The REDOR transform: direct calculation of internuclear couplings from dipolar-dephasing NMR data

Mueller, Karl T.; Jarvie, Thomas; Aurentz, David J.; Roberts, B. W.

doi:10.1016/0009-2614(95)00773-w

Cited by 131 publications

(153 citation statements)

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“…Dephasing was calculated using the modified Bessel function expressions given by Mueller et al (25) and de la Caillerie and Fretigny (26) for a spin-1/2 pair. The REDOR dephasing function for CF 3 was approximated by treating the three fluorines as a single super spin (with two spin quantum numbers, I = 1/2 and 3/2) placed at the center of the plane defined by the positions of the three fluorines.…”

Section: Calculated Redor Dephasingmentioning

confidence: 99%

Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by ¹³C{¹⁹F} and ¹⁵N{¹⁹F} Rotational-Echo Double Resonance

et al. 2006

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Solid-state NMR has been used to examine isolated cell walls and intact whole cells of Staphylococcus aureus complexed to 5 different vancomycin, eremomycin, and chloroeremomycin derivatives. The cell walls and whole cells were specifically labeled with D-[1-13 C]alanine, or a combination of [1-13 C]glycine and [ε-15 N]lysine. Each of the bound glycopeptides had a 19 F-labeled substituent at either its C-terminus or disaccharide position. The 13 C{ 19 F} rotational-echo doubleresonance (REDOR) dephasing for the cell-wall 13 C-labeled bridging pentaglycyl segment connecting a glycopeptide-complexed peptidoglycan stem with its neighboring stem indicates that the fluorine labels for all bound glycopeptides are positioned at one end or the other of the bridge. An exception is N'-(p-trifluoromethoxybenzyl)chloroeremomycin whose hydrophobic substituent differs in length by one phenyl group compared to that of oritavancin, N'-4- [(4-chlorophenyl) benzyl)]chloroeremomycin. For this drug the fluorine label is near the middle of the pentaglycyl segment. The 15 N{ 19 F} REDOR dephasing shows proximity of the fluorine to the bridge-link site of the pentaglycyl bridge for C-terminus-substituted moieties, and to the cross-link site for disaccharide-substituted moieties. Full-echo REDOR spectra of cell-wall complexes from cells labeled by D-[1-13 C]alanine (in the presence of an alanine racemase inhibitor) reveal three different carbonyl-carbon chemical-shift environments, arising from the D-Ala-D-Ala binding site and the DAla-Gly-1 cross-link site. The REDOR results indicate a single fluorine dephasing center in each peptidoglycan complex. Molecular models of the mature cell-wall complexes that are consistent with internuclear distances obtained from 13 C{ 19 F} and 15 N{ 19 F} REDOR dephasing allow a correlation of structure and antimicrobial activity of the glycopeptides. KeywordsDipolar coupling; glycopeptide antibiotic; magic-angle spinning; peptidoglycan; solid-state NMR; transglycosylase Vancomycin is a potent antibiotic that is effective against multi-drug-resistant Gram-positive bacteria including methicillin-resistant S. aureus. As many as 60% of clinically isolated strains of S. aureus are methicillin resistant (1), which means that vancomycin is one of the most important antibiotics in use today. Vancomycin inhibits the transglycosylation step in the † This paper is based on work supported by the National Institutes of Health under grant number EB02058. * Jacob Schaefer, NIH Public Access Author ManuscriptBiochemistry. Author manuscript; available in PMC 2008 August 9. The emergence of vancomycin-resistant enterococci (VRE) has limited vancomycin usage against methicillin-resistant S. aureus. In 2002, vancomycin-resistant S. aureus (VRSA) with a minimum inhibitory concentration (MIC) of greater than 128 μg/mL was recovered from a patient in Michigan who was being treated with multiple antibiotics (5). E. faecalis, a vancomycin-resistant enterococcus, was also recovered from the patient. The VRSA isolat...

