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Generation and reactions of nitroxyl (HNO) and nitric oxide and quantum mechanical investigation of nitroxide spin labels.

机译：硝氧基（HNO）和一氧化氮的产生和反应以及一氧化氮自旋标记的量子力学研究。

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摘要

This dissertation details the results of experimental and theoretical investigations of the synthesis and decomposition of substituted secondary amine diazeniumdiolate (NONOates), the mechanisms of reactions of N-hydroxysulfenamides from thiols and nitroxyl, the calculation of theoretical reduction potentials for biologically relevant nitrogen oxides and sulfur oxoanions, and the conformational analysis of nitroxide spin labeled side chains in proteins.;In Chapter 1, the effect of the substituent on the decomposition of secondary amine NONOates is discussed. Amino NONOates with strong electron-withdrawing substituents are predicted to primarily generate HNO upon decomposition in aqueous solution. 1-(Bis-(2,2,2-trifluoroethyl)amino)diazen-1-ium-1,2-diolate was synthesized and was shown to be a dual HNO and NO donor.;Chapter 2 describes the reaction of mono- and disubstituted N-methylanilines with nitric oxide. Quantum mechanical calculations support a stepwise addition mechanism of NO in the synthesis of diazeniumdiolate from N-methyl-4-nitroaniline, but not from anilines without powerful electron-withdrawing substituents.;In Chapter 3, the mechanism of sulfenic acid formation from hindered aromatic thiols and nitroxyl is discussed. The thermodynamics of N-hydroxysulfenamide reactions with various reagents are assessed.;Chapter 4 reports improved theoretical reduction potentials for a series of nitrogen oxide related species and sulfur oxoanions, determined with the high accuracy complete basis set method, CBS-QB3, and SM6 continuum solvation model for aqueous solvation energies.;In Chapter 5, the preferred conformations of nitroxide spin labels are studied through density functional theory and ab initio calculations. The contribution of CalphaH...S, NH...S, and CH...O interactions to the stabilization of some rotamers is also evaluated.
机译：本论文详细介绍了取代仲胺二重氮二醇二甲酸酯（NONOates）的合成和分解的实验和理论研究的结果，硫醇和硝氧基的N-羟基亚磺酰胺反应的机理，生物学上相关的氮氧化物和硫的理论还原电位的计算。氧阴离子，以及蛋白质中氮氧化物自旋标记侧链的构象分析。;在第一章中，讨论了取代基对仲胺NONOates分解的影响。带有强吸电子取代基的氨基NONOates预计在水溶液中分解时主要生成HNO。合成了1-（双-（2,2,2-三氟乙基）氨基）重氮-1-1,2-二醇盐，显示其为HNO和NO双重供体。第二章描述了单-和一氧化二氮取代的N-甲基苯胺。量子力学计算支持由N-甲基-4-硝基苯胺合成二氮烯二烯酸酯的NO逐步加成机理，但不支持不具有强吸电子取代基的苯胺合成NO .;在第三章中，受阻芳族硫醇形成亚磺酸的机理并讨论了硝氧基。评估了N-羟基亚磺酰胺与各种试剂的热力学反应。;第4章报告了一系列氮氧化物相关物质和硫氧阴离子的理论还原电位的提高，这些还原电位是通过高精度完全基集方法，CBS-QB3和SM6连续介质测定的在第五章中，通过密度泛函理论和从头算计算研究了氮氧化物自旋标记的优选构象。还评估了CalphaH ... S，NH ... S和CH ... O相互作用对某些旋转异构体稳定的贡献。

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  • 作者

    Serbulea, Laura Liliana.;

  • 作者单位

    University of California, Los Angeles.;

  • 授予单位 University of California, Los Angeles.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 123 p.
  • 总页数 123
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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