A 13C field-cycling NMR relaxometry investigation of proton tunnelling in the hydrogen bond: dynamic isotope effects, the influence of heteronuclear interactions and coupled relaxation

Concerted double proton transfer in the hydrogen bonds of a carboxylic acid dimer has been studied using 13C field-cycling NMR relaxometry. Heteronuclear 13C-1H dipolar interactions dominate the 13C spin-lattice relaxation which is significantly influenced by the polarisation state of the 1H Zeeman reservoir. The methodology of field-cycling experiments for such heteronuclear spin-coupled systems is studied experimentally and theoretically, including an investigation of various saturation-recovery and polarisation-recovery pulse sequence schemes. A theoretical model of the spin-lattice relaxation of this coupled system is presented which is corroborated by experiment. Spectral density components with frequencies omega(C), omega(C) + omega(H), and omega(C) - omega(H) are mapped out experimentally from the magnetic field dependence of the 13C and 1H spin-lattice relaxation and the proton transfer rate at low temperature is determined from their widths. Any dynamic isotope effect on the proton tunnelling in the hydrogen bond arising from 13C enrichment in the skeletal framework of the dimer is found to be smaller than experimental uncertainties (approximately 5%).     

Field-cycling NMR investigations of (13)C-(1)H cross-relaxation and cross-polarisation: the nuclear solid effect and dynamic nuclear polarisation

A field-cycling NMR investigation of (1)H-(13)C polarisation transfer using cross-relaxation and the nuclear solid effect (NSE) is described. Dynamic nuclear polarisation (DNP) of the (13)C spins is observed when forbidden transitions are driven by r.f. irradiation at the sum and difference Larmor frequencies of the two nuclei. When the (1)H spins are pre-polarised, a significant transfer of polarisation to the (13)C nuclei is achieved in a time short compared with the spin-lattice relaxation time of (13)C. The cross-polarisation arising from the NSE is studied as a function of B-field and time. These results are compared with the solutions of the differential equations that govern the coupled system of (1)H-(13)C spins. The effects of cross-relaxation are incorporated into the model for the first time and good agreement between theory and experiment is obtained. The experiments have been conducted at 20K on a (13)C-enriched sample of benzoic acid.     

A field-cycling NMR investigation of resonant spin-lattice relaxation features arising from tunnelling methyl groups

(1)H nuclear spin-lattice relaxation has been investigated in sodium acetate trihydrate and sorbic acid using field-cycling NMR in the solid state. The relaxation is dominated by the reorientation of the methyl groups. Resonant features arising from coherent tunnelling are observed in both the magnetic field dependence of the spin lattice relaxation rate, T(1)(-1)(B(z)) and in the inverse temperature dependence, T(1)(-1)(1/T). The two systems have different barrier heights and tunnelling frequencies, providing different perspectives on the tunnel resonance phenomena. The magnetic field dependence enables different spectral density components to be separately investigated and in the carboxylic acid, sorbic acid, concerted proton transfer in the hydrogen bonds is also identified at low field and low temperature. The methyl hindering barriers and the correlation times characterising the reorientational dynamics has been accurately determined in both materials.     

Long-lived nuclear spin states in the solution NMR of four-spin systems

The existence of long-lived nuclear spin states in four-spin systems is explored by solution-state NMR experiments. Long-lived states are proved to exist in three different natural product molecules, each containing either a AA'BB' or a AA'XX' proton spin system. The measured state lifetimes are between four and eight times the spin-lattice relaxation time constants.     

