NMR with Hyperpolarised Protons in Metals

Proton pulse NMR, established as a versatile method in Solid State Physics, Chemistry, Biology and Medical Science, requires on the order of 10¹⁸ nuclei to detect an electromagnetic signal in a free induction decay (FID). The main cause for this small sensitivity is the low polarisation in the order of a few ppm due to the Boltzmann distribution in the magnetic field. Thus, NMR experiments on hydrogen are limited to metals with extremely high hydrogen solubility like Pd near room temperature. Using a polarised proton beam, a NMR signal is possible with as few as 10¹³ implanted nuclei. For the first time spin–spin and spin–lattice relaxation times were measured in Au and W with this technique at the Bonn cyclotron.     

Recent progress in NMR studies on organic conductors

Recent ¹³\mathrmC\mbox-NMR studies on a family of quasi‐two‐dimensional organic conductors based on BEDT‐TTF molecules are reviewed in the light of the role of electron–electron correlation in a variety of electronic states and of the symmetry of electron pairing in the superconducting state. Comparison of the nuclear spin‐lattice relaxation rate, conducting property and molecular arrangement indicates a close relationship between the molecular arrangement and manifestation of electron correlation. The metal/nonmetal phases in the isostructural \kappa\mbox- (BEDT\mbox-TTF)₂X systems, which are in the strong dimeric regime, are understood as highly correlated metals and insulators crossing the Mott transition. For the 10‐K superconducting phase situated near the Mott transition, the absence of Hebel–Slichter coherence peak and a low‐temperature T³-dependence of the nuclear spin‐lattice relaxation rate suggest unconventional superconductivity with line nodes in gap parameter or highly anisotropic one. This revised version was published online in July 2006 with corrections to the Cover Date.     

Use of Additional Fast-Relaxing Paramagnetic Species for Improvement of RIDME Performance

A method of improving relaxation-induced dipolar modulation enhancement (RIDME) performance by an artificial increase of electron spin–lattice relaxation rate is introduced and tested on a model nitroxide biradical. A substantial increase of its electron spin–lattice relaxation rate is achieved by the addition of a fast-relaxing paramagnetic holmium complex to the sample solution. The electron spin–spin relaxation rate of the nitroxide does not change dramatically upon this addition. The suggested method allows obtaining a deep dipolar modulation in the RIDME experiment, which is free from distortions caused by spectral diffusion processes.     

Pseudo spin gap in high‐Tc oxides observed by NMR

From the temperature dependence of the ⁶³Cu nuclear spin‐lattice relaxation rate, 1/T₁T, in the planar Cu(2) sites, it is now well established that a highly enhanced and strongly temperature dependent relaxation process due to antiferromagnetic Cu spin fluctuations exists in all of the high‐T_c’s. The data also exhibit the opening of a gap in the low‐lying magnetic excitations with an energy comparable to the superconducting gap, particularly for the so‐called low doping regime. It is also found that, irrespective of the system, the temperature at which the spin‐gap opens, T_sg, determined as the peak of 1/T₁T vs. T, has a linear decrease with increasing of the doping concentration. A spin‐gap phase diagram is proposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Solid-State NMR Studies on the Guest Ordering and Dynamics in α,ω-Dibromoalkane/Urea Inclusion Compounds

Solid-state nuclear magnetic resonance (NMR) spectroscopy is utilized to study the molecular behavior of 1,10-dibromodecane and 1,11-dibromoundecane in their urea inclusion compounds. The guest dynamics and conformational order are explored by ¹³C cross polarization magic-angle spinning (CP/MAS) and ¹H MAS NMR spectroscopy which confirm an all-trans conformation of the guest chains. Dynamic ²H NMR experiments are carried out on two guest molecules selectively deuterated at both end groups. A quantitative analysis of the experimental data, obtained from variable-temperature line shape, spin–spin and spin–lattice relaxation measurements, shows that both guest molecules undergo similar motions within the investigated temperature range between 100 and 298 K. The combination of nondegenerate 6-site (or 3-site) rotational jumps and small-angle overall chain wobbling provides an appropriate motional model for the guest motions in these compounds. It is found that the populations of the jump sites exhibit a characteristic temperature dependence, although a discontinuity is missing at the solid–solid phase transition. The same holds for the guest motions which also remain unaffected by the change of the urea lattice structure. Rather, a discontinuity of the guest dynamics at about 30 and 10 degrees above the corresponding solid–solid phase transition is observed for 1,10-dibromodecane and 1,11-dibromoundecane in urea, respectively. Likewise, there is no clear evidence for an odd–even effect due to the change of the guest chain length on the molecular properties of the present inclusion compounds. As a general result, it is concluded that the intermolecular interactions in the present materials are stronger than in n-alkane/urea inclusion compounds. Authors' address: Klaus Müller, Institut für Physikalische Chemie, Universit?t Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany     

