RADIATION INDUCED LIPID AND SULFHYDRYL AUTOXIDATION

这个项目提出了一项关于辐射诱导的研究 部分生物脂类和硫化物的自氧化 重要性，包括化学、结构和运动 由此产生的过氧基。电子自旋共振(ESR) 光谱学，从头算和半经验分子轨道 我们将使用计算来阐明这些关系 这些系统中的结构、运动和反应性之间的关系。我们的 拟议的项目打算侧重于LID的以下方面 和硫氧基化学；通过ESR澄清 光谱学，关于自氧化循环的一些细节 不饱和脂肪和饱和脂肪在低温下。在这 建立和损失率的工作动力学分析 与脂质自氧化有关的自由基 温度将被用来找出活化能 LIPIL的氧气动员和氢气提取 过氧基。脂质过氧化自由基下一步研究 在不饱和度增加的脂质中形成的将被执行 观察非饱和度对运动平均化的影响 过氧基探头。硫氧阴离子自由基在脑损伤中的作用 将研究自氧化过程。使用技巧 在我们实验室开发的，我们将确定 自由基(S)，由硫醇和二硫化物照射在 在低温下氧气的存在，并确定 这些自由基在硫自氧化反应中的重要性 含有化合物的。理论与实验并重 硫氧自由基的表征将被执行。 硫氧自由基在大鼠脑损伤中作用的初步研究 就会引发脂质氧化。从头算(高斯B2)和 半经验分子轨道计算将用于 开发和测试脂质和硫氧自由基结构的模型， 运动性和反应性。

This project proposes a study of the radiation induced autoxidation of selected lipids and sulfur compounds of biological importance, including the chemistry, structure and motion of the resulting peroxyl radicals. Electron Spin Resonance (ESR) spectroscopy, and ab initio and semiempirical molecular orbital calculations will be employed to elucidate the relationships between structure, motion and reactivity in these systems. Our proposed project intends to focus on the following aspects of lipid and sulfur oxy radical chemistry; Elucidation, through ESR spectroscopy, of the details of the autoxidation cycle in a number of unsaturated and saturated lipids at low temperatures. In this work kinetic analyses of the rates of build up and loss of the radicals involved in lipid autoxidation as a function of temperature will be performed to find the activation energies for both oxygen mobilization, and hydrogen abstraction by lipil peroxyl radicals. Next investigation of lipid peroxyl radicals formed in lipids with increasing unsaturation will be performed to observe the effect of unsaturation on the motional averaging of the peroxyl probe. The role of sulfuroxygen radicals in autoxidation processes will be studied. Using techniques developed in our laboratory, we will determine the identify of the radical(s) formed when thiols and disulfides are irradiated in the presence of oxygen at low temperatures, and determine the importance of these radicals to the autoxidation of sulfur containing compounds. Theoretical as well as experimental characterization of the sulfur oxygen radicals will be performed. Preliminary investigations of the role of sulfuroxygen radicals in lipid oxidation will be initiated. Ab initio (Gaussian B2) and semiempirical molecular orbital calculations will be employed to develop and test models of lipid and sulfur oxy radical structure, motion, and reactivity.