Study of slow molecular motions in α-Crystallin by proton magnetic spin-lattice relaxation in the doubly rotating frame

Proton magnetic spin-lattice relaxation in the effective field H₂ acting in the doubly rotating frame (DRF) was first applied to the study of slow internal protein dynamics in the submillisecond range of correlation times in the solid state. In this method the local dipolar magnetic field is reduced by the magic-angle rotating-frame method so that the resonance frequency of the relaxation experiment may be set below the value of the local field. As a result, unachievable by the standard nuclear magnetic resonance (NMR) relaxation techniques, slow molecular motions become experimentally accessible. The second effective field H₂ is produced by the shallow sine-wave phase modulation of the H₁ pulse. The registration of the DRF spin-lattice relaxation signal takes place directly during the continuous H₁ pulse by means of an additional low-frequency radio-frequency coil oriented along the H₀ field and operating at the rotating-frame NMR frequency of 100 kHz. The measurements of the spin-lattice relaxation time in the DRF within a wide temperature range have been performed in dry and hydrated α-crystallin powders. This is the major protein in the eye lens, which prevents the uncontrolled aggregation of proteins and keeps the lens transparent. The results demonstrate that the protein hydration does not change the amplitude of slow side-chain motions but significantly shortens its correlation time: from about 50 to about 0.5 μs in dry and hydrated samples, respectively. The hydration also decreases the activation energy and restricts the distribution of the correlation times.     

Rapid computer simulation of E.S.R. spectra

A fast computer algorithm is presented which permits simulation of the effects of rotational diffusion, electron and nuclear relaxation, microwave power, and modulation frequency upon saturation transfer (passage) E.S.R. spectra. Comparison of theoretical and experimental spectra for nitroxide spin-labelled biomolecules suggests that while the dependence of electron spin-lattice relaxation time upon rotational correlation time is weak, the variation of the ratio of the electron to nuclear spin-lattice relaxation times is significant and consideration of strong nuclear relaxation is necessary for the simulation of spectra characterized by correlation times near the reciprocal of the nitrogen nuclear resonance frequency.     

13C spin-lattice relaxation in natural diamond: Zeeman relaxation at 4.7 T and 300 K due to fixed paramagnetic nitrogen defects

13C spin-lattice relaxation times in the laboratory frame, ranging from 1.4 to 36 h, have been measured on a suite of five natural type Ia and Ib diamonds at 4.7 T and 300 K. Each of the diamonds contains two types of fixed paramagnetic centers with overlapping inhomogeneous electron paramagnetic resonance (EPR) lines. EPR techniques have been employed to identify these defects and to determine their concentrations and relaxation times at X-band. Spin-lattice relaxation behavior of 13C in diamonds containing paramagnetic P1, P2, N2. and N3 centers are discussed. Depending on the paramagnetic impurity types and concentrations present in each diamond, three different nuclear spin-lattice relaxation (SLR) paths exist, namely that due to electron SLR mechanisms and two types of three-spin processes (TSPs). The one three-spin process (TSP1) involves a simultaneous transition of two electron spins belonging to the same hyperfine EPR line and a flip of a 13C spin, while the other process (TSP2) involves two electron spins belonging to different hyperfine EPR lines and a 13C spin. It is shown that the thermal contact between the 13C nuclear Zeeman and electron dipole-dipole interaction reservoirs is field dependent, thus forming a bottleneck in the 13C relaxation path due to TSP1 at high magnetic fields.     

Nuclear magnetic resonance study of ultrananocrystalline diamonds

We report on a nuclear magnetic resonance (NMR) study of ultrananocrystalline diamond (UNCD) materials produced by detonation technique. Analysis of the ¹³C and ¹H NMR spectra, spin-spin and spin-lattice relaxation times in purified UNCD samples is presented. Our measurements show that UNCD particles consist of a diamond core that is partially covered by a sp ²-carbon fullerene-like shell. The uncovered part of outer diamond surface comprises a number of hydrocarbon groups that saturate the dangling bonds. Our findings are discussed along with recent calculations of the UNCD structure. Significant increase in the spin-lattice relaxation rate (in comparison with that of natural diamond), as well as stretched exponential character of the magnetization recovery, are attributed to the interaction of nuclear spins with paramagnetic centers which are likely fabrication-driven dangling bonds with unpaired electrons. We show that these centers are located mainly at the interface between the diamond core and shell.     

