉尔博士获得了一个月的研究奖学金，与瑞士联邦水产科学技术研究所的Silvio Canonica博士和瑞士联邦理工学院的J. Samuel Arey博士一起工作。沃茨具有通过多种反应途径降解的潜力。对这些污染物的最终结果和影响的评估往往在很大程度上取决于对导致其去除或转化为其他化合物的主要降解过程的量化。人们越来越认识到，光诱导过程在许多水生污染物的降解中起着重要而复杂的作用。该项目将使用最先进的计算方法预测化合物的单电子氧化电位和反应动力学，这些化合物可在光激发时发生电子转移到三重激发态（磺胺和苯基脲除草剂），以及溶解有机物的类似物（富电子苯酚和取代苯胺），这是一种在所有天然表面沃茨中普遍存在的异质物质。一种新的计算方法将计算水溶液中的电离自由能，以提供有机污染物的水单电子氧化自由能的可靠计算，误差在1-2千卡/摩尔内。将采用Weller模型描述三重态DOM的氧化动力学。这些模型的开发将使我们能够更好地评估3DOM* 对水生系统中更广泛的目标污染物的环境降解的重要性。