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High-field dynamic nuclear polarization for solid and solution biological NMR

机译:用于固体和溶液生物NMR的高场动态核极化

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Dynamic nuclear polarization (DNP) results in a substantial nuclear polarization enhancement through a transfer of the magnetization from electrons to nuclei. Recent years have seen considerable progress in the development of DNP experiments directed towards enhancing sensitivity in biological nuclear magnetic resonance (NMR). This review covers the applications, hardware, polarizing agents, and theoretical descriptions that were developed at the Francis Bitter Magnet Laboratory at Massachusetts Institute of Technology for high-field DNP experiments. In frozen dielectrics, the enhanced nuclear polarization developed in the vicinity of the polarizing agent can be efficiently dispersed to the bulk of the sample via H-1 spin diffusion. This strategy has been proven effective in polarizing biologically interesting systems, such as nanocrystalline peptides and membrane proteins, without leading to paramagnetic broadening of the NMR signals. Gyrotrons have been used as a source of high-power (5-10 W) microwaves up to 460 GHz as required for the DNP experiments. Other hardware has also been developed allowing in situ microwave irradiation integrated with cryogenic magic-angle-spinning solid-state NMR. Advances in the quantum mechanical treatment are successful in describing the mechanism by which new biradical polarizing agents yield larger enhancements at higher magnetic fields. Finally, pulsed methods and solution experiments should play a prominent role in the future of DNP.
机译:动态核极化(DNP)通过将磁化强度从电子转移到原子核而导致实质性的核极化增强。近年来,在旨在增强生物核磁共振(NMR)灵敏度的DNP实验的开发中已经取得了可观的进展。这篇综述涵盖了麻省理工学院弗朗西斯·波特磁铁实验室针对高场DNP实验开发的应用,硬件,极化剂和理论描述。在冻结的电介质中,可以通过H-1自旋扩散将在偏振剂附近形成的增强核极化有效地分散到大部分样品中。事实证明,该策略可有效极化生物感兴趣的系统(例如纳米晶体肽和膜蛋白),而不会导致NMR信号顺磁性变宽。根据DNP实验的要求,回旋加速器已被用作高达460 GHz的高功率(5-10 W)微波源。还开发了其他硬件,可将原位微波辐射与低温魔术角旋转固态NMR集成在一起。量子力学处理方面的进展成功地描述了新型双自由基偏振剂在较高磁场下产生更大增强的机理。最后,脉冲方法和溶液实验应在DNP的未来中扮演重要角色。

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