Relaxation (NMR)

About: Relaxation (NMR) is a research topic. Over the lifetime, 29342 publications have been published within this topic receiving 689851 citations.

Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: The importance of level crossings

Abstract: We present theoretical calculations of dynamic nuclear polarization (DNP) due to the cross effect in nuclear magnetic resonance under magic-angle spinning (MAS). Using a three-spin model (two electrons and one nucleus), cross effect DNP with MAS for electron spins with a large g-anisotropy can be seen as a series of spin transitions at avoided crossings of the energy levels, with varying degrees of adiabaticity. If the electron spin-lattice relaxation time T1e is large relative to the MAS rotation period, the cross effect can happen as two separate events: (i) partial saturation of one electron spin by the applied microwaves as one electron spin resonance (ESR) frequency crosses the microwave frequency and (ii) flip of all three spins, when the difference of the two ESR frequencies crosses the nuclear frequency, which transfers polarization to the nuclear spin if the two electron spins have different polarizations. In addition, adiabatic level crossings at which the two ESR frequencies become equal serve to maintain non-uniform saturation across the ESR line. We present analytical results based on the Landau-Zener theory of adiabatic transitions, as well as numerical quantum mechanical calculations for the evolution of the time-dependent three-spin system. These calculations provide insight into the dependence of cross effect DNP on various experimental parameters, including MAS frequency, microwave field strength, spin relaxation rates, hyperfine and electron-electron dipole coupling strengths, and the nature of the biradical dopants.

Entropic Barriers, Activated Hopping and the Glass Transition in Colloidal Suspensions

Abstract: A microscopic kinetic description of single-particle transient localization and activated transport in glassy fluids is developed which combines elements of idealized mode-coupling theory, density functional theory, and activated rate theory. Thermal fluctuations are included via a random force which destroys the idealized glass transition and restores ergodicity through activated barrier hopping. The approach is predictive, containing no adjustable parameters or postulated underlying dynamic or thermodynamic divergences. Detailed application to hard-sphere colloidal suspensions reveals good agreement with experiment for the location of the kinetic glass transition volume fraction, the dynamic incoherent scattering relaxation time, apparent localization length, and length scale of maximum nongaussian behavior. Multiple connections are predicted between thermodynamics, short-time dynamics in the nearly localized state, and long-time relaxation by entropic barrier crossing. A critical comparison of the fluid volume fraction dependence of the hopping time with fit formulas which contain ideal divergences has been performed. Application of the derivative Stickel analysis suggests that the fit functions do not provide an accurate description over a wide range of volume fractions. Generalization to treat the kinetic vitrification of more complex colloidal and nanoparticle suspensions, and thermal glass-forming liquids, is possible.

Virtual and solution conformations of oligosaccharides.

Abstract: The possibility that observed nuclear Overhauser enhancements and bulk longitudinal relaxation times, parameters measured by 1H NMR and often employed in determining the preferred solution conformation of biologically important molecules, are the result of averaging over many conformational states is quantitatively evaluated. Of particular interest was to ascertain whether certain 1H NMR determined conformations are "virtual" in nature; i.e., the fraction of the population of molecules actually found at any time within the subset of conformational space defined as the "solution conformation" is vanishingly small. A statistical mechanics approach was utilized to calculate an ensemble average relaxation matrix from which (NOE)'s and (T1)'s are calculated. Model glycosidic linkages in four oligosaccharides were studied. The solution conformation at any glycosidic linkage is properly represented by a normalized, Boltzmann distribution of conformers generated from an appropriate potential energy surface. The nature of the resultant population distributions is such that 50% of the molecular population is found within 1% of available microstates, while 99% of the molecular population occupies about 10% of the ensemble microstates, a number roughly equal to that sterically allowed. From this analysis we conclude that in many cases quantitative interpretation of NMR relaxation data, which attempts to define a single set of allowable torsion angle values consistent with the observed data, will lead to solution conformations that are either virtual or reflect torsion angle values possessed by a minority of the molecular population. On the other hand, calculation of ensemble average NMR relaxation data yields values in agreement with experimental results. Observed values of NMR relaxation data are the result of the complex interdependence of the population distribution and NOE (or T1) surfaces in conformational space. In conformational analyses, NMR data can therefore be used to test different population distributions calculated from empirical potential energy functions.

Protein rotational relaxation as studied by solvent 1H and 2H magnetic relaxation.

Abstract: Earlier studies of the magnetic field dependence of the nuclear spin magnetic relaxation rate of solvent protons in solutions of diamagnetic proteins have indicated that this dependence (called relaxation dispersion) is related to the rotational Brownian motion of solute proteins. In essence, the dispersion is such that 1/T1 (the proton spin-lattice relaxation rate) decreases monotonically as the magnetic field is increased from a very low value (approximately 10 Oe); the dispersion has a point of inflection at a value of magnetic field which depends on protein size, shape, concentration, temperature, and solvent composition. The value of the proton Larmor precession frequency nu(c) at the inflection field appears to relate to tau (R), the rotational relaxation time of the protein molecules. We have measured proton relaxation dispersions for solutions of various proteins that span a three-decade range of molecular weights, and for one sample of transfer ribonucleic acid. We have also measured deuteron relaxation dispersions for solutions of three proteins: lysozyme, carbonmonoxyhemoglobin, and Helix pomatia hemocyanin with molecular weight 900 000. A quantitative relationship between both proton and deuteron dispersion data and protein rotational relaxation is confirmed, and the point is made that magnetic dispersion measurements are of very general applicability for measuring the rotational relaxation rate of macromolecules in solution. It has been previously shown that the influence of proton motion on the relaxation behavior of the solvent is not due to exchange of solvent molecules between the bulk solvent and a hydration region of the protein. In the present paper, we suggest that the interaction results from a long range hydrodynamic effect fundamental to the situation of large Brownian particles in an essentially continuum fluid. The general features of the proposed mechanism are indicated, but no theoretical computations are presented.

Electronic Structures of Single-Walled Carbon Nanotubes Determined by NMR

Abstract: Single-walled carbon nanotubes were studied by 13C nuclear magnetic resonance (NMR). Two types of 13C nuclear spins were identified with different spin-lattice relaxation rates. The fast-relaxing component, assigned to metallic tubes, followed the relaxation behavior expected in metals, and the density-of-states at the Fermi level increased with decreasing tube diameter. The slow-relaxing component has a significantly lower density-of-states at the Fermi level. Exposure to oxygen has a substantial effect on relaxation rates of both components.