Project 1: Formation and Reactions of Environmentally Persistent Free Radicals in

项目1：环境持久性自由基的形成和反应

基本信息

批准号：
8097836
负责人：
Barry Dellinger
金额：
$ 14.23万
依托单位：
LOUISIANA STATE UNIV A&M COL BATON ROUGE
依托单位国家：
美国
项目类别：
财政年份：
2009
资助国家：
美国
起止时间：
2009-08-15 至 2016-03-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/8097836
关键词：
Affect Binding Biochemistry Biological Breathing Caliber Cardiac Chemistry Chlorobenzene Chlorophenols Collaborations Complex Copper Data Defect Devices Electron Spin Resonance Spectroscopy Electron Transport Environment Free Radical Formation Free Radicals Fright Functional disorder Gases Genetic Recombination Hazardous Substances Hazardous Waste Hydroxyl Radical Kinetics Knowledge Laboratories Lead Literature Lung Measurement Measures Mediating Metals Modeling Modification Molecular Oxidation-Reduction Oxidative Stress Oxides Oxygen Particle Size Particulate Matter Pathway interactions Pentachlorophenol Phase Reaction Relative (related person)Reporting Research Roentgen Rays Role Sampling Silicon Dioxide Soil Soot Source Spectroscopy, Fourier Transform Infrared Structure Superfund Surface System Techniques Toxic effect Transition Elements Wood material base chemical property chlorobenzene density dibenzo(1,4)dioxin dibenzofuran fly ash innovation iron oxide metal complex metal oxide particle phenoxy radical pollutant reaction rate remediation semiquinone radicals superfund site theories

项目摘要

Environmentally persistent free radicals (EPFRs) are formed on the surfaces of transition metal-containing particles by chemisorption of a molecular precursor and electron transfer from the organic to the metal, resulting in reduction of the metal and formation of the EPFR. Association of some radicals with the metal increases their stability and reduces their rate of reaction with oxygen such that they can persist for several days in the environment. EPFRs have been found associated with soot and fly-ash produced from the combustion of hazardous wastes and Superfund soils from a former wood-treatment facility contaminated with pentachlorophenol. EPFRs are formed in high concentrations in the thermal and cool-zones of incinerators and other thermal treatment devices for remediation of Superfund sites where they can also react, primarily by radical-radical recombination, to form polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This project explores the origin and fate of EPFRs in thermal treatment devices through four Specific Aims: 1) Identify the mechanisms of EPFR formation and stabilization on transition metal surfaces; 2) Determine the role of iron oxide-containing, combustion-generated particles in the formation of PCDD/F from chlorobenzenes and chlorophenols; 3) Assess the effect of particle size on EPFR and PCDD/F formation for Fe2O3 - containing particles; and 4) Develop Reaction Kinetic Models of Surface-Mediated Formation of EPFRs and PCDD/Fs. This project provides the basic chemistry needed for the other projects in the Center. Collaboration with Project 6 will lead to understanding how the structure and chemical properties of particles affect EPFR formation and reactivity. It provides the background for study of formation and stabilization of EPFRs in contaminated Superfund soils in Project 3. It also provides the basic biological chemistry necessary to understand the cardiac and pulmonary dysfunction induced by inhalation of EPFRs demonstrated in Biomedical Projects 2, 4, and 5. Collaboration with the Oxidative Stress Core, Materials Core, and Computational Core has already shown EPFR-particle systems participate in long chain cycles in biological media producing hydroxyl radical that initiates oxidative stress in the exposed host.

环境持续的自由基（EPFR）是通过化学吸附分子前体的化学吸附在过渡金属颗粒的表面上形成的，并从有机物到金属的电子转移，从而减少了金属和EPFR的形成。某些自由基与金属的关联会增加其稳定性，并降低其与氧气的反应速率，从而可以在环境中持续几天。已经发现EPFR与煤烟和苍蝇灰烬相关，该烟灰和苍蝇是由危险废物和超级基金土壤的燃烧产生的与五氯苯酚。 EPFR在焚化炉的热和冷区和其他热处理设备中以高浓度形成，用于修复超级基金位点，在这些地点中，它们也可以主要通过自由基的重组反应，以形成多氯联苯二苯并二苯并-P-二恶英和Dibenzofurans（PCDD/FS）。该项目通过四个特定目的探索热处理设备中EPFR的起源和命运：1）确定EPFR形成的机制和过渡时稳定的机理金属表面； 2）确定含氧化铁，燃烧生成的颗粒在氯苯和氯苯酚中形成PCDD/F中的作用； 3）评估粒径对含有颗粒的Fe2O3的EPFR和PCDD/F形成的影响； 4）开发了EPFR和PCDD/FS的表面介导的形成的反应动力学模型。该项目提供了中心其他项目所需的基本化学反应。与项目6的合作将导致了解颗粒的结构和化学特性如何影响EPFR的形成和反应性。它为研究提供了背景在项目3中，EPFR的形成和EPFR的形成和稳定。它还提供了必要的基本生物学化学，以了解由吸入EPFR引起的心脏和肺功能障碍所必需的生物医学项目2、4和5中所证明的EPFRS，其与氧化应激核心和计算机群体的合作相结合。在暴露的宿主中引发氧化应激的根本。