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M H Levitt

Publications and source records attributed to M H Levitt.

At least 19 recordsLinked to original sources
PubMed2006

Cryogenic NMR spectroscopy of endohedral hydrogen-fullerene complexes.

We have observed 1H NMR spectra of hydrogen molecules trapped inside modified fullerene cages under cryogenic conditions. Experiments on static samples were performed at sample temperatures down to 4.3 K, while magic-angle-spinning (MAS) experiments were performed at temperatures down to 20 K at spinning frequencies of 15 kHz. Both types of NMR spectra show a large increase in the intramolecular 1H-1H dipolar coupling at temperatures below 50 K, revealing thermal selection of a small number of spatial rotational states. The static and MAS spectra were compared to estimate the degree of sample heating in high-speed cryogenic MAS-NMR experiments. The cryogenic MAS-NMR data show that the site resolution of magic-angle-spinning NMR may be combined with the high signal strength of cryogenic operation and that cryogenic phenomena may be studied with chemical site selectivity.

Journal Article↗
PubMed2002

Signal enhancement in the triple-quantum magic-angle spinning NMR of spins-3/2 in solids: the FAM-RIACT-FAM sequence.

We achieve a significant signal enhancement for the triple-quantum magic-angle spinning NMR of a spin-3/2 system, by using an amplitude-modulated radiofrequency field, followed by a selective 90 degrees pulse and a phase-shifted strong rf field, for the triple-quantum excitation, and an amplitude-modulated radiofrequency field for the conversion of triple-quantum coherence to observable single-quantum coherence. The experiment is demonstrated on the (87)Rb NMR of polycrystalline rubidium nitrate.

Journal Article↗
PubMed2002

Double-quantum solid-state NMR of 13C spin pairs coupled to 14N.

We examine the double-quantum magic angle spinning NMR spectra of pairs of 13C nuclei coupled to one or more 14N nuclei. The experimental spectra of 13C(2)-glycine and glycyl-[13C(2)]-glycyl-glycine are used to demonstrate the sensitivity of the spectra to the orientation of 14N quadrupole interaction tensors and to the molecular torsional angles.

Carbon Isotopes↗
PubMed2001

Estimation of carbon-carbon bond lengths and medium-range internuclear distances by solid-state nuclear magnetic resonance.

We describe magic-angle-spinning NMR methods for the accurate determination of internuclear dipole-dipole couplings between homonuclear spins-(1/2) in the solid state. The new sequences use symmetry principles to treat the effect of magic-angle sample-rotation and resonant radio frequency fields. The pulse-sequence symmetries generate selection rules which reduce the interference of undesirable interactions and improve the robustness of the pulse sequences with respect to chemical shift anisotropies. We show that the pulse sequences may be used to estimate distances between 13C spins in organic solids, including bond lengths in systems with large chemical shift anisotropies, such as conjugated systems. For bond-length measurements, the precision of the method is +/-2 pm with a systematic overestimate of the internuclear distance by 3 +/- 1 pm. The method is expected to be a useful tool for investigating structural changes in macromolecules.

Alanine↗
PubMed2001

Double-quantum excitation in the NMR of spinning solids by pulse-assisted rotational resonance.

We describe a new technique for double-quantum excitation in magic-angle-spinning NMR of powdered solids. The technique is designed to efficiently excite double-quantum coherence in the vicinity of a rotational resonance condition. The offset from rotational resonance allows the double-quantum filtered signals to be observed with high resolution and sensitivity. The method uses rotational excitation of zero-quantum coherence, assisted by radiofrequency pulse cycles. The zero-quantum coherence is converted into double-quantum coherence by a frequency-selective inversion sequence. Experiments on [(13)C(2), (15)N]-glycine demonstrate a double-quantum filtering efficiency of approximately 41% at a sample rotation frequency of 8.300 kHz, which is 1.600 kHz away from the n = 1 rotational resonance. We achieve 32% double-quantum filtering efficiency at a spinning frequency of 9.250 kHz, which is 2.550 kHz away from rotational resonance.

Journal Article↗
PubMed2001

Conformation of the glycosidic linkage in a disaccharide investigated by double-quantum solid-state NMR.

Double-quantum heteronuclear local field NMR is performed on a sample of a 13C2-labeled disaccharide, in which the two 13C spins are located on opposite sides of the glycosidic linkage. The evolution of the double-quantum coherences is found to be consistent with the solid-state conformation of the molecule, as previously determined by X-ray diffraction. The dependence of the double-quantum evolution on the glycosidic torsional angles is examined by using a graphical molecular manipulation program interfaced to a numerical spin simulation module.

Carbohydrate Conformation↗
PubMed2000

BII nucleotides in the B and C forms of natural-sequence polymeric DNA: A new model for the C form of DNA.