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Section: Calculated Redor Dephasingmentioning

confidence: 99%

Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by ¹³C{¹⁹F} and ¹⁵N{¹⁹F} Rotational-Echo Double Resonance

et al. 2006

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“…If the individual couplings are sufficiently strong this evaluation can be solved by the so-called REDOR transform. [18,19] Alternatively a full simulation of the experimental spin system can be performed [20][21][22] or specialized REDOR sequences like REDOR 3D, [23] FDR-REDOR, [24,25] q-REDOR, [26] or MS REDOR [27] can be employed, which however cause substantially longer measuring times.…”

Section: Introductionmentioning

confidence: 99%

Revealing the Configuration and Crystal Packing of Organic Compounds by Solid‐State NMR Spectroscopy: Methoxycarbonylurea, a Case Study

Macholl

Börner

Buntkowsky

2004

Chemistry A European J

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The molecular configuration and intermolecular arrangement of polycrystalline methoxycarbonylurea (MCU) has been studied by a combination of chemical editing, rotational echo double resonance (REDOR) spectroscopy and ab initio calculations. From the multispin IS(n) REDOR experiments several dipolar couplings were determined and converted into distance constraints. Intra- and intermolecular dipolar couplings were distinguished by isotope dilution. The configuration of the MCU molecule can be determined from three torsion angles Psi1, Psi2, and Psi3. Ab initio calculations showed that these angles are either 0 degrees or 180 degrees (Z or E). From the REDOR experiments, the E configuration was found for Psi1 and Psi2 and the Z configuration for Psi3. Thus the configuration of MCU in the solid state was determined to be EEZ. Distance constraints for the intermolecular arrangement of MCU were obtained by performing REDOR experiments on 13C15N2 MCU with different degrees of isotope dilution and on a cocrystallized 1:1 mixture of 13C(urea) MCU and 15N(amide) MCU. By combining these distance constraints with molecular modeling, three different possible packing motifs for MCU molecules were found. The molecules in these motifs are arranged as linear chains with methoxy groups at the borders of the chains. All the intermolecular hydrogen bond donors and acceptors in the interior of the chain are saturated.

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“…57 The theoretical expression in Eq. ͑54͒may be evaluated very rapidly and has proved to be invaluable in structure-determination procedures.…”

Section: Symmetrical Protocolmentioning

confidence: 99%

“…Analytical expressions for integrals of this type have been found in the context of the REDOR experiment. 57 The theoretical double-quantumfiltered trajectory for SR26, in a symmetrical incrementation protocol, is given by…”

Section: Symmetrical Protocolmentioning

confidence: 99%

Theory and applications of supercycled symmetry-based recoupling sequences in solid-state nuclear magnetic resonance

Kristiansen

Carravetta

Beek

et al. 2006

The Journal of Chemical Physics

158

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We present the theoretical principles of supercycled symmetry-based recoupling sequences in solid-state magic-angle-spinning NMR. We discuss the construction procedure of the SR26 pulse sequence, which is a particularly robust sequence for double-quantum homonuclear dipole-dipole recoupling. The supercycle removes destructive higher-order average Hamiltonian terms and renders the sequence robust over long time intervals. We demonstrate applications of the SR26 sequence to double-quantum spectroscopy, homonuclear spin counting, and determination of the relative orientations of chemical shift anisotropy tensors.

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The REDOR transform: direct calculation of internuclear couplings from dipolar-dephasing NMR data

Cited by 131 publications

References 11 publications

Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by ¹³C{¹⁹F} and ¹⁵N{¹⁹F} Rotational-Echo Double Resonance

Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by ¹³C{¹⁹F} and ¹⁵N{¹⁹F} Rotational-Echo Double Resonance

Revealing the Configuration and Crystal Packing of Organic Compounds by Solid‐State NMR Spectroscopy: Methoxycarbonylurea, a Case Study

Theory and applications of supercycled symmetry-based recoupling sequences in solid-state nuclear magnetic resonance

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The REDOR transform: direct calculation of internuclear couplings from dipolar-dephasing NMR data

Cited by 131 publications

References 11 publications

Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by 13C{19F} and 15N{19F} Rotational-Echo Double Resonance

Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by 13C{19F} and 15N{19F} Rotational-Echo Double Resonance

Revealing the Configuration and Crystal Packing of Organic Compounds by Solid‐State NMR Spectroscopy: Methoxycarbonylurea, a Case Study

Theory and applications of supercycled symmetry-based recoupling sequences in solid-state nuclear magnetic resonance

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Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by ¹³C{¹⁹F} and ¹⁵N{¹⁹F} Rotational-Echo Double Resonance

Structures of Staphylococcus aureus Cell-Wall Complexes with Vancomycin, Eremomycin, and Chloroeremomycin Derivatives by ¹³C{¹⁹F} and ¹⁵N{¹⁹F} Rotational-Echo Double Resonance