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Gas-phase reactivity of aromatic carbon-centered sigma-type mono- and biradicals towards simple organic substrates and aliphatic amino acids using ion trap mass spectrometers.

机译:使用离子阱质谱仪,以芳族碳为中心的sigma型单自由基和双自由基对简单的有机底物和脂肪族氨基酸的气相反应性。

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摘要

The study of radical reactions has become a rapidly growing area of research because radicals initiate many chemical processes. These chemical processes include reactions in the atmosphere that cause depletion of the ozone layer, combustion reactions and certain biochemical processes, which proceed through radical intermediates. Radicals' reactivity towards biomolecules, such as proteins and DNA, has become of great interest since para-benzyne derivatives were discovered to be the biologically active intermediates of the potent enediyne anti-tumor antibiotics. Understanding the factors that govern the reactivity of these para-benzyne derivatives would be beneficial in helping to control their reactivity. Unfortunately, only limited experimental data have been reported on the parameters that play a role on the reactivity of para-benzyne derivatives. Their short lifetimes and high reactivities make studies in solution challenging. Fortunately, these challenges can be avoided by carrying out gas-phase experiments. Utilizing the distonic ion approach and tandem mass spectrometers, the gas-phase reactivities of several para-benzyne derivatives, as well as related sigma-type monoradicals and biradicals, are reported in this thesis.
机译:由于自由基引发许多化学过程,因此自由基反应的研究已成为快速发展的研究领域。这些化学过程包括在大气中引起臭氧层消耗的反应,燃烧反应和某些生物化学过程,这些过程通过自由基中间体进行。自由基对生物分子(例如蛋白质和DNA)的反应性已引起人们极大的兴趣,因为发现对苯甲酰衍生物是有效的烯二炔抗肿瘤抗生素的生物活性中间体。了解控制这些对联苯并衍生物的反应性的因素将有助于控制其反应性。不幸的是,仅报道了有限参数的实验数据,这些参数对对苯并zy衍生物的反应性起着作用。它们的短寿命和高反应活性使对溶液的研究具有挑战性。幸运的是,通过进行气相实​​验可以避免这些挑战。本文利用Disonic离子方法和串联质谱仪,报道了几种对-苄基衍生物的气相反应性,以及相关的σ型单基和双基。

著录项

  • 作者

    Archibold, Enada F.;

  • 作者单位

    Purdue University.;

  • 授予单位 Purdue University.;
  • 学科 Chemistry Organic.;Chemistry Physical.
  • 学位 Ph.D.
  • 年度 2012
  • 页码 271 p.
  • 总页数 271
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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