Mechanistic Studies of Free Radicals and Molecular Aggregates

有机和高分子化学项目的这项拨款支持Ned Porter博士的研究，旨在解释涉及自由基作为反应中间体的化学反应机制的特点。这种反应在有机化学和生命过程的化学中非常常见，如脂质氧化、组织损伤和衰老。这笔赠款涵盖的三个研究领域是：(A)自由基氢过氧化氢重排；(B)作为化学反应和立体化学潜在扰动的疏水效应的检查；以及(C)涉及自由基大环化和跨环环化的因素的研究。脂肪和油与分子氧的反应，这是一种产生过氧化氢的自由基反应，与老化过程有关。波特博士的研究涉及有机分子与分子氧反应所涉及的化学过程的基础研究。自由基在有机合成中也被广泛使用，Porter团队发现了一种利用自由基构建大环分子的新方法。这项工作将探索这种新反应的局限性和可能性。最后，将研究水对含有混合溶液(如肥皂)的有机分子的化学反应和立体化学的影响。早期证据表明，由类似肥皂的分子在水中形成的分子聚集体可以对这些分子产生戏剧性和不同寻常的立体化学效应。

This grant in the Organic and Macromolecular Chemistry Program supports research by Dr. Ned Porter aimed at explaining features of the mechanisms of chemical reactions which involve free radicals as reaction intermediates. Such reactions are quite common in organic chemistry and in the chemistry of life processes, such as lipid oxidation, tissue damage, and aging. The three areas of research covered in this grant are: (a) free radical hydroperoxide rearrangements; (b) examination of the hydrophobic effect as a potential perturbation of chemical reactivity and stereochemistry; and (c) the study of factors involved in free radical macrocyclization and transannular cyclization. The reaction of fats and oils with molecular oxygen, a free radical reaction that generates hydroperoxides, has been implicated in the aging process. Dr. Porter's research involves fundamental studies of the chemical processes involved in the reaction of organic molecules with molecular oxygen. Free radicals are also being used extensively in organic synthesis and the Porter group has discovered a new method for construction of large-ring molecules using free radicals. This work will explore the limitations and possibilities of this new reaction. Finally, the effect of water on the chemical reactivity and stereochemistry of organic molecules that have mixed solutions such as soaps will be investigated. Early evidence indicates that molecular aggregates formed from soap-like molecules in water can exert dramatic and unusual stereochemical effects on these molecules.