Molecular Mechanism of Overhauser Dynamic Nuclear Polarization in Insulating Solids

被引：54

作者：

Pylaeva, Svetlana ^{[1
]}

Ivanov, Konstantin L. ^{[2
,3
,4
]}

Baldus, Marc ^{[4
]}

Sebastiani, Daniel ^{[1
]}

Elgabarty, Hossam ^{[1
]}

机构：

[1] MLU Halle Wittenberg, Chem Dept, D-06120 Halle, Saale, Germany

[2] RAS, Int Tomog Ctr, SB, Novosibirsk 630090, Russia

[3] Novosibirsk State Univ, Novosibirsk 630090, Russia

[4] Univ Utrecht, Bijvoet Ctr Biomol Res, NMR Spect, NL-3584 CH Utrecht, Netherlands

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2017年 / 8卷 / 10期

基金：

俄罗斯科学基金会;

关键词：

THEORETICAL ASPECTS; MAGNETIC-FIELDS; STATE; NMR;

D O I：

10.1021/acs.jpclett.7b00561

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Dynamic nuclear polarization (DNP), a technique that significantly enhances NMR signals, is experiencing a renaissance owing to enormous methodological developments. In the heart of DNP is a polarization transfer mechanism that endows nuclei with much larger electronic spin polarization. Polarization transfer via the Overhauser effect (OE) is traditionally known to be operative only in liquids and conducting solids. Very recently, surprisingly strong OE-DNP in insulating solids has been reported, with a DNP efficiency that increases with the magnetic field strength. Here we offer an explanation for these perplexing observations using a combination of molecular dynamics and spin dynamics simulations. Our approach elucidates the underlying molecular stochastic motion, provides cross-relaxation rates, explains the observed sign of the NMR enhancement, and estimates the role of nuclear spin diffusion. The presented theoretical description opens the door for rational design of novel polarizing agents for OE-DNP in insulating solids.

引用

页码：2137 / 2142

页数：6

共 41 条

[1] OVERHAUSER EFFECT IN NONMETALS [J].

ABRAGAM, A .

PHYSICAL REVIEW, 1955, 98 (06) :1729-1735

[2] Gromacs: High performance molecular simulations through multi-level parallelism from laptops to supercomputers [J].

Abraham, Mark James ;

Murtola, Teemu ;

Schulz, Roland ;

Páll, Szilárd ;

Smith, Jeremy C. ;

Hess, Berk ;

Lindah, Erik .

SoftwareX, 2015, 1-2 :19-25

[3] Increase in signal-to-noise ratio of >10,000 times in liquid-state NMR [J].

Ardenkjaer-Larsen, JH ;

Fridlund, B ;

Gram, A ;

Hansson, G ;

Hansson, L ;

Lerche, MH ;

Servin, R ;

Thaning, M ;

Golman, K .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2003, 100 (18) :10158-10163

[4] Correlation experiments for assignment and structure elucidation of immobilized polypeptides under magic angle spinning [J].

Baldus, M .

PROGRESS IN NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY, 2002, 41 (1-2) :1-47

[5]

Barone V, 1995, Recent advances in density functional methods, P287

[6] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[7] Pushing NMR sensitivity limits using dynamic nuclear polarization with closed-loop cryogenic helium sample spinning [J].

Bouleau, E. ;

Saint-Bonnet, P. ;

Mentink-Vigier, F. ;

Takahashi, H. ;

Jacquot, J. -F. ;

Bardet, M. ;

Aussenac, F. ;

Purea, A. ;

Engelke, F. ;

Hediger, S. ;

Lee, D. ;

De Paepe, G. .

CHEMICAL SCIENCE, 2015, 6 (12) :6806-6812

[8] Overhauser effects in insulating solids [J].

Can, T. V. ;

Caporini, M. A. ;

Mentink-Vigier, F. ;

Corzilius, B. ;

Walish, J. J. ;

Rosay, M. ;

Maas, W. E. ;

Baldus, M. ;

Vega, S. ;

Swager, T. M. ;

Griffin, R. G. .

JOURNAL OF CHEMICAL PHYSICS, 2014, 141 (06)

[9] Protein Folding Studied by Dissolution Dynamic Nuclear Polarization [J].

Chen, Hsueh-Ying ;

Ragavan, Mukundan ;

Hilty, Christian .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (35) :9192-9195

[10] Mechanism of dynamic nuclear polarization in high magnetic fields [J].

Farrar, CT ;

Hall, DA ;

Gerfen, GJ ;

Inati, SJ ;

Griffin, RG .

JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (11) :4922-4933

← 1 2 3 4 5 →