BRIGE: Redox Noninnocent Ligands - Application to the Reductive Transformation of Veterinary Pharmaceuticals Containing Carbon-Nitrogen Double Bonds

BRIGE：氧化还原非无害配体——在含碳氮双键兽药还原转化中的应用

• 批准号: 1125713
• 负责人: Huichun Zhang
• 金额: $ 17.5万
• 依托单位: Temple University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-10-01 至 2014-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1125713&HistoricalAwards=false
• 关键词: BRIGE; Redox; Noninnocent; Ligands; Application; BRIGE; Redox; Noninnocent; Ligands; Application

PI: Zhang, Huichun J.Proposal Number: 1125713Research Objectives and Approach: Redox noninnocent ligands (RNILs) have been extensively studied by inorganic chemists on the redox-nature of the complexes formed with many transition metals. Yet, little information is available regarding the redox activity of RNILs, particularly as it pertains to the fate and transformation of emerging contaminants. On the other hand, soluble Fe(II) complexes with organic cathechol- and thiol-ligands, considered only as redox ligands in the literature, have been recently recognized for their ability to reduce a number of organic contaminants. Given the ubiquitous presence and fast redox reactivity of Fe(II) complexes in the environment, this lack of understanding of the nature of the ligands (., redox innocent versus noninnocent) will significantly prevent accurate estimation of the fate and transformation of emerging contaminants in reducing environments. For this reason, the proposed study will apply the concept of redox noninnocent ligands to the overall reductive transformation of a group of veterinary pharmaceuticals (VPs) containing carbon-nitrogen double bonds; the role and transformation of both the VPs and RNILs will be investigated from mechanistic perspective. Based on our preliminary results and the literature, we hypothesize that this group of VPs will undergo fast redox reaction with Fe(II) complexes with a number of RNILs including -catecholate, o'diaminophenylene, o-aminophenolate, o-dithiolene, and o-aminothiolate ligands. To test this hypothesis, a series of experiments have been structured (1) to illustrate the redox noninnocent nature of the complexes, (2) to determine the reaction kinetics and mechanism of the selected VPs and structurally related model compounds, and (3) to develop quantitative structural-activity relationships (QSARs) that can be used to predict reductive transformation of other structurally similar contaminants. Methodologically, the study will rely on diverse methods including but not limited to cyclic voltammatry, FTIR, HPLC, LC-MS-MS, NMR, and UV-visible measurements coupled with analytical determinations. Intellectual Merit: This study is one of the first to examine the redox noninnocent behavior of environmentally relevant Fe(II) complexes. Advanced experimental and interpretative methods will be used to generate knowledge that is critical for accurate modeling of environmental fates of an important group of VPs containing carbon-nitrogen double bonds, which are also a common structural moiety for many other emerging contaminants such as human pharmaceutical and personal care products and pesticides. The intellectual merit of this project is based on: 1) fundamental understanding of the redox noninnocent behavior of a number of Fe(II) complexes; 2) mechanistic understanding of the reduction reaction between the complexes and a group of VPs; and 3) development of QSARs that can be used to estimate the fate of other structurally related contaminants beyond VPs. On the basis of this project, the PI will be able to systematically study the role of many other metal(II)-RNIL complexes in the fate and transformation of a variety of emerging contaminants. Broader Impacts: Results of this project can be used by environmental scientists/engineers to develop environmental fate models to accurately predict the fate and transformation of organic contaminants in redox-active environments. Moreover, this project will contribute to training, mentoring and overall development of our graduate, undergraduate and high school students. Underrepresented minority and female students will be particularly encouraged to participate through a variety of activities planned with the pioneering CEET (Chemistry for the Environment - Education and Training) program, the Chapter of the Society of Women Engineers, College?s senior design course, Alliance For Minority Participation program, one-week residential summer program "Women's Engineering Exploration" and Department?s weekly seminars. Results and techniques of this study will be integrated into the environmental curriculum at the Temple University through a combination of lectures, experiments and demonstrations. In addition, findings from this project will be broadly disseminated to over 30 industrial partners at the annual industrial advisory board meetings of the Water and Environmental Technology (WET) Center at the Temple University.

PI：张，Huichun J.Proposal编号：1125713研究目标和方法：氧化还原的配体（RNILS）已被无机化学家对形成的复合物的氧化还原 - 形式的无机化学家进行了广泛的研究，形成了许多过渡金属。然而，关于RNIL的氧化还原活性的信息很少，特别是与新兴污染物的命运和转化有关的信息。另一方面，最近被认为是文献中的氧化还原配体的可溶性Fe（II）配合物，由于其减少许多有机污染物的能力而被认为是文献中的氧化还原配体。鉴于Fe（II）复合物在环境中的无处不在的存在和快速的氧化还原反应性，因此对配体性质（。，氧化还原无无关与非知名度）的理解不足将显着防止对还原环境中新兴污染物的命运和转化的准确估计。因此，拟议的研究将应用氧化还原非认证配体的概念应用于一组含有碳氮双键的兽医药物（VPS）的总体还原性转化； VP和RNIL的作用和转变将从机械的角度进行研究。基于我们的初步结果和文献，我们假设这组VPS将与Fe（II）复合物进行快速氧化还原反应，其中包括 - 钙齐酸酯，o'diaminophenylene，o-氨基苯基酸酯，O-氨基苯基酸酯，O-二硫代基因，O-二硫代基因和o-氨基氨基硫酸盐。为了检验这一假设，已经进行了一系列实验（1）来说明复合物的氧化还原性质，（2）确定所选VPS的反应动力学和机制以及（3），以及（3），以发展定量结构性关系（QSAR），以预测其他结构性转化的结构转换。从方法上讲，该研究将依赖于包括但不限于环状伏安，FTIR，HPLC，LC-MS-MS，NMR和UV可见度测量结果以及分析确定的紫外可见度测量值。智力优点：这项研究是最早检查与环境相关的FE（II）复合物的氧化还原行为的一项。先进的实验和解释方法将用于生成知识，这对于对含有碳氮的重要VP的环境命运的准确建模至关重要，这些VP含有碳氮双键，这对于许多其他新兴污染物（例如人类的药物和个人护理产品和诸如人类的污染物）也是常见的结构部分。该项目的智力优点是基于：1）对许多Fe（II）络合物的氧化还原行为的基本理解； 2）对复合物与一组VP之间的还原反应的机械理解； 3）QSAR的开发，可用于估计VPS以外的其他结构相关污染物的命运。在该项目的基础上，PI将能够系统地研究许多其他金属（II） - Rnil复合物在各种新兴污染物的命运和转化中的作用。更广泛的影响：环境科学家/工程师可以使用该项目的结果来开发环境命运模型，以准确预测氧化还原活性环境中有机污染物的命运和转化。 此外，该项目将有助于我们的毕业生，本科和高中生的培训，指导和整体发展。将特别鼓励代表人数不足的少数民族和女学生参加开创性的CEET（环境化学 - 教育与培训）计划，女性工程师协会的分会，大学高级设计课程，少数群体参与联盟的高级设计课程，一周的居住夏季夏季计划“女性工程探险”和部门的一周 /年。这项研究的结果和技术将通过讲座，实验和示范的结合组合到寺庙大学的环境课程中。此外，该项目的调查结果将在Temple University的水与环境技术中心的年度工业顾问委员会会议上广泛传播给30多个工业伙伴。