TY  - JOUR
A1  - Dai, Danhua
A1  - Wang, Xianwei
A1  - Liu, Yiwei
A1  - Yang, Xiao-Liang
A1  - Glaubitz, Clemens
A1  - Denysenkov, Vasyl
A1  - He, Xiao
A1  - Prisner, Thomas
A1  - Mao, Jiafei
T1  - Room-temperature dynamic nuclear polarization enhanced NMR spectroscopy of small biological molecules in water
T2  - Nature Communications
N2  - 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.
KW  - Analytical chemistry
KW  - Biophysical chemistry
KW  - Theoretical chemistry
Y1  - 2021
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/69789
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-697899
SN  - 2041-1723
N1  - The ODNP NMR data have been deposited in Figshare (https://doi.org/10.6084/m9.figshare.14774433, https://doi.org/10.6084/m9.figshare.14774415). The results of DFT calculations have been deposited in GitHub (https://github.com/xiaohegroup/Simulations-of-Tempol). The full QM/MM trajectory is available from the corresponding authors upon reasonable requests. Source data are provided with this paper.
N1  - All input files for the DFT calculations and QM/MM simulations are available via GitHub (https://github.com/xiaohegroup/Simulations-of-Tempol, https://doi.org/10.5281/zenodo.5150908). The codes for analyzing the QM/MM trajectory are available from the corresponding authors upon reasonable requests.
N1  - Open Access funding enabled and organized by Projekt DEAL.
VL  - 12
IS  - art. 6880
SP  - 1
EP  - 15
PB  - Nature Publishing Group UK
CY  - [London]
ER  -