Factors Affecting Early-Age Hydration of Ordinary Portland Cement Studied by NMR: Fineness,Water-to-Cement Ratio and Curing Temperature

The aim of the present study was to apply nuclear magnetic resonance (NMR) relaxation measurements for understanding the microstructure evolution of cement paste during hydration. Ordinary Portland cement powder was mixed with double-distilled water, and hydration process was analyzed via ¹H proton NMR spin–spin relaxation time. In order to induce strong modification of the rate of hydration, water-to-cement ratio, curing temperature and cement fineness were varied. The evolution of the NMR spin–spin relaxation time, T ₂, of hydrating water versus the hydration time was monitored from the very first few minutes after the mixing up to several hours. Authors' address: Marcella Alesiani, Department of Physics, University La Sapienza, Piazzale Aldo Moro 5, 00185 Rome, Italy     

Molecular Dynamics in a New Solid Glucofuranose-Based Low-Molecular-Weight Organogelator as Studied by 1H NMR

The proton spin–lattice relaxation time T ₁ and the nuclear magnetic resonance second moment were used to study the molecular dynamics of 1,2-O-(1-ethylpropylidene)-α-D-glucofuranose, a new low-molecular-weight organogelator, in the temperature range of 85–308 K. The observed T ₁ minima were attributed to the motion of methyl groups. The experimental data were interpreted in terms of Haupt's theory assuming the tunneling-assisted relaxation process. Authors' address: Jadwiga Tritt-Goc, Institute of Molecular Physics, Polish Academy of Sciences, M. Smoluchowskiego 17, Poznań 60-179, Poland     

Separation of quadrupolar and magnetic contributions to spin-lattice relaxation in the case of a single isotope

We present a NMR pulse double-irradiation method which allows one to separate magnetic from quadrupolar contributions in the spin–lattice relaxation. The pulse sequence fully saturates one transition while another is observed. In the presence of a Δm = 2 quadrupolar contribution, the intensity of the observed line is altered compared to a standard spin-echo experiment. We calculated analytically this intensity change for spins I = 1, , , thus providing a quantitative analysis of the experimental results. Since the pulse sequence we used takes care of the absorbed radiofrequency power, no problems due to heating arise. The method is especially suited when only one NMR sensitive isotope is available. Different cross-checks were performed to prove the reliability of the results obtained. The applicability of this method is demonstrated by a study of the plane oxygen ¹⁷O (I = ) in the high-temperature superconductor YBa₂Cu₄O₈: the ¹⁷O spin–lattice relaxation rate consists of magnetic as well as quadrupolar contributions.     

Knight shifts for short-lived β emitters in Pt

The Knight shifts K for short-lived β emitters ¹²N and ²⁷Si implanted in Pt have been measured by means of β-NMR technique. The results were K(¹²N in Pt)= +(5.8 ± 2.1)× 10^-4 and K(²⁷Si in Pt)= +(1.4 ± 0.8)× 10^-3. The spin–lattice relaxation time T₁ was measured for ¹²N in Pt. The result was T₁(¹²N in Pt, T=300 K)= 66 ± 8 ms, thus, T₁T= 20 ± 2 Ks. The present Knight shifts are in good agreement with the KKR band structure calculation with local lattice relaxation determined theoretically. This revised version was published online in August 2006 with corrections to the Cover Date.     

