Research Project 9: Biomimetic Remediation of Hazardous Substances

拟议的研究集中在开发用于修复的氧化过程 受卤化和非卤化有机物污染的地下水和土壤/沉积物 疑似生殖和发育后果。治疗依赖于催化铁试剂。 其工作模式最好是模仿生物加氧酶(P-450，sMMO)的工作模式，并且是 因此比其他利用不加区别的羟基的高级氧化技术更具选择性 激进分子。具体地说，拟议的工作将为单铁家族提供新的和更强大的成员 试剂(P-450类似物)，由设计用于稳定的富电子三脚架配体支撑 高价铁氧氧化剂和以配体为中心的自由基同时存在。此外，一个新的家庭 双铁试剂(sMMO类似物)将被引入，以提供用于 持久性污染物底物的氧化作用。将研究合适的试剂来降解 各种底物，包括氯化溶剂、苯系物、邻苯二甲酸酯、甲基叔丁基醚和氯苯酚，如 以及对顽固的亲脂底物，如多氯二苯并对二恶英、二苯并呋喃 还有联苯。与金属、配体和底物为中心的事件相关的机制研究将是 继续报告手头试剂的适宜性，并评估其仿生作用模式。 这项机械性的工作也有望提供与当前争论的氧合作用有关的见解 生物加氧酶途径(P-450，sMMO)。最成功的试剂将成为主题 在顺序还原(Fe(0))和氧化处理区中的实验室规模、柱可处理性研究 旨在实现有机污染物的完全降解。氧化区将由以下部分组成 在这项研究中开发的氧合试剂，经过适当的修改，以提供异构化版本的 惰性基质负载的催化剂。对化学混合物的有效性将进行详细研究。

The proposed research concentrates on the development of oxidative processes for remediation of groundwater and soils/sediments contaminated with halogenated and non-halogenated organics with suspected reproductive and developmental consequences. The treatment relies on catalytic iron reagents whose mode of operation is preferably mimicking that of biological oxygenases (P-450, sMMO), and are thus more selective than other advanced oxidative technologies that make use of indiscriminate hydroxyl radicals. Specifically, the proposed work will provide new and more robust members of a family of monoiron reagents (P-450 analogs), which are supported by electron-rich tripodal ligands designed to stabilize high-valent iron-oxo oxidants and ligand-centered radicals simultaneously. In addition, a new family of diiron reagents (sMMO analogs) will be introduced to afford highly electrophilic oxidants for use in oxygenations of persistent pollutant substrates. Suitable reagents will be investigated in the degradation of a wide range of substrates, including chlorinated solvents, BTEX, phthalates, MTBE and chlorophenols, as well as against recalcitrant lipophilic substrates such as polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls. Mechanistic studies associated with metal, ligand, and substrate-centered events will be pursued to report on the suitability of the reagents at hand and evaluate their biomimetic mode of action. The mechanistic work is also expected to provide insights in relation to the currently debated oxygenation pathways of biological oxygenases (P-450, sMMO). The most successful reagents will become the subject of bench-scale, column treatability studies in sequential reductive (Fe(0)) and oxidative treatment zones designed to effect complete degradation of organic contaminants. The oxidative zone will be composed of the oxygenation reagents developed in this study, suitably modified to afford heterogeriized versions of the catalysts supported on inert matrices. The effectiveness on chemical mixtures will be studied in detail.