CAS: Elucidating Mechanisms of Perfluoroalkyl Substances Degradation in the Environment: A Coupled Computational Experimental Approach

CAS：阐明全氟烷基物质在环境中降解的机制：耦合计算实验方法

• 批准号: 2109210
• 负责人: Shubham Vyas
• 金额: $ 45.57万
• 依托单位: Colorado School of Mines
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2109210&HistoricalAwards=false
• 关键词: CAS; Elucidating; Mechanisms; Perfluoroalkyl; Substances

With support from the Environmental Chemical Sciences (ECS) Program in the Division of Chemistry at NSF, Shabham Vyas and his students at the Colorado School of Mines will study the reactivity of per- and polyfluoroalkyl substances (PFAS) in the environment. The project focuses on chemical reactions of PFAS with various reactive species, such as carbonate radicals, and the role metal ions play in this process. PFAS are among the most persistent anthropogenic chemicals that quietly proliferated throughout the world. The unique properties of PFAS, especially their chemical stability, lent them to diverse applications. However, research in the last two decades points to potential adverse effects of PFAS on the environment and in biological systems. This project will be carried out using cutting edge computer modeling and targeted experimentation with the overall objective of establishing methods to achieve complete breakdown of such environmental contaminants. This project will provide graduate and undergraduate students opportunities to participate in interdisciplinary research. Dr. Vyas also will participate in K-12 outreach programs to encourage students to pursue careers in STEM (science, technology, engineering and mathematics) fields. Kinetic and thermodynamic parameters for various chemical transformations, including electron transfer reactions, will be obtained using density functional theory and post-Hartree-Fock-based chemical computations. Concurrently, targeted experiments will be performed using techniques such as laser flash photolysis, time-dependent photolysis, electron paramagnetic resonance and mass spectrometry. The first objective of this work is to quantitatively measure the reactivity of PFAS with radical species and probe mechanisms of associated electron transfer reactions. The second objective will be to investigate the role of environmentally relevant transition metal ions in radical-mediated degradation of PFAS. The third objective of this project is to delineate the degradation mechanisms of PFAS and the impact of radicals and metal ions. Collectively, this research work will quantitatively establish the reactivity of PFAS and their degradation with the available reactive species in the environment. The ultimate goal would be to establish fundamental science that might one day lead to complete mineralization of PFAS.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在国家科学基金会化学部环境化学科学(ECS)项目的支持下，Shabham Vyas和他在科罗拉多矿业学院的学生将研究全氟烷基物质(PFAS)和多氟烷基物质(PFAS)在环境中的反应性。该项目的重点是全氟辛烷磺酸与各种活性物种的化学反应，如碳酸盐自由基，以及金属离子在这一过程中所起的作用。全氟辛烷磺酸是在世界各地悄悄扩散的最持久的人为化学物质之一。全氟辛烷磺酸的独特性质，特别是其化学稳定性，使其具有广泛的应用前景。然而，过去二十年的研究指出，全氟辛烷磺酸对环境和生物系统有潜在的不利影响。该项目将利用尖端的计算机模拟和有针对性的实验进行，总体目标是建立彻底分解这种环境污染物的方法。该项目将为研究生和本科生提供参与跨学科研究的机会。Vyas博士还将参加K-12推广计划，以鼓励学生在STEM(科学、技术、工程和数学)领域追求职业生涯。各种化学转化的动力学和热力学参数，包括电子转移反应，将使用密度泛函理论和基于后Hartree-Fock的化学计算得到。同时，将利用激光闪光光解、时间相关光解、电子顺磁共振和质谱学等技术进行有针对性的实验。这项工作的第一个目标是定量测量PFAS与自由基物种的反应性，并探索相关电子转移反应的机理。第二个目标将是研究与环境相关的过渡金属离子在自由基介导的全氟辛烷磺酸降解中的作用。本项目的第三个目标是描述全氟辛烷磺酸的降解机理以及自由基和金属离子的影响。总而言之，这项研究工作将定量地确定全氟辛烷磺酸的反应性及其与环境中可用活性物种的降解。最终目标将是建立基础科学，有朝一日可能导致PFAS的完全矿化。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Conformational distributions of helical perfluoroalkyl substances and impacts on stability

螺旋全氟烷基物质的构象分布及其对稳定性的影响

• DOI: 10.1002/jcc.26967
• 发表时间: 2022
• 期刊: Journal of Computational Chemistry
• 影响因子: 3
• 作者: Mifkovic, Maleigh;Van Hoomissen, Daniel J.;Vyas, Shubham
• 通讯作者: Vyas, Shubham

Computational protocol for predicting 19F NMR chemical shifts for PFAS and connection to PFAS structure

• DOI: 10.1002/jcc.26939
• 发表时间: 2022-06
• 期刊: Journal of Computational Chemistry
• 影响因子: 3
• 作者: Maleigh Mifkovic;Jessica Pauling;Shubham Vyas