物理化学学报 >> 2016, Vol. 32 >> Issue (2): 399-404.doi: 10.3866/PKU.WHXB201511272

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固态Photo-CIDNP效应

王孝杰1,*(),THAMARATH Smitha Surendran2,3,ALIA A.2,3,4,BODE BelaE.5,MATYSIK Jörg2,3,*()   

  1. 1 国防科技大学理学院化学与生物学系, 长沙 410073
    2 莱比锡大学分析化学研究所, 莱比锡04103, 德国
    3 莱顿大学化学院, 莱顿2300RA, 荷兰
    4 莱比锡大学医学物理与生物物理研究所,莱比锡D-04107,德国
    5 圣安德鲁斯大学化学与生物医学研究院,圣安德鲁斯KY169ST,苏格兰
  • 收稿日期:2015-09-21 发布日期:2016-01-30
  • 通讯作者: 王孝杰,MATYSIK Jörg E-mail:yj605@126.com;joerg.matysik@uni-leipzig.de
  • 基金资助:
    荷兰科学研究组织(NWO)(713.012.001)

The Solid-State Photo-CIDNP Effect

Xiao-Jie WANG1,*(),Smitha Surendran THAMARATH2,3,A. ALIA2,3,4,E. BODE Bela5,Jörg MATYSIK2,3,*()   

  1. 1 Department of Chemistry and Biology, College of Science, National University of Defense Technology, Changsha 410073, P. R. China
    2 Institut für Analytische Chemie, Universität Leipzig, Linnéstr. 3, 04103 Leipzig, Gemany
    3 Leiden Institute of Chemistry, Einsteinweg 55, 2300 RA Leiden, The Netherlands
    4 Institute of Medical Physics and Biophysics, University of Leipzig, D-04107 Leipzig, Germany
    5 EaStCHEM School of Chemistry and Biomedical Sciences Research Complex, University of St Andrews, St Andrews, KY16 9ST, Scotland
  • Received:2015-09-21 Published:2016-01-30
  • Contact: Xiao-Jie WANG,Jörg MATYSIK E-mail:yj605@126.com;joerg.matysik@uni-leipzig.de
  • Supported by:
    the Netherlands Organization for Scientific Research (NWO)(713.012.001)

摘要:

光化学诱导动态核极化(photo-CIDNP)是一种在光照条件下由于产生非玻尔兹曼核自旋极化而使核磁共振(NMR)波谱信号强度发生明显变化的效应。这种效应在液体NMR中已为人所熟知,并通过经典的自由基对机理得到解释。固态photo-CIDNP效应发现的较晚,本文介绍了在光合反应中心及蓝光受体中发现的固态photo-CIDNP效应,详细阐述了固态photo-CIDNP效应产生的自由基对自旋动力学的机理,包括三旋混合(TSM)、衰变差异(DD)和弛豫差异(DR),重点介绍了类球红杆菌光合反应中心固态photo-CIDNP效应的磁场依赖性,这种场依赖性在同一分子中的不同核之间表现出明显的差异。本文综述了固态photo-CIDNP效应的现象、理论及其磁场依赖特性的最新进展。

关键词: 光化学诱导动态核极化, 魔角旋转, 核磁共振, 自由基对, 自旋化学

Abstract:

Photochemically induced dynamic nuclear polarization (photo-CIDNP) is an effect that produces non-Boltzmann nuclear spin polarization, which can be observed as a modification of signal intensity in nuclear magnetic resonance (NMR) spectroscopy. The effect is well known in liquid-state NMR, where it is explained most generally by the classical radical pair mechanism (RPM). In the solid-state, additional mechanisms are operative in the spin-dynamics of radical pairs, such as three-spin mixing (TSM), differential decay (DD) and differential relaxation (DR). The observed solid-state photo-CIDNP effect is strongly magnetic field dependent, and this field-dependence is well distinguished for the various nuclei. Here, we provide an account of the phenomenology, theory and properties of the magnetic field dependence of the solid-state photo-CIDNP effect.

Key words: Photo-CIDNP, Magic angle spinning, Nuclear magnetic resonance, Radical pair, Spin chemistry

MSC2000: 

  • O646.8