Microscopic evidence for co-ionic conductivity in (Na,Li) β-alumina

Measurements of nuclear spin-lattice relaxation times T₁ as a function of temperature are reported for ⁷Li in Liβ-alumina and mixed (Na,Li) β-alumina at several frequencies. In the mixed case the T₁ data exhibit a nearly symmetric minimum below room temperature. For Liβ-alumina the T₁ curve has, in addition, a high-temperature “shoulder” or unresolved secondary minimum which corresponds to the activation energy and attempt frequency obtained from tracer diffusion and Raman spectroscopy, respectively. We conclude that the addition of Na eliminates this high-barrier diffusional motion of the Li ions, in accord with electrochemical studies. Our results are discussed in terms of competing models which describe nuclear spin-lattice relaxation.     

Nuclear magnetic resonance relaxometry of the normal heart: Relationship between collagen content and relaxation times of the four chambers

The use of nuclear magnetic resonance (NMR) relaxation time measurements for characterization of abnormal cardiac tissue depends upon knowledge of variations of relaxation times of normal myocardium and determinants of these variations. We calculated in vitro NMR T₁ and T₂ relaxation times of canine myocardium from the four cardiac chambers, and determined hydroxyproline concentration (as a measure of collagen) and percent water content of the samples. We found both water content and T₁ relaxation time of the right ventricle to be significantly greater than the left atrium (p < 0.05). T₂ relaxation time of the left ventricle was found to be shorter than each of the other three chambers (p < 0.05). There were significant correlations between the spin-lattice relaxation time and both percent water content (r = 0.58) and hydroxyproline concentration (r = 0.45). A significant correlation was also found between T₂ relaxation time and hydroxyproline concentration (r = 0.49). When T₁ and T₂ were adjusted for water and hydroxyproline content, there was no longer any evidence for significant interchamber differences for either T₁ or T₂. These data suggest that differences in NMR relaxation times exist among the four chambers of the normal canine heart. Furthermore, a major determinant of myocardial spin-lattice relaxation time is tissue water content while both collagen content and percent water content significantly contribute to variability in cardiac chamber T₂ relaxation times.     

Nuclear quadrupolar spin-lattice relaxation in the amorphous state

It is proposed that the nuclear quadrupole spin-lattice relaxation in glasses is due to interaction of solitons with the nuclear quadrupole moment. The magnitude of the interaction is estimated and the resulting temperature dependence of the spin-lattice relaxation time is compared to experiment.     

The influence of macromolecular polymerization of spin-lattice relaxation of aqueous solutions

The docking or polymerization of globular proteins is demonstrated to cause changes in proton NMR spin-lattice (T1) relaxation times. Studies on solutions of lysozyme, bovine serum albumin, actin, and tubulin are used to demonstrate that two mechanisms account for the observed changes in T1. Polymerization displaces the hydration water sheath surrounding globular proteins in solution that causes an increase in T1. Polymerization also slows the average tumbling rate of the proteins, which typically causes a contrary decrease in T1. The crystallization reaction of lysozyme in sodium chloride solution further demonstrates that the "effective" molecular weight can either decrease or increase T1 depending on how much the protein is slowed. The displacement of hydration water increases T1 because it speeds up the mean motional state of water in the solution. Macromolecular docking typically decreases T1 because it slows the mean motional state of the solute molecules. Cross-relaxation between the proteins and bound water provides the mechanism that allows macromolecular motion to influence the relaxation rate of the solvent. Fast chemical exchange between bound, structured, and bulk water accounts for monoexponential spin-lattice relaxation. Thus the spin-lattice relaxation rate of water in protein solutions is a complex reflection of the motional properties of all the molecules present containing proton magnetic dipoles. It is expected, as a result, that the characteristic relaxation times of tissues will reflect the influence of polymerization changes related to cellular activities.     

