中华医学超声杂志

应用化学 ›› 1988, Vol. 0 ›› Issue (1): 57-61.

• 研究论文 • 上一篇    下一篇

卟啉衍生物的ESR与光化动力学研究

林青松, 张田林, 袁履冰   

  1. 大连工学院化学系
  • 收稿日期:1986-07-09 修回日期:1987-04-21 出版日期:1988-02-10 发布日期:1988-02-10
  • 基金资助:
    中国科学院科学基金资助课题

STUDY OF ESR SPECTRA AND PHOTOCHEMICAL REACTION OF PORPHYRIN DERIVATIVES

Lin Qingsung, Zhang Tianlin, Yuan Lubing   

  1. College of Chemical Engineering, Dalian Institute of Technology, Dalian
  • Received:1986-07-09 Revised:1987-04-21 Published:1988-02-10 Online:1988-02-10

PDF

461

被引次数

2

摘要： 本文测定了2,4-二(α-亚氨基乙酸乙基)次卟啉Ⅸ和2,4-二(α-巯乙基)次卟啉Ⅸ的g因子、ΔHpp、线型及自旋浓度;它们的ESR信号强度对微波功率的饱和效应及对温度的响应;同时测定了在不同温度下UV-辐照的ESR相对强度.发现它们的ESR由两种顺磁中心所贡献;卟啉环中的未偶非定域电子与环上的磁性核相互作用产生的超精细结构和卟啉与氧有关的自由基.与氧有关的自由基的ESR信号强度对微波功率的饱和效应与各化合物析出的等电点pH值有关;对温度的响应情况比较复杂;光化反应对与氧有关的自由基呈现零级动力学行为,整个反应受三态氧向激发态卟啉"活动范围"的扩散所控制.

关键词: 卟啉, 光化学反应, 电子自旋共振波谱法, 动力学

Abstract: In this paper, the values of g factor, ΔHpp, line shape and spin concentration of 2,4-di-(α-imino acetic acid ethyl) bcuteroporphyrin Ⅸ and 2,4-di-(α-mcrcaptoethyl) deutcroporphyrin Ⅸ on X-band were determined. The relationships of the ESR line intensity to saturation effect of microwave power, as well as the temperature were also determined. It is postulated that the ESR spectra registcd under the UV-irradiation at various temperatures were originated from single delocalized electron of porphyrin ring and oxygen dependent radical; the dependence of ESR line intensity on the saturation effect of microwave power is related to isoelectric point (pH value), but the effect of temperature is more complicated. The photochemical reaction is of zero order with respect to oxygen dependent radical and is controlled by the diffusion of the triplet oxygen to the around site of cxcited state of porphyrin.

Key words: Porphyrin(P), Photochemical reaction, Electron spin resonance spectrometry, Kinetics

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