Eaton Sandra S, Eaton Gareth R
Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80210 USA.
Appl Magn Reson. 2021 Oct;52(10):1223-1236. doi: 10.1007/s00723-021-01353-y. Epub 2021 May 31.
It has been known from the pioneering and approximately simultaneous work of Freed and Frankel, Hausser and Deguchi (1959 -1960) that collisions with O in fluid solutions broaden the electron paramagnetic resonance (EPR) spectra of free radicals. Freed showed Hausser the effect of degassing solutions on the hyperfine of DPPH. Hausser and Deguchi published spectra illustrating the effect. The effect of O on CW EPR spectra and on relaxation times have been applied to the problem of measuring O concentration in vivo. Various aspects of the effect of O on biological EPR and on the biological systems have been studied. A large literature has developed about in vivo O measurements using nitroxyl radicals, triarylmethyl radicals (trityl, TAM), carbon particles, and analogues of lithium phthalocyanine (LiPc). All of these measurements correctly assume that the O electron spin relaxation time is short relative to the relaxation time of the sensor molecules. There has been no prior review of the EPR spectra and electron spin relaxation of O in the gas phase, dissolved in fluid solution, and in frozen solutions. A summary of the relevant literature is presented here as a resource for the O measurement community.
从弗里德和弗兰克尔、豪泽和出木口(1959 - 1960年)开创性的几乎同时期的研究工作中可知,自由基在流体溶液中与氧气(O)发生碰撞会使电子顺磁共振(EPR)光谱变宽。弗里德向豪泽展示了溶液脱气对二苯基苦味酰基自由基(DPPH)超精细结构的影响。豪泽和出木口发表了说明该影响的光谱。氧气对连续波电子顺磁共振光谱(CW EPR)和弛豫时间的影响已应用于体内氧气浓度测量问题。人们研究了氧气对生物电子顺磁共振以及生物系统影响的各个方面。关于使用硝酰自由基、三芳基甲基自由基(三苯甲基,TAM)、碳颗粒和锂酞菁类似物(LiPc)进行体内氧气测量,已经形成了大量文献。所有这些测量都正确地假定,相对于传感器分子的弛豫时间,氧气的电子自旋弛豫时间很短。此前尚未有关于气相、溶解于流体溶液以及冷冻溶液中的氧气的电子顺磁共振光谱和电子自旋弛豫的综述。本文呈现相关文献的总结,作为氧气测量领域的参考资料。