High-frequency dynamic nuclear polarization in the nuclear rotating frame

A proton dynamic nuclear polarization (DNP) NMR signal enhancement (epsilon) close to thermal equilibrium, epsilon = 0.89, has been obtained at high field (B(0) = 5 T, nu(epr) = 139.5 GHz) using 15 mM trityl radical in a 40:60 water/glycerol frozen solution at 11 K. The electron-nuclear polarization transfer is performed in the nuclear rotating frame with microwave irradiation during a nuclear spin-lock pulse. The growth of the signal enhancement is governed by the rotating frame nuclear spin-lattice relaxation time (T(1rho)), which is four orders of magnitude shorter than the nuclear spin-lattice relaxation time (T(1n)). Due to the rapid polarization transfer in the nuclear rotating frame the experiment can be recycled at a rate of 1/T(1rho) and is not limited by the much slower lab frame nuclear spin-lattice relaxation rate (1/T(1n)). The increased repetition rate allowed in the nuclear rotating frame provides an effective enhancement per unit time(1/2) of epsilon(t) = 197. The nuclear rotating frame-DNP experiment does not require high microwave power; significant signal enhancements were obtained with a low-power (20 mW) Gunn diode microwave source and no microwave resonant structure. The symmetric trityl radical used as the polarization source is water-soluble and has a narrow EPR linewidth of 10 G at 139.5 GHz making it an ideal polarization source for high-field DNP/NMR studies of biological systems.     

High-resolution magnetic relaxation dispersion measurements of solute spin probes using a dual-magnet system.

The magnetic field dependence of the nuclear spin-lattice relaxation rate provides a detailed report of the spectral density functions that characterize the intra- and intermolecular fluctuations that drive magnetic relaxation. We have addressed the difficult sensitivity and resolution problems associated with low magnetic field strengths by using two magnets in close proximity and shielded from each other. The sample is stored in the high magnetic field, pneumatically driven to the variable satellite field, then returned to the high field for detection at high resolution. A magnetic shield effectively decouples the two magnets so that varying the satellite field strength has minimal effect on the field strength and shim of the high field magnet. The disadvantage of the sample-shuttle magnet-pair system is the restriction imposed on the relaxation times by the finite shuttle times. Experiments not described here have shown this rate maximum to be about 20 s(-1) for most practical solutions. However, we demonstrate here that the sensitivity gains over switched-current magnet systems permit characterization of solute inter- and intramolecular dynamics over the time scale range from tens of microseconds to less than a picosecond. This range permits investigation of a number of crucial chemical dynamics questions, while high sensitivity permits examination of a variety of solute spins. Representative data are presented for (1)H, (111)Cd, and (7)Li.     

Measurement of spin-lattice relaxation times with longitudinal detection

New experimental schemes to measure spin-lattice relaxation times T₁ on the basis of inversion-recovery and saturation-recovery experiments with longitudinal detection are introduced. With this approach, paramagnetic species with T₁ values as short as 20 ns can be measured. Possibilities to reduce unwanted signals and instrumental artifacts are analyzed. An experiment where the signal is induced directly by the time-dependent M₂ magnetization is also proposed. Experimental results for organic radicals and defect centers are presented and compared with data obtained with conventional techniques, and a metal complex at 250 K is analyzed where it is very difficult to get information about relaxation times with established methods because of fast spin-spin relaxation.     

Beyond the T1 limit: singlet nuclear spin states in low magnetic fields

Low-field nuclear spin singlet states may be used to store nuclear spin order in a room temperature liquid for a time much longer than the spin-lattice relaxation time constant T1. The low-field nuclear spin singlets are unaffected by intramolecular dipole-dipole relaxation, which is generally the predominant relaxation mechanism. We demonstrate storage of nuclear spin order for more than 10 times longer than the measured value of T1. This phenomenon may facilitate the development of nuclear spin hyperpolarization methods and may allow the study of motional processes which occur too slowly for existing NMR techniques. This is the first time that the memory of nuclear spins has been extended well beyond the T1 limit in a system lacking intrinsic magnetic equivalence.     

