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首次通过 X 波段电子自旋回波确定溶液中硝酰氮自由基的自旋弛豫性质:与 Tempone 的比较。

First determination of the spin relaxation properties of a nitronyl nitroxide in solution by electron spin echoes at X-band: a comparison with Tempone.

机构信息

Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, I-35131 Padova, Italy.

出版信息

J Magn Reson. 2012 Oct;223:180-6. doi: 10.1016/j.jmr.2012.07.011. Epub 2012 Jul 22.

DOI:10.1016/j.jmr.2012.07.011
PMID:22975247
Abstract

We studied by electron spin echo pulse methods the spin relaxation properties of a phenyl nitronyl nitroxide radical (2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide, PTIO) at X-band in fluid toluene solution in a wide temperature range, and in a water/glycerol 1:1 mixture near room temperature. The relaxation properties of PTIO have been compared with that of Tempone, as a widely used nitroxide. By a new procedure, based on experimental results on the temperature dependences of the relaxation times T(1) and T(2), and on the approximation of an isotropic brownian rotational diffusion, we separated non-secular, spin rotational and residual terms from the transverse relaxation rate to isolate secular and pseudosecular contributions. By comparing the results for the two radicals we found the differences in the magnetic properties that give rise to slower transverse (T(2)) and longitudinal (T(1)) electron spin relaxation for PTIO in the whole temperature range explored in this work.

摘要

我们通过电子自旋回波脉冲方法研究了苯基硝酮自由基(2-苯基-4,4,5,5-四甲基咪唑啉-1-氧-3-氧化物,PTIO)在 X 波段在流体甲苯溶液中的自旋弛豫性质,研究范围很宽,包括在接近室温的水/甘油 1:1 混合物中。我们将 PTIO 的弛豫性质与广泛使用的 Tempone 进行了比较。通过一种新的方法,基于对弛豫时间 T(1)和 T(2)随温度的依赖关系的实验结果,以及对各向同性布朗旋转扩散的近似,我们从横向弛豫率中分离出非定域、自旋旋转和剩余项,以分离定域和伪定域贡献。通过比较这两种自由基的结果,我们发现了它们在磁性质上的差异,这导致了在我们研究的整个温度范围内,PTIO 的横向(T(2))和纵向(T(1))电子自旋弛豫速度较慢。

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