A combination of solid-state (31)P and (13)C NMR, X-ray diffraction, and model building is used to show that the B and C forms of fibrous macromolecular DNA consist of two distinct nucleotide conformations, which correspond closely to the BI and BII nucleotide conformations known from oligonucleotide crystals. The proportion of the BII conformation is higher in the C form than in the B form. We show structural models for a 10(1) double helix involving BI nucleotides and a 9(1) double helix involving BII nucleotides. The 10(1) BI model is similar to a previous model of B-form DNA, while the 9(1) BII model is novel. The BII model has a very deep and narrow minor groove, a shallow and wide major groove, and highly inclined bases. This work shows that the B to C transition in fibers corresponds to BI to BII conformational changes of the individual nucleotides.

DNA↗
PubMed2000

Signs of frequencies and phases in NMR: the role of radiofrequency mixing.

This article analyzes the influence of the radiofrequency mixing scheme on the sign of phase shifts experienced by the nuclear spins. It is an addendum to a previous article on the signs of phases and frequencies in NMR (M. H. Levitt, J. Magn. Reson. 126, 164 (1997)).

Magnetic Resonance Spectroscopy↗
PubMed2000

Determination of molecular geometry by high-order multiple-quantum evolution in solid-state NMR.

The principles of molecular geometry determination by high-quantum heteronuclear local field spectroscopy in solid-state NMR are discussed. The extreme multiple-quantum coherences in a cluster of nuclear spins are allowed to evolve in the presence of heteronuclear through-space couplings to two spins of a different type. The multiple-quantum dephasing curve is independent of the homonuclear spin-spin couplings and may be described in terms of geometric parameters. The triple-quantum version of the experiment is demonstrated by determining the psi torsion angle in a [(15)N(2), (13)C(3)]-labeled sample of the peptide ala-ala-gly. Two regions of torsion angle space fit the experimental data, one in the neighborhood of -152 degrees and one in the neighborhood of +161 degrees. The latter determination is in excellent agreement with the X-ray estimate of +160.5 degrees.

Magnetic Resonance Spectroscopy↗
PubMed2000

Efficient double-quantum excitation in rotational resonance NMR.

We present a new technique for double-quantum excitation in magic-angle-spinning solid-state NMR. The method involves (i) preparation of nonequilibrium longitudinal magnetization; (ii) mechanical excitation of zero-quantum coherence by spinning the sample at rotational resonance, and (iii) phase-coherent conversion of the zero-quantum coherence into double-quantum coherence by frequency-selective spin inversion. The double-quantum coherence is converted into observable magnetization by reversing the excitation process, followed by a pi/2 pulse. The method is technically simple, does not require strong RF fields, and is feasible at high spinning frequencies. In [(13)C(2),(15)N]-glycine, with an internuclear (13)C-(13)C distance of 0.153 nm, we achieve a double-quantum filtering efficiency of approximately 56%. In [11, 20-(13)C(2)]-all-E-retinal, with an internuclear (13)C-(13)C distance of 0.296 nm, we obtain approximately 45% double-quantum filtering efficiency.

Carbon Isotopes↗
PubMed2000

NMR experiments for the sign determination of homonuclear scalar and residual dipolar couplings.

A modified version of the JHH-TOCSY experiment, 'signed COSY', is presented that allows the determination of the sign of residual dipolar 1H-1H coupling constants with respect to the sign of one-bond 1H-X coupling constants in linear three-spin systems X-1H-1H, where X = 13C or 15N. In contrast to the original JHH-TOCSY experiments, the signs of J(HH) couplings may be determined for CH2-CH2 moieties and for uniformly 13C/15N-labelled samples. In addition, sensitivity is enhanced, diagonal peaks are suppressed and cross peaks are observed only between directly coupled protons, as in a COSY spectrum.

Aprotinin↗
PubMed2000

Determination of a molecular torsional angle in the metarhodopsin-I photointermediate of rhodopsin by double-quantum solid-state NMR.

We present a solid-state NMR study of metarhodopsin-1, the pre-discharge intermediate of the photochemical signal transduction cascade of rhodopsin, which is the 41 kDa integral membrane protein that triggers phototransduction in vertebrate rod cells. The H-C10-C11-H torsional angles of the retinylidene chromophore in bovine rhodopsin and metarhodopsin-I were determined simultaneously in the photo-activated membrane-bound state, using double-quantum heteronuclear local field spectroscopy. The torsional angles were estimated to be [phi] = 160+/-10 degrees for rhodopsin and phi = 180+/-25 degrees for metarhodopsin-I. The result is consistent with current models of the photo-induced conformational transitions in the chromophore, in which the 11-Z retinal ground state is twisted, while the later photointermediates have a planar all-E conformation.

