实验证据表明,在阿金氨基基中存在反向的迁移
Shigeo Hayakawa1, Hiroshi Matsubara, Subhasis Panja
1Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Osaka, Japan.
电子转移到阿尔金因基因导致原子迁移到瓜尼丁碳. 这种反向迁移,经过实验证实,在质谱学中影响了氨酸基的行为.
科学领域:
- 化学动力学 化学动力学
- 质谱测量质量谱测量
- 计算化学是一种计算化学.
背景情况:
- 理论研究预测了阿尔金因基的逆迁移.
- 对这种现象的实验证据在阿尔金因及其胺中缺乏.
研究的目的:
- 实验证实了阿尔金因基的逆迁移.
- 调查影响这种重新排列的因素及其对质谱学的影响.
主要方法:
- 电子转移反应产生氨酸基.
- 基离子的电荷逆转,随后与 (Cs) 原子发生碰撞.
- 高级计算化学 (RRKM在B3-PMP2/aug-cc-pVTZ潜在能量表面上的计算).
主要成果:
- 实验证实了氨酸和氨酸胺基基的部分逆迁移的实验证实.
- 检测重新排列的C ((α) 基作为稳定的离子.
- 计算分析显示了快速的侧链旋转,促进了C ((alpha) -H转移 (k > 10 ((9) s ((-1)).
- 瓜尼丁组被确定为一个贫穷的H原子供体,但高效的H原子受体,作为一个激进陷.
结论:
- 瓜尼丁组的特性解释了在含氨酸的质谱中非解离性离子基的稳定性.
- 反向迁移是基激素的重要途径,影响它们的反应性和检测.
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