Critical point and the nature of the pseudogap of single-layered copper-oxide Bi2Sr2-xLaxCuO6+delta superconductors

We apply strong magnetic fields of H=28.5 to 43 T to suppress superconductivity (SC) in the cuprates Bi2Sr2-xLaxCuO6+delta (x=0.65, 0.40, 0.25, 0.15, and 0), and investigate the low temperature (T) normal state by 63Cu nuclear spin-lattice relaxation rate (1/T1) measurements. We find that the pseudogap (PG) phase persists deep inside the overdoped region but terminates at x approximately 0.05, which corresponds to the hole doping concentration of approximately 0.21. Beyond this critical point, the normal state is a Fermi liquid that persists as the ground state when superconductivity is removed by the magnetic field. A comparison of the superconducting state with the H-induced normal state in the x=0.40 (Tc=32 K) sample indicates that there remains substantial part of the Fermi surface even in the fully developed PG state, which suggests that the PG and SC are coexisting matters.     

Effects of paramagnetic cations on the nonexponential spin-lattice relaxation of rare spin nuclei in solids

Nonexponential spin-lattice relaxation is often observed for rare spin nuclei in the solid state. Deviation from single-component decay may be amplified by the coupling of rare spin nuclei to paramagnetic centers. Nonexponential spin-lattice relaxation was observed in derivatized silica gels resins. This phenomenon was localized and enhanced when paramagnetic transition metal cations were bound to surface functional groups. A stretched exponential analysis method was determined to be robust in fitting nonexponential relaxation curves for silica gels both with and without bound paramagnetic ions. Spin-lattice relaxation rates (T₁⁻¹) for functional group nuclei increased as a function of percent surface coverage with metal ion. The magnitude of the relaxation rate increase was dependent upon internuclear distances from the paramagnetic center. At low surface coverages, a semi-random distribution of paramagnetic centers increased the degree of stretching of spin-lattice relaxation decays, as measured by decreases in the calculated stretching parameter β. At higher surface coverages, calculated β values reached a limiting value, indicating that while the spin-diffusion mechanism in metal-ex-changed silica gels is restricted, it is not completely diminished.     

Delocalized quasiparticles in the vortex state of an overdoped high-T(c) superconductor probed by 63Cu NMR

We report the spin Knight shift (K(s)) and the nuclear spin-lattice relaxation rate (1/T1) in the vortex state as a function of magnetic field (H) up to 28 T in the high-Tc superconductor TlSr2CaCu2O6.8 (Tc = 68 K). At low temperatures well below Tc, both K(s) and 1/T1 measured around the middle point between the two nearest vortices (saddle point) increase substantially with increasing field, which indicate that the quasiparticle states with an ungapped spectrum are extended outside the vortex cores in a d-wave superconductor. The density of states (DOS) around the saddle point is found to be kappaN(0)square root[H/H(c2)], with kappa = 0.5-0.7 and N0 being the normal-state DOS.     

Measurement of spin-lattice relaxation times of C in organic solids

A transient nuclear Overhauser effect (NOE) makes measurements of the ¹³C spin-lattice relaxation times in organic solids complicated. Extended Solomon equations are applied in order to describe ¹³C spin-lattice relaxation with ¹H r.f. field irradiation. Spin-lattice relaxation under r.f. irradiation is shown to be generally a triple-exponential process, but it can be reduced to be single-exponential under stronger r.f. field irradiation as well as in the absence of ¹H initial magnetizations. Based on numerical calculations, the difference between spin-lattice relaxation curves obeying T₁^C < T₁^H and those obeying T₁^C < T₁^H is clearly indicated. The methyl group resonances in solid-state -valine are examined, and the experimental results agree well with the theoretical results.