Improving the spectral sensitivity and resolution of biological solids is one of the long-standing problems in nuclear magnetic resonance (NMR) spectroscopy. In this report, we introduce low-power supercycled variants of two-pulse phase-modulated (TPPM) sequence for heteronuclear decoupling. The utility of the sequence is shown by improvements in the transverse relaxation time of observed nuclei (with H decoupling) with its application to different samples (uniformly C, N, H-labeled GB1 back-exchanged with 25% HO and 75% DO, uniformly C, N, H-labeled human derived Asyn fibril back-exchanged with 100% HO and uniformly C, N -labeled human derived Asyn fibril) at fast MAS using low radiofrequency (RF) fields. To understand the effect of spinning speed, the transverse relaxation time is monitored under different spinning frequencies. In comparison to existing heteronuclear decoupling sequences, the supercycled TPPM (sTPPM) sequence significantly improves the spectral sensitivity and resolution and is robust towards B inhomogeneity and decoupler offset.
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http://dx.doi.org/10.1016/j.jmr.2024.107726 | DOI Listing |
J Magn Reson
August 2024
Department of Biochemistry, University of Wisconsin-Madison, Madison, WI, 53706, United States; National Magnetic Resonance Facility at Madison (NMRFAM), University of Wisconsin-Madison, Madison, WI, 53706, United States; Morgridge Institute for Research, University of Wisconsin-Madison, Madison, WI, 53715, United States. Electronic address:
Improving the spectral sensitivity and resolution of biological solids is one of the long-standing problems in nuclear magnetic resonance (NMR) spectroscopy. In this report, we introduce low-power supercycled variants of two-pulse phase-modulated (TPPM) sequence for heteronuclear decoupling. The utility of the sequence is shown by improvements in the transverse relaxation time of observed nuclei (with H decoupling) with its application to different samples (uniformly C, N, H-labeled GB1 back-exchanged with 25% HO and 75% DO, uniformly C, N, H-labeled human derived Asyn fibril back-exchanged with 100% HO and uniformly C, N -labeled human derived Asyn fibril) at fast MAS using low radiofrequency (RF) fields.
View Article and Find Full Text PDFJ Chem Phys
September 2016
Physical Chemistry, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland.
We present a generalized theoretical framework that allows the approximate but rapid analysis of residual couplings of arbitrary decoupling sequences in solid-state NMR under magic-angle spinning conditions. It is a generalization of the tri-modal Floquet analysis of TPPM decoupling [Scholz et al., J.
View Article and Find Full Text PDFSolid State Nucl Magn Reson
July 2011
Ecole Normale Supérieure, Département de Chimie, 24 rue Lhomond, 75005 Paris, France.
The performance of two recently developed heteronuclear decoupling schemes designed to quench rotary resonance, phase-inverted supercycled sequence for attenuation of rotary resonance (PISSARRO) and high-phase two-pulse phase modulation (high-phase TPPM), are probed at high spinning frequencies. High-phase TPPM may be useful at the n=1 rotary resonance condition while PISSARRO permits efficient decoupling over a broad commonly used range of rf amplitudes, even at very high spinning frequencies. New insights into the response of spin systems to both decoupling schemes have been gained.
View Article and Find Full Text PDFJ Magn Reson
April 2011
Department of Chemistry, Indian Institute of Technology, New Delhi 110 016, India.
The performance of a supercycled SW(f)-TPPM sequence for heteronuclear dipolar decoupling in solid-state NMR is analyzed here. The decoupling performance of this sequence with respect to experimental parameters, such as, the phase angle, proton offset and MAS frequency is studied. A comparison is made with two other commonly used decoupling schemes in solid-state NMR namely, SPINAL-64 and SW(f)-TPPM, on a sample of U-¹³C-labeled tyrosine.
View Article and Find Full Text PDFMagn Reson Chem
October 2010
Department of Chemistry, Indian Institute of Technology, New Delhi 110016, India.
Heteronuclear dipolar decoupling is an essential requirement for extracting structural information from the (13)C NMR spectra of liquid crystals. Efficient schemes for heteronuclear dipolar decoupling in such systems are formulated here by supercycling SW(f)-TPPM, a sequence introduced recently for this purpose in rotating solids. These sequences are compared with two other commonly used decoupling schemes in liquid-crystal NMR, SPINAL-64 and SW(f)-TPPM, by analyzing the intensities of various resonances in the proton decoupled (13)C spectrum of the liquid-crystal 4-n-pentyl-4'-cyanobiphenyl (5CB).
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