Issue 20, 2012
From the journal:

Physical Chemistry Chemical Physics

Compensated second-order recoupling: application to third spin assisted recoupling†

Mathilde Giffard,a   Sabine Hediger,a   Józef R. Lewandowski,b   Michel Bardet,a   Jean-Pierre Simorre,c   Robert G. Griffind  and  Gaël De Paëpe*a  

* Corresponding authors

a Laboratoire de Chimie Inorganique et Biologique, UMR-E3 (CEA/UJF) and CNRS, CEA/DSM/INAC – 38054, Grenoble, France
E-mail: gael.depaepe@cea.fr
Fax: +33 4 38 78 58 30
Tel: +33 4 38 78 58 30

b Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK

c Institut de Biologie Structurale, 38027 Grenoble, France

d Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, Massachusetts 02139, Cambridge, USA

Abstract

We consider the effect of phase shifts in the context of second-order recoupling techniques in solid-state NMR. Notably we highlight conditions leading to significant improvements for the Third Spin Assisted Recoupling (TSAR) mechanism and demonstrate the benefits of resulting techniques for detecting long-distance transfer in biomolecular systems. The modified pulse sequences of PAR and PAIN-CP, Phase-Shifted Proton Assisted Recoupling (AH-PS-PAR) and Phase-Shifted Proton-Assisted Insensitive Nuclei Cross Polarization (ABH-PS-PAIN-CP), still rely on cross terms between heteronuclear dipolar couplings involving assisting protons that mediate zero-quantum polarization transfer between low-γ nuclei (13C–13C, 15N–15N, 15N–13C polarization transfer). Using Average Hamiltonian Theory we show that phase inversion compensates off-resonance contributions and yields improved polarization transfer as well as substantial broadening of the matching conditions. PS-TSAR greatly improves on the standard TSAR based methods because it alleviates their sensitivity to precise RF settings which significantly enhances robustness of the experiments. We demonstrate these new methods on a 19.6 kDa protein (U–[15N, 13C]-YajG) at high magnetic fields (up to 900 MHz 1H frequency) and fast sample spinning (up to 65 kHz MAS frequency).

Graphical abstract: Compensated second-order recoupling: application to third spin assisted recoupling

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Article information

DOI
https://doi.org/10.1039/C2CP40406K
Article type
Paper
Submitted
10 Feb 2012
Accepted
28 Mar 2012
First published
18 Apr 2012

Phys. Chem. Chem. Phys., 2012,14, 7246-7255

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Compensated second-order recoupling: application to third spin assisted recoupling

M. Giffard, S. Hediger, J. R. Lewandowski, M. Bardet, J. Simorre, R. G. Griffin and G. De Paëpe, Phys. Chem. Chem. Phys., 2012, 14, 7246 DOI: 10.1039/C2CP40406K

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