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地球磁场能够使与酰胺基团中快速弛豫的四极 14N 核偶合的 13C 核弛豫。

Earth's magnetic field enabled scalar coupling relaxation of 13C nuclei bound to fast-relaxing quadrupolar 14N in amide groups.

机构信息

GE Global Research, Munich, Germany.

出版信息

J Magn Reson. 2013 Feb;227:35-8. doi: 10.1016/j.jmr.2012.11.016. Epub 2012 Nov 29.


DOI:10.1016/j.jmr.2012.11.016
PMID:23262330
Abstract

Scalar coupling relaxation, which is usually only associated with closely resonant nuclei (e.g., (79)Br-(13)C), can be a very effective relaxation mechanism. While working on hyperpolarized [5-(13)C]glutamine, fast liquid-state polarization decay during transfer to the MRI scanner was observed. This behavior could hypothetically be explained by substantial T(1) shortening due to a scalar coupling contribution (type II) to the relaxation caused by the fast-relaxing quadrupolar (14)N adjacent to the (13)C nucleus in the amide group. This contribution is only effective in low magnetic fields (i.e., less than 800 μT) and prevents the use of molecules bearing the (13)C-amide group as hyperpolarized MRS/MRI probes. In the present work, this hypothesis is explored both theoretically and experimentally. The results show that high hyperpolarization levels can be retained using either a (15)N-labeled amide or by applying a magnetic field during transfer of the sample from the polarizer to the MRI scanner.

摘要

标量偶合弛豫通常仅与近共振核(例如(79)Br-(13)C)有关,它可以是一种非常有效的弛豫机制。在研究高极化[5-(13)C]谷氨酰胺时,在转移到 MRI 扫描仪期间观察到快速的液相极化衰减。这种行为可以假设通过与酰胺基团中(13)C 核相邻的快速弛豫四极(14)N 对弛豫的标量偶合贡献(II 型)引起的实质性 T1 缩短来解释,这种贡献仅在低磁场中有效(即小于 800μT),并防止使用带有(13)C-酰胺基团的分子作为高极化 MRS/MRI 探针。在本工作中,从理论和实验两个方面探讨了这一假设。结果表明,使用(15)N 标记的酰胺或在从极化器向 MRI 扫描仪转移样品期间施加磁场,可以保留高的高极化水平。

相似文献

[1]
Earth's magnetic field enabled scalar coupling relaxation of 13C nuclei bound to fast-relaxing quadrupolar 14N in amide groups.

J Magn Reson. 2012-11-29

[2]
Measuring amide nitrogen quadrupolar coupling by high-resolution 14N/13C NMR correlation under magic-angle spinning.

J Am Chem Soc. 2006-5-10

[3]
Probing amide bond nitrogens in solids using 14N NMR spectroscopy.

Solid State Nucl Magn Reson. 2008-5

[4]
Mechanism of 1H-14N cross-relaxation in immobilized proteins.

J Magn Reson. 2010-1-25

[5]
Measuring nitrogen quadrupolar coupling with 13C detected wide-line 14N NMR under magic-angle spinning.

Chem Commun (Camb). 2008-2-21

[6]
Coherence transfer between spy nuclei and nitrogen-14 in solids.

J Magn Reson. 2008-1

[7]
NMR at earth's magnetic field using para-hydrogen induced polarization.

J Magn Reson. 2011-7-20

[8]
(14)N quadrupolar coupling of amide nitrogen and Peptide secondary structure as studied by solid-state NMR spectroscopy.

J Am Chem Soc. 2010-3-31

[9]
A dynamic nuclear polarization strategy for multi-dimensional Earth's field NMR spectroscopy.

J Magn Reson. 2008-12

[10]
Estimating quadrupole couplings of amide deuterons in proteins from direct measurements of 2H spin relaxation rates.

J Magn Reson. 2009-12-24

引用本文的文献

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Sci Rep. 2025-4-12

[2]
Zero-field J-spectroscopy of quadrupolar nuclei.

Nat Commun. 2024-5-27

[3]
Extended Bloch-McConnell equations for mechanistic analysis of hyperpolarized C magnetic resonance experiments on enzyme systems.

Magn Reson (Gott). 2021-6-15

[4]
Nitrogen-15 dynamic nuclear polarization of nicotinamide derivatives in biocompatible solutions.

Sci Adv. 2023-8-25

[5]
Hyperpolarized [5-C,4,4-H,5-N]-L-glutamine provides a means of annotating in vivo metabolic utilization of glutamine.

Proc Natl Acad Sci U S A. 2022-5-10

[6]
Structure-guided design enables development of a hyperpolarized molecular probe for the detection of aminopeptidase N activity in vivo.

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[7]
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[8]
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[9]
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[10]
Application and methodology of dissolution dynamic nuclear polarization in physical, chemical and biological contexts.

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