Animals↗
PubMed2000

NaDNA-bipyridyl-(ethylenediamine)platinum (II) complex: structure in oriented wet-spun films and fibers.

Complexes of NaDNA with bipyridyl-(ethylenediamine)platinum(II) (abbreviated [(bipy)Pt(en)](2+)) in solid, oriented films, prepared with a wet-spinning method, have been studied using x-ray diffraction, elastic neutron scattering, two-dimensional magic-angle-spinning nuclear magnetic resonance (NMR), infrared (IR) linear dichroism, and IR absorption. All of these experiments indicate that the DNA in this complex is in the B conformation. The neutron diffraction experiments reveal that the rise per residue is 3.31 A, indicating that the [(bipy)Pt(en)](2+) molecular ion causes a small distortion of the B conformation. The neutron data in the direction perpendicular to the helical axis are consistent with a centered orthorhombic unit cell with a=22.65 A and b=32.2 A. The NMR and IR experiments show that the orientation of phosphate groups in the DNA small middle dot[(bipy)Pt(en)](2+) complex is the same as that observed for pure DNA in the B conformation. The IR experiments also show that the [(bipy)Pt(en)](2+) molecular ion stabilizes the B conformation of DNA down to 59% relative humidity, a low water activity. Mechanochemical experiments on wet-spun NaDNA fibers in 68% ethanol with and without [(bipy)Pt(en)](2+) reveal a 9% elongation of the DNA fibers as the complex is formed.

2,2'-Dipyridyl↗
PubMed1999

Anomalous rotational resonance spectra in magic-angle spinning NMR.

Magic-angle spinning NMR spectra of samples containing dilute spin-1/2 pairs display broadenings or splittings when a rotational resonance condition is satisfied, meaning that a small integer multiple of the spinning frequency matches the difference in the two isotropic shift frequencies. We show experimental rotational resonance NMR spectra of a 13C2-labeled retinal which are in qualitative disagreement with existing theory. We propose an explanation of these anomalous rotational spectra involving residual heteronuclear couplings between the 13C nuclei and the neighboring 1H nuclei. These couplings strongly influence the rotational resonance 13C spectrum, despite the presence of a strong radiofrequency decoupling field at the 1H Larmor frequency. We model the residual heteronuclear couplings by differential transverse relaxation of the 13C single-quantum coherences. We present a superoperator theory of the phenomenon and describe a numerical algorithm for rapid Liouville space simulations in periodic systems. Good agreement with experimental results is obtained by using a biexponential transverse relaxation model for each spin site.

Magnetic Resonance Spectroscopy↗
PubMed1999

High-order spin diffusion mechanisms in (19)F 2-D NMR of oxyfluorides.

Negative cross-peaks have been observed in the (19)F 2-D magnetization-exchange MAS NMR spectra of Ba(2)MoO(3)F(4) under fast-spinning conditions. The polarization transfer dynamics are studied as a function of the spinning frequency and the frequency separation of the resonances. The results are consistent with a novel mechanism, in which four spins simultaneously exchange Zeeman magnetization with each other, in an energy-conserving process.

Chemical Phenomena↗
PubMed1999

Multiple-quantum relaxation in the magic-angle-spinning NMR of 13C spin pairs.

We determine the decay rate constants of zero-, double- and single-quantum coherence for 13C spin pairs in magic-angle-spinning solid-state NMR. The double-quantum coherence is excited by a C7 pulse sequence and converted into zero-quantum coherence by a frequency-selective pair of pi/2 pulses. The zero-quantum coherence is reconverted into observable magnetization by a second pair of pi/2 pulses followed by a second C7 sequence. In a magnetically dilute system where the 13C-13C distance is 0.296 nm, the relaxation rate constants are consistent with a model of uncorrelated random fields at the two labeled 13C sites. In a fully-labelled system with a short 13C-13C distance of 0.153 nm, the measured rate constants are inconsistent with the uncorrelated random field model.

Carbon Isotopes↗
PubMed1999

Rotational resonance NMR of 13C2-labelled retinal: quantitative internuclear distance determination.

Rotational resonance phenomena are investigated in the solid-state magic-angle spinning NMR of all-E-[11,20-13C2]-retinal at a magnetic field of 4.7 T. We find good agreement between experiments and numerical simulations for the rotational resonance spectral peakshapes and for the rotor-driven magnetization exchange. The internuclear distance between the 13C-labelled C11 and C20 sites is determined to be 0.301 +/- 0.008 nm (from rotational resonance spectra) and 0.300 +/- 0.010 nm (from rotor-driven magnetization exchange), in agreement with the X-ray crystallographic distance of 0.296 nm. We show rotational resonance spectra which display perturbations from intermolecular homonuclear spin-spin interactions.

Carbon Isotopes↗