水化动力学的定量cw Overhauser DNP分析
Quantitative cw Overhauser DNP Analysis of Hydration Dynamics
摘要:
近年来,液态奥弗豪泽效应动态核极化(ODNP)又引起了人们的兴趣.特别地,ODNP测量的新表现测量了ESR活性自旋探针的5-10 μ m内的水的平移迁移率(即,电子自旋共振活性分子附近的局部平移扩散率D_{local})。这样的自旋探针,通常是稳定的氮氧自由基,已被连接到大分子,包括蛋白质,聚合物和膜囊泡的表面或内部。尽管这种测量具有独特的特异性,但它只需要标准的X波段(~10 GHz)连续波(cw)电子自旋共振(ESR)光谱仪,以及标准的核磁共振(NMR)光谱仪。在这里,我们提出了一组的发展和校正,使我们能够提高定量ODNP的准确性,并将其应用到样品比以前可行的低两个数量级以上。
英文摘要:
Liquid state Overhauser Effect Dynamic Nuclear Polarization (ODNP) has experienced a recent resurgence of interest. In particular, a new manifestation of the ODNP measurement measures the translational mobility of water within 5-10 Å of an ESR-active spin probe (i.e. the local translational diffusivity D_{local} near an electron spin resonance active molecule). Such spin probes, typically stable nitroxide radicals, have been attached to the surface or interior of macromolecules, including proteins, polymers, and membrane vesicles. Despite the unique specificity of this measurement, it requires only a standard X-band (~10 GHz) continuous wave (cw) electron spin resonance (ESR) spectrometer, coupled with a standard nuclear magnetic resonance (NMR) spectrometer. Here, we present a set of developments and corrections that allow us to improve the accuracy of quantitative ODNP and apply it to samples more than two orders of magnitude lower than were previously feasible.
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