Proton Spin–Lattice Relaxation Study of the Setting Reaction in Conventional and Resin-Modified Glass-Ionomer Dental Cements

The setting processes in KetacCem, AquaCem and Fuji I glass-ionomer dental cements (GIC) as well as in the resin-modified glass-ionomer dental cement (RM-GIC) Fuji Plus have been studied by proton spin–lattice, T ₁, and spin–spin, T ₂, relaxation. The setting time dependence of the degree of hydration was studied as well. In contrast to zinc oxide dental cements, the changes in T ₁ and T ₂ are determined by the interactions of the water with the internal surface. Proton nuclear magnetic resonance relaxation is thus suitable to follow the setting of GIC and RM-GIC and gives valuable information on the GIC hardening dynamics. Authors' address: Tomaz Apih, J. Stefan Institute, Jamova 39, Ljubljana 1000, Slovenia     

Dynamics of α-Tocopherol Acetate: Proton Relaxation Studies Supported by Molecular Dynamics Simulations

Dynamical properties of α-tocopherol acetate (commonly known as vitamin E) have been investigated in a broad temperature range (below and above the glass transition) by means of proton spin–lattice relaxation. Two distinct relaxation processes have been detected in the studied temperature range. One of them, present in the solid phase, has been attributed to reorientation of methyl groups. In order to identify the motional process leading to the proton relaxation above the glass transition temperature (T _g), molecular dynamics (MD) simulations have been performed, which provided time correlation functions for several internuclear vectors in the molecule. The high-temperature relaxation process is primarily due to dynamics of the aromatic rings of the tocopherol molecule; however, a considerable contribution of diffusion of the aliphatic chain cannot be excluded. Comparing the nuclear magnetic resonance (NMR) results with MD and relaxation data of dielectric spectroscopy (DS) available in the literature (K. Kamiński, S. Maślanka, J. Zioło, M. Paluch, K.J. McGrath, C.M. Roland, Phys Rev E 75:011903-7, 2007; E. Szwajczak, J. Świergiel, R. Stagraczyński, J. Jadżyn, Phys Chem Liq 47:460–466, 2009), the motional process observed in NMR relaxation studies above T _g has been identified with the δ process observed in DS.     

EPR Studies of DOPA–Melanin Complexes with Fe(III)

Paramagnetic centers in 3,4-dihydroxyphenylalanine–melanin and its complexes with Fe(III) were examined by electron paramagnetic resonance (EPR) spectroscopy. Paramagnetic centers of melanin play an important role in detoxification of environment and they reveal high activity in binding of metal ions. Two different signals were observed in EPR spectra: lines of o-semiquinone free radicals and lines of paramagnetic Fe(III). Amplitudes of EPR lines of both free radicals and iron ions decrease with increasing Fe(III) content in melanin–metal ion complexes. Free radical concentrations in the melanin samples, g-factors, amplitudes and line widths of EPR spectra were determined. It was stated that fast spin–lattice relaxation processes exist in both free radical system and paramagnetic iron ions in melanin complexes.     

Molecular Dynamics of Alkenylphenol Derivatives in Solution as Studied by NMR Spectroscopy

The formation of hydrogen bonds and molecular dynamics of alkenylphenol derivatives has been investigated in solution using nuclear magnetic resonance. The results confirm formation of an N···H, O···H-type intramolecular hydrogen bond. The spin–lattice relaxation times (T ₁) and activation energy of molecular dynamics have been investigated confirming the importance of relaxation times as a very sensitive tool for studying molecular mobility.     

Contributions of Spin–Lattice Relaxation to the Echo Decay of Planar Cu in High-Temperature Superconductors

Measurement ofT_2G, the Gaussian component of the spin-echo envelope of planar Cu nuclei in high-temperature superconductors, gives important information about the real part of the Cu electron spin susceptibility. In the traditional picture of the planar Cu echo decay, the internuclear coupling is assumed to remain static with respect to spin–lattice relaxation and mutual exchange fluctuations. In some circumstances, however, this assumption breaks down. We calculate the internuclear corrections arising from spin–lattice relaxation to the conventional theory ofT_2Gand show thatT_2Gcan be easily corrected for these effects. We argue that mutual exchanges due to the perpendicular indirect couplings are suppressed in these materials. For YBa₂Cu₄O₈, we find a correction on the order of 10% inT_2Gand using the corrected values we find that the isotope ratio⁶³T_2G/⁶⁵T_2Gagrees with theory.     

