Research Project 9: Biomimetic Remediation of Hazardous Substances

拟议的研究集中在发展氧化过程的修复 被卤化和非卤化有机物污染的地下水和土壤/沉积物， 怀疑生殖和发育的后果。这种治疗依赖于催化铁试剂 其操作模式优选模拟生物加氧酶（P-450，sMMO）的操作模式，并且 因此比利用无差别羟基的其他先进氧化技术更具选择性， 根的具体来说，拟议的工作将提供新的和更强大的成员的家庭monoiron 试剂（P-450类似物），其由富电子三脚架配体支持，设计用于稳定 高价铁氧氧化剂和配体中心的自由基。此外，一个新的家庭， 二铁试剂（sMMO类似物）将被引入以提供高度亲电氧化剂用于 持久性污染物基质的氧化。将研究合适的试剂在降解 广泛的底物，包括氯化溶剂、BTEX、邻苯二甲酸酯、MTBE和氯酚， 以及对抗多氯二苯并-对-二恶英、二苯并呋喃 和联苯。与金属，配体和底物为中心的事件相关的机制研究将在 致力于报告手头试剂的适用性并评估其仿生作用模式。 机械的工作也有望提供有关目前争论的氧合的见解 生物加氧酶途径（P-450，sMMO）。最成功的试剂将成为 连续还原（Fe（0））和氧化处理区的实验室规模柱可处理性研究 设计成实现有机污染物的完全降解。氧化区将由以下物质组成： 在本研究中开发的氧合试剂，经适当修饰以提供异源化形式的 负载在惰性基质上的催化剂。将详细研究对化学混合物的有效性。

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.