波谱学杂志 ›› 1996, Vol. 13 ›› Issue (6): 509-518.

• 研究论文 •    下一篇

手性和构型的识别Ⅰ.开链氮氧化物的ESR研究

石型   

  1. 台湾私立元智工学院化工系, 中坜 32026
  • 收稿日期:1996-05-19 修回日期:1996-08-21 出版日期:1996-12-05 发布日期:2018-01-17

RECOGNITION OF CHIRALITY AND CONFORMATION-Ⅰ.Studies of Open Chain Nitroxide by ESR Spectroscopy

Shawn Shih   

  1. Department of Chemital Engineering Yuan-Tze Institute of Technology Nei-Li, Taiwan 32026
  • Received:1996-05-19 Revised:1996-08-21 Online:1996-12-05 Published:2018-01-17

摘要: 我们将微波电子自族共振仪的吸收谐振腔为光化学反应器.在其各种流体及温度的范围内讨论其光化学效应.作者所用的模型乃是有机烷基-亚硝酸类在醇类的动力研究,许多不同的双氢氧烷基及烷氧基-烷基与一氧化氮所结合的自由基均由光分解而产生不同的电子自旋共振光谱.最有兴趣的是产生对映结构的双氢氧乙烷基与一氧化氮所结合的异构物自由基,它们的几何形态可用分子振动理论及共价键理论来解析.自标准化学键长及化学键角度,这些烷氧基-烷基与一氧化氛所结合的自由基还存在很强的氢键,这些将会在科学上,如生物化学、生物学及医学上的氧化及还原反应有相当重要的位置.

关键词: 有机自由基, 光化学反应, 电子自族共振, 非对称性自由基

Abstract: We have considered the ESR cavity as a photo-chemical reactor under various flow and temperature conditions.Our model system under investigation is the kinetic studies of alkyl nitrites in alcohol media.Various di-hydroxyalkyl and alkoxy-alkyl nitroxide free radial were formed and characterized by their ESR spectra.Of particular interests are the unequivocal detection of enantiomeric di-hydroxylethyl nitroxide radicals and other alkyl-alkoxyl nitroxide radicals. The determination of their conformations has been in terms of vibronic interactions and we find,from the standard valence theory,bond lengths and bond angles,the strong evidence for the intramolecular hydrogen bond formation in these nitroxide radicals,which may be of greater greater importance in other areas of science,such as biochemistry,biology and medicine.

Key words: Organic radical, Photochemical reaction, ESR, Asymmetric radical