Recoupled Polarization-Transfer Methods for Solid-State 1H–13C Heteronuclear Correlation in the Limit of Fast MAS

Saalwächter, Kay; Graf, Robert; Spiess, Hans Wolfgang

doi:10.1006/jmre.2000.2259

Cited by 79 publications

(158 citation statements)

References 58 publications

(98 reference statements)

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“…In addition, the sequences can be incorporated into existing experiments which use rotorencoding of spin-pair coherences in a second time dimension to determine internuclear distances. 45 It is also possible to use them in the single-or multiple-quantum dimension in MQMAS experiments, following the approach in refs 43 and 44. All these experiments will benefit from the better homonuclear decoupling properties of the symmetry-based recoupling sequences.…”

Section: Resultsmentioning

confidence: 99%

Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological ¹⁷O Solid-State NMR

Brinkmann

Kentgens

2006

J. Phys. Chem. B

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In this contribution we present a comprehensive approach to study hydrogen bonding in biological and biomimetic systems through 17 O and 17 O-1 H solid-state NMR combined with density functional theory calculations of 17 O and 1 H NMR parameters. We explore the signal enhancement of 17 O in L-tyrosine‚HCl using repetitive double-frequency swept radio frequency pulses in solid-state NMR. The technique is compatible with high magnetic fields and fast magic-angle spinning of the sample. A maximum enhancement by a factor of 4.3 is obtained in the signal-to-noise ratio of the selectively excited 17 O central transition in a powdered sample of 17 O η -L-tyrosine‚HCl at an external field of 14.1 T and a spinning frequency of 25 kHz. As little as 128 transients lead to meaningful 17 O spectra of the same sample at an external field of 18.8 T and a spinning frequency of 50 kHz. Furthermore we employed supercycled symmetry-based pulse sequences on the protons to achieve heteronuclear longitudinal two-spin-order (I z S z ) recoupling to determine 17 O-1 H distances. These sequences recouple the heteronuclear dipolar 17 O-1 H couplings, where dipolar truncation is absent, while decoupling the homonuclear proton dipolar interactions. They can be applied at fast magic-angle-spinning frequencies up and beyond 50 kHz and are very robust with respect to 17 O quadrupolar couplings and both 17O and 1 H chemical shift anisotropies, which makes them suitable for the use at high external magnetic fields. The method is demonstrated by determining the 17 O η -1 H distance in L-tyrosine‚HCl at a spinning frequency of 50 kHz and an external field of 18.8 T.

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Section: Resultsmentioning

confidence: 99%

Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological ¹⁷O Solid-State NMR

Brinkmann

Kentgens

2006

J. Phys. Chem. B

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“…This difference results from the fact that, in the REREDOR experiment, no particular spin state is selected; whereas the HDOR experiment detects only signal contributions which have passed through a state of dipolar order (i.e., I Z S Z ) between the two recoupling blocks. [14,27] Both REREDOR and HDOR experiments yield signal modulations and, after Fourier transformation, characteristic sideband patterns which allow for precise determinations of the underlying dipole-dipole couplings. An advantage of HDOR is that the selection of a dipolar-ordered state renders the experiment insensitive to additional modulations potentially introduced by perturbing interactions, such as chemical shift anisotropies.…”

Section: Differences Between Reredor and Hdor Sideband Patternsmentioning

confidence: 99%

“…Such measurements can be performed in a particularly simple, robust and sensitive manner by using rotor-encoded recoupling schemes. [5,[13][14][15] In two-dimensional experiments, the signal is amplitude-modulated in the indirect (t 1 ) dimension and can readily be converted into a characteristic pattern of spinning sidebands by Fourier transformation. These patterns are resolved in the direct (t 2 or F 2 ) dimension according to the chemical shift of the detected nuclei and sensitively reflect the strength of the underlying dipole-dipole couplings.…”