Investigation of nuclear-spin couplings in the lithium fluorides as possible candidates for crystal nuclear magnetic resonance quantum computing devices

We have performed ⁷Li and ¹⁹F nuclear magnetic resonance (NMR) in two lithium fluorides BaLiF₃ and YLiF₄ to explore the possibility of a crystal NMR quantum computing device. We find that (1) both the absolute values and the angular dependences of the line widths can primarily be accounted for by the nuclear dipolar fields, and (2) the spin–lattice relaxation times are long enough for quantum computations. These characteristics indicate that these crystals can be possible candidates for quantum computing devices. We also find that, in the perovskite structures like BaLiF₃, magic angles are quite effective to diminish the nuclear dipole fields, which enables us to treat some nuclei as ‘isolated’. We propose using this feature to create low-dimensional nuclear-spin networks in the crystals. Received: 29 January 2001 / Accepted: 6 February 2001 / Published online: 3 April 2001     

Magnetic hyperfine field of Hg in nickel and the sign of magnetic moment of 197mAu by NMR-ON

Nuclear magnetic resonance on oriented nuclei (NMR-ON) measurements were performed on the successive decay of ^197mHg–^197mAu in Ni. The NMR-ON resonance spectra of ^197mHgNi were obtained by detecting the 134 keV γ-ray from the decay of ^197mHg and the 279 keV γ-ray from the decay of ^197mAu. The magnetic hyperfine splitting frequency of ^197mHgNi in an external magnetic field of 0.2 T has been determined as 16.55(6) MHz. With the known g-factor of ^197mHg the hyperfine field of B₈₂(^197mHgNi)= -13.53(6) T was deduced. The anisotropy of the 279 keV γ-ray (^197mAu to ¹⁹⁷Au) increased at the resonance. This phenomenon was explained using the spin inversion process including the lifetime of the isomer and the spin–lattice relaxation time. The sign of the g-factor of ^197mAu was determined to be positive. This revised version was published online in August 2006 with corrections to the Cover Date.     

Influencing the satellite transitions of half-integer quadrupolar nuclei for the enhancement of magic angle spinning spectra

Double frequency sweeps can induce spin transitions in a set of satellites of a half-integer quadrupolar nucleus by simultaneously passing through resonance for a satellite pair. It is shown that by transferring population from the outer spin levels to the inner |1/2 and |−1/2 levels an increased intensity for central transition spectra is obtained. Although Magic Angle Spinning in principle interferes with this process, and the adiabaticity of the passages is different for every crystallite in a powder, enhanced spectra with undistorted line shapes are obtained for I=3/2 (²³Na) and 5/2 (²⁷Al) spins experiencing quadrupolar interactions with ω_Q in the range 0.1–3 MHz. Even at spinning speeds up to 30 kHz significant enhancements are obtained. An analysis of the combined effects of double frequency sweeps (DFS) and MAS indeed shows strongly different effects for different crystallites in powder ranging from no gain at all to the theoretical maximum gain of 2I. As the effects are randomly distributed over all orientations on a sphere this is averaged over the whole line shape. Therefore, undistorted powder patterns are obtained enhanced by the average gain over the individual crystallites. Saturation of the satellite transitions, which can only be achieved if spin–spin relaxation is sufficiently strong, leads to identical results. Optimization of the sweeps should be toward an optimal effect on the population transfer to the central levels and chosen short with respect to spin–lattice relaxation times.     

