Room-temperature Dynamic Nuclear Polarization Enhanced NMR Spectroscopy of Small Biological Molecules in Water

Overview

Journal Nat Commun

Specialty Biology

Date 2021 Nov 26

PMID 34824218

Citations 11

Authors

Danhua Dai

Xianwei Wang

Yiwei Liu

Xiao-Liang Yang

Clemens Glaubitz

Vasyl Denysenkov

Xiao He

Thomas Prisner

Jiafei Mao

Affiliations

Soon will be listed here.

Abstract

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 C enhancement factor and paramagnetic C 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.

Citing Articles

Overhauser Dynamic Nuclear Polarization Enables Single Scan Benchtop C NMR Spectroscopy in Continuous-Flow.

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Overhauser enhanced liquid state nuclear magnetic resonance spectroscopy in one and two dimensions.

Levien M, Yang L, van der Ham A, Reinhard M, John M, Purea A Nat Commun. 2024; 15(1):5904.

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Glycan Shape, Motions, and Interactions Explored by NMR Spectroscopy.

Widmalm G JACS Au. 2024; 4(1):20-39.

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Triplet dynamic nuclear polarization of pyruvate supramolecular chemistry.

Hamachi T, Nishimura K, Sakamoto K, Kawashima Y, Kouno H, Sato S Chem Sci. 2023; 14(47):13842-13850.

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Polarizing agents beyond pentacene for efficient triplet dynamic nuclear polarization in glass matrices.

Sakamoto K, Hamachi T, Miyokawa K, Tateishi K, Uesaka T, Kurashige Y Proc Natl Acad Sci U S A. 2023; 120(44):e2307926120.

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