Section: Introductionmentioning

confidence: 99%

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Determining the Geometry of Hydrogen Bonds in Solids with Picometer Accuracy by Quantum‐Chemical Calculations and NMR Spectroscopy

et al. 2005

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The structure of multiply hydrogen‐bonded systems is determined with picometer accuracy by a combined solid‐state NMR and quantum‐chemical approach. On the experimental side, advanced 1H15N dipolar recoupling NMR techniques are capable of providing proton–nitrogen distances of up to about 250 pm with an accuracy level of ±1 pm for short distances (i.e., around 100 pm) and ±5 pm for longer ones (i.e., 180 to 250 pm). The experiments were performed under fast magic‐angle spinning, which ensures sufficient dipolar decoupling and spectral resolution of the 1H resonance lines. On the quantum‐chemical side, the structures of the hydrogen‐bonded systems were computationally optimised, yielding complete sets of nitrogen–proton and proton–proton distances, which are essential for correctly interpreting the experimental NMR data. In this way, nitrogen–proton distances were determined with picometer accuracy, so that vibrational averaging effects on dipole–dipole couplings need to be considered. The obtained structures were finally confirmed by the complete agreement of computed and experimental 1H and 15N chemical shifts. This demonstrates that solid‐state NMR and quantum‐chemical methods ideally complement each other and, in a combined manner, represent a powerful approach for reliable, high‐precision structure determination whenever scattering techniques are inapplicable.

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“…[73] [38,42,65,74] Figure 3a presents a rotor-synchronised 1 H (700 MHz) DQ MAS NMR spectrum of 2@3. [38] The assignment of the resolved 1 H DQ peaks is aided by reference to Figure 3b, where the aromatic region of a 1 H- 13 C heteronuclear correlation spectrum of 2@3, recorded with the REPT-HSQC experiment, [75,76] Figure 3b to the guest CHs (labelled 3a and 3b), with the corresponding 1 H chemical shifts being 5.6 and 2.0 ppm, respectively. The pair of cross peaks at a DQ frequency of 7.6 ppm in Figure 3a can thus be identified as being due to two neighbouring guest CH protons.…”

Section: Aromatic Ring Current Effects In Host-guest Complexesmentioning

confidence: 99%

Recent Advances in Solid‐State MAS NMR Methodology for Probing Structure and Dynamics in Polymeric and Supramolecular Systems

Brown

2009

Macromol. Rapid Commun.

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This article reviews recent applications of novel (1) H, (2) H, (13) C, (15) N and (17) O solid-state MAS NMR methods that provide new insight into the structural and dynamic processes that determine the bulk properties of polymeric and supramolecular materials. The review highlights methods that exploit the sensitivity to structure and dynamics of the NMR chemical shift and quadrupolar coupling as well as the through-space dipolar coupling and through-bond J coupling. In particular, it is shown that solid-state NMR exhibits marked sensitivity to key intra- and intermolecular hydrogen-bonding and π-π interactions, allowing, for example, the very accurate determination of internuclear distances as well as the probing of dynamics over a very wide range of timescales.

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Recoupled Polarization-Transfer Methods for Solid-State 1H–13C Heteronuclear Correlation in the Limit of Fast MAS

Cited by 79 publications

References 58 publications

Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological ¹⁷O Solid-State NMR

Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological ¹⁷O Solid-State NMR

Determining the Geometry of Hydrogen Bonds in Solids with Picometer Accuracy by Quantum‐Chemical Calculations and NMR Spectroscopy

Recent Advances in Solid‐State MAS NMR Methodology for Probing Structure and Dynamics in Polymeric and Supramolecular Systems

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Recoupled Polarization-Transfer Methods for Solid-State 1H–13C Heteronuclear Correlation in the Limit of Fast MAS

Cited by 79 publications

References 58 publications

Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological 17O Solid-State NMR

Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological 17O Solid-State NMR

Determining the Geometry of Hydrogen Bonds in Solids with Picometer Accuracy by Quantum‐Chemical Calculations and NMR Spectroscopy

Recent Advances in Solid‐State MAS NMR Methodology for Probing Structure and Dynamics in Polymeric and Supramolecular Systems

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Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological ¹⁷O Solid-State NMR

Sensitivity Enhancement and Heteronuclear Distance Measurements in Biological ¹⁷O Solid-State NMR