Consequences of Xe–H Cross Relaxation in Aqueous Solutions

We have investigated the transfer of polarization from ¹²⁹Xe to solute protons in aqueous solutions to determine the feasibility of using hyperpolarized xenon to enhance ¹H sensitivity in aqueous systems at or near room temperatures. Several solutes, each of different molecular weight, were dissolved in deuterium oxide and although large xenon polarizations were created, no significant proton signal enhancement was detected in -tyrosine, α-cyclodextrin, β-cyclodextrin, apomyoglobin, or myoglobin. Solute-induced enhancement of the ¹²⁹Xe spin–lattice relaxation rate was observed and depended on the size and structure of the solute molecule. The significant increase of the apparent spin–lattice relaxation rate of the solution phase ¹²⁹Xe by α-cyclodextrin and apomyoglobin indicates efficient cross relaxation. The slow relaxation of xenon in β-cyclodextrin and -tyrosine indicates weak coupling and inefficient cross relaxation. Despite the apparent cross-relaxation effects, all attempts to detect the proton enhancement directly were unsuccessful. Spin–lattice relaxation rates were also measured for Boltzmann ¹²⁹Xe in myoglobin. The cross-relaxation rates were determined from changes in ¹²⁹Xe relaxation rates in the α-cyclodextrin and myoglobin solutions. These cross-relaxation rates were then used to model ¹H signal gains for a range of ¹²⁹Xe to ¹H spin population ratios. These models suggest that in spite of very large ¹²⁹Xe polarizations, the ¹H gains will be less than 10% and often substantially smaller. In particular, dramatic ¹H signal enhancements in lung tissue signals are unlikely.     

<Superscript>1</Superscript>H Spin–Lattice Relaxation Study of Dynamical Inequivalence of Methyl Groups in Solid 1,2-<Emphasis Type="Italic">O</Emphasis>-(1-Ethylpropylidene)-α-<Emphasis Type="SmallCaps">d</Emphasis>-Glucofuranose

We investigated the dynamics of methyl groups in organic polycrystalline 1,2-O-(1-ethylpropylidene)-α-d-glucofuranose by the proton spin–lattice relaxation method. The temperature and nuclear magnetic resonance Larmor frequency dependence of relaxation time is presented and interpreted in terms of simple possible dynamical model for the reorientation of methyl groups: the random hopping for methyl groups, which are in a, b, and c sites in the crystal. The energy E _a of 13.5 kJ mol⁻¹ for the a-type methyl groups is typical for methyl groups in ethyl groups. In contrast, the b- and c-methyl groups characterized by the lower E _a values of 9.5 and 6.5 kJ mol⁻¹ are located in the crystal structure where the intermolecular interactions significantly influence the potential, leading to a decrease in the total energy.     

Giant dielectric relaxation in SrTiO3-SrMg1/3Nb2/3O3 and SrTiO3-SrSc1/2Ta1/2O3 solid solutions

Ceramic samples of (1−x)SrTiO₃-xSrMg_1/3Nb_2/3O₃ and (1−x)SrTiO₃-xSrSc_1/2Ta_1/2O₃ were prepared, and their dielectric properties were studied at x=0.005–0.15 and 0.01–0.1, respectively, at frequencies 10 Hz–1 MHz and at temperatures 4.2–350 K. A giant dielectric relaxation was observed in the temperature range 150–300 K, and not so strong but well-developed relaxation was found in the temperature range 20–90 K. The activation energy U and the relaxation time τ₀ were determined to be 0.21–0.3 eV and from 10⁻¹¹ to 10⁻¹² s for the high-temperature relaxation and 0.01–0.02 eV and 10⁻⁸–10⁻¹⁰ s for the low-temperature relaxation, respectively. The additional local charge compensation of the heterovalent impurities Mg²⁺ and Nb⁵⁺ (or Sc³⁺ and Ta⁵⁺) by free charge carriers or the host ion vacancies is suggested to be the underlying physical mechanism of the relaxation phenomena. On the basis of this mechanism, the Maxwell-Wagner model and the model of reorienting dipole centers Mg²⁺ (or Sc³⁺) associated with the oxygen vacancy are proposed to explain the high-temperature relaxation with some arguments in favor of the latter model. The polaron-like model with the Nb⁵⁺-Ti³⁺ center is suggested as the origin of the low-temperature relaxation. The reasons for the absence of ferroelectric phase transitions in the solid solutions under study are also discussed. From Fizika Tverdogo Tela, Vol. 44, No. 11, 2002, pp. 1948–1957. Original English Text Copyright ? 2002 by Lemanov, Sotnikov, Smirnova, Weihnacht. This article was submitted by the authors in English.