Room-temperature dynamic nuclear polarization enhanced NMR spectroscopy of small biological molecules in water.
Room-temperature dynamic nuclear polarization enhanced NMR spectroscopy of small biological molecules in water.
复制标题
水中生物小分子的室温动态核极化增强核磁共振波谱。
DOI：
10.1038/s41467-021-27067-0
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发表时间：
2021-11-25
影响因子：
16.6
通讯作者：
Mao J
中科院分区：
文献类型：
--
作者：
Dai D;Wang X;Liu Y;Yang XL;Glaubitz C;Denysenkov V;He X;Prisner T;Mao J
核磁共振（NMR）光谱是一种强大的和流行的技术，用于探测分子结构，动力学和化学性质。然而，传统的核磁共振波谱法因其灵敏度低而受到限制。动态核极化（DNP）将NMR灵敏度提高了几个数量级，并解决了这一限制。在液态下，这种革命性的技术仅限于有机溶剂中的几种特定的非生物模型分子。在这里，我们表明，在小的生物分子，包括碳水化合物和氨基酸，可以大大增强原位Overhauser DNP（ODNP）在水中在室温和高磁场下。ODNP 13 C增强因子和顺磁13 C NMR位移之间观察到的联系导致了生物相关杂环化合物吲哚的探索。QM/MM MD模拟强调了分子间氢键的动力学作为驱动力的标量ODNP在长寿命的自由基-基板复合物。我们的工作调和DNP光谱，顺磁NMR和计算化学得到的结果，并提供了新的机制的见解到高场标量ODNP。动态核极化（DNP）极大地提高了NMR灵敏度，但其在水溶液中的实施具有挑战性。在这里，作者证明了在室温和高磁场下，通过原位Overhauser DNP在水中的小生物分子中的碳极化增强。
Nuclear magnetic resonance (NMR) spectroscopy is a powerful and popular technique for probing the molecular structures, dynamics and chemical properties. However the conventional NMR spectroscopy is bottlenecked by its low sensitivity. Dynamic nuclear polarization (DNP) boosts NMR sensitivity by orders of magnitude and resolves this limitation. In liquid-state this revolutionizing technique has been restricted to a few specific non-biological model molecules in organic solvents. Here we show that the carbon polarization in small biological molecules, including carbohydrates and amino acids, can be enhanced sizably by in situ Overhauser DNP (ODNP) in water at room temperature and at high magnetic field. An observed connection between ODNP 13C enhancement factor and paramagnetic 13C NMR shift has led to the exploration of biologically relevant heterocyclic compound indole. The QM/MM MD simulation underscores the dynamics of intermolecular hydrogen bonds as the driving force for the scalar ODNP in a long-living radical-substrate complex. Our work reconciles results obtained by DNP spectroscopy, paramagnetic NMR and computational chemistry and provides new mechanistic insights into the high-field scalar ODNP. Dynamic nuclear polarization (DNP) greatly improves the NMR sensitivity, but its implementation in aqueous solutions is challenging. Here the authors demonstrate carbon polarization enhancement via in situ Overhauser DNP in small biomolecules in water at room temperature and high magnetic field.
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DOI：
10.1002/anie.201410653
发表时间：
2015-08-03
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Ardenkjaer-Larsen JH;Boebinger GS;Comment A;Duckett S;Edison AS;Engelke F;Griesinger C;Griffin RG;Hilty C;Maeda H;Parigi G;Prisner T;Ravera E;van Bentum J;Vega S;Webb A;Luchinat C;Schwalbe H;Frydman L
通讯作者：
Frydman L
影响因子：
2.2
作者：
Denysenkov, Vasyl;Prisner, Thomas
通讯作者：
Prisner, Thomas
DOI：
10.1007/s00775-018-1552-x
发表时间：
2018-06
期刊：
Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry
影响因子：
--
作者：
Banci L;Camponeschi F;Ciofi-Baffoni S;Piccioli M
通讯作者：
Piccioli M
影响因子：
--
作者：
Denysenkov, Vasyl P.;Prisner, Thomas F.
通讯作者：
Prisner, Thomas F.
影响因子：
4.4
作者：
Can, T. V.;Caporini, M. A.;Griffin, R. G.
通讯作者：
Griffin, R. G.