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水-甘油玻璃中的动力学解耦:氮氧化物、三苯甲基自由基和钆配合物的比较

Dynamical decoupling in water-glycerol glasses: a comparison of nitroxides, trityl radicals and gadolinium complexes.

作者信息

Soetbeer Janne, Millen Marthe, Zouboulis Konstantin, Hülsmann Miriam, Godt Adelheid, Polyhach Yevhen, Jeschke Gunnar

机构信息

Laboratory of Physical Chemistry, ETH Zürich, Vladimir-Prelog-Weg 2, CH-8093 Zürich, Switzerland.

Bielefeld University, Department of Chemistry, Universitätsstr. 25, D-33615 Bielefeld, Germany.

出版信息

Phys Chem Chem Phys. 2021 Mar 11;23(9):5352-5369. doi: 10.1039/d1cp00055a.

Abstract

Our previous study on nitroxides in o-terphenyl (OTP) revealed two separable decoherence processes at low temperatures, best captured by the sum of two stretched exponentials (SSE) model. Dynamical decoupling (DD) extends both associated dephasing times linearly for 1 to 5 refocusing pulses [Soetbeer et al., Phys. Chem. Chem. Phys., 2018, 20, 1615]. Here we demonstrate an analogous DD behavior of water-soluble nitroxides in water-glycerol glass by using nitroxide and/or solvent deuteration for component assignment. Compared to the conventional Hahn experiment, we show that Carr-Purcell and Uhrig DD schemes are superior in resolving and identifying active dephasing mechanisms. Thereby, we observe a partial coherence loss to intramolecular nitroxide and trityl nuclei that can be alleviated, while the zero field splitting-induced losses for gadolinium labels cannot be refocused and contribute even at the central transition of this spin-7/2 system. Independent of the studied spin system, Uhrig DD leads to a characteristic convex dephasing envelope in both protonated water-glycerol and OTP glass, thus outperforming the Carr-Purcell scheme.

摘要

我们之前关于邻三联苯(OTP)中氮氧化物的研究揭示了在低温下存在两个可分离的退相干过程,用两个拉伸指数(SSE)模型的总和能最好地描述。动态解耦(DD)对于1至5个重聚焦脉冲可使两个相关的去相位时间线性延长[Soetbeer等人,《物理化学化学物理》,2018年,20,1615]。在此,我们通过使用氮氧化物和/或溶剂氘化进行成分归属,证明了水溶性氮氧化物在水 - 甘油玻璃中的类似DD行为。与传统的哈恩实验相比,我们表明卡尔 - 珀塞尔(Carr - Purcell)和乌里格(Uhrig)DD方案在解析和识别活性去相位机制方面更具优势。由此,我们观察到分子内氮氧化物和三苯甲基核存在部分相干损失,这种损失可以减轻,而钆标签的零场分裂引起的损失无法重新聚焦,即使在这个自旋 - 7/2系统的中心跃迁处也有贡献。与所研究的自旋系统无关,乌里格DD在质子化水 - 甘油和OTP玻璃中均导致特征性的凸形去相位包络,因此优于卡尔 - 珀塞尔方案。

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