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Electron-Spin Relaxation of Triarylmethyl Radicals in Glassy Trehalose

机译:在玻璃状海藻糖中的三芳基甲基自由基的电子旋转

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摘要

Trehalose was recently proposed as a promising immobilizer of biomolecules for room-temperature electron paramagnetic resonance (EPR) structural studies. The most crucial parameter in these investigations is electron-spin relaxation (namely, phase memory time T ~(m)). Recently, triarylmethyl (TAM) spin labels attached to DNA in trehalose were found to have the longest T ~(m)at room temperature as compared to the existing spin labels and immobilizers. Therefore, in this work, we investigated TAM radicals in trehalose including Finland trityl (H36 form), perdeuterated Finland trityl (D36 form), and a deuterated version of OX063. The temperature dependence of electron-spin relaxation time of these radicals immobilized in trehalose was measured at X-band frequency, and possible mechanisms of relaxation were considered. OX063D in glassy trehalose has longer T ~(m)up to 200?K as compared to Finland trityl, but at higher temperatures, OX063D is inferior in its relaxation properties, and the deuterated form of Finland trityl is preferable for pulse dipolar EPR spectroscopy experiments at 298?K. The influence of various deuterations (TAM or trehalose) on the observed relaxation times was studied, being controlled by the electron-spin-echo envelope modulation at room temperature.
机译:最近提出了海藻糖作为室温电子顺磁共振(EPR)结构研究的有前途的生物分子的抗身。这些研究中最重要的参数是电子 - 旋弛弛豫(即,相位存储时间T〜(m))。最近,在室温下,与现有的旋转标签和固定剂相比,发现与海藻糖中的DNA连接的三芳基甲基(TAM)旋转标签在室温下具有最长的T〜(m)。因此,在这项工作中,我们调查了海藻糖中的TAM基质,包括芬兰Trityl(H36形式),掺产芬兰TRITYL(D36形式)和OX063的氘代版。在X波段频率下测量固定在海藻糖中的这些基团的电子 - 自旋弛豫时间的温度依赖性,并且考虑了可能的松弛机制。与芬兰TRITYL相比,玻璃状海藻糖中的OX063D在玻璃状海藻糖中最长至200μl,但在较高的温度下,OX063D在其弛豫特性下较差,并且对于脉冲偶极EPR光谱实验,优选芬兰Trityl的氘代形式在298?k。研究了各种氘代(TAM或海藻糖)对观察到的弛豫时间的影响,通过在室温下通过电子 - 旋转回波包络调制控制。

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