Nuclear Spin-lattice Relaxation Time Research Articles

Controlled Sublimation Rate of Guest Drug from Polymorphic Forms of a Cyclodextrin-Based Polypseudorotaxane Complex and Its Correlation with Molecular Dynamics as Probed by Solid-State NMR.

Encapsulation of active pharmaceutical ingredients (APIs) in confined spaces has been extensively explored as it dramatically alters the molecular dynamics and physical properties of the API. Herein, we explored the effect of encapsulation on the molecular dynamics and physical stability of a guest drug, salicylic acid (SA), confined in the intermolecular spaces of γ-cyclodextrin (γ-CD) and poly(ethylene glycol) (PEG)-based polypseudorotaxane (PPRX) structure. The sublimation tendency of SA encapsulated in three polymorphic forms of the γ-CD/PEG-based PPRX complex, monoclinic columnar (MC), hexagonal columnar (HC), and tetragonal columnar (TC), was investigated. The SA sublimation rate was decreased by 3.0-6.6-fold and varied in the order of MC form > HC form > TC form complex. The 13C and 1H magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectra and 13C spin-lattice relaxation time (T1) indicated that the encapsulated SA molecules existed as the monomeric form, and its molecular mobility increased in the order of MC form > HC form > TC form complex. In the complexes, a rapid chemical exchange between two dynamic states of SA (free and bound) was suggested, with varying adsorption/desorption rates accounting for its distinct molecular mobility. This adsorption/desorption process was influenced by proton exchange at the interaction site and interaction strength of SA in the complexes, as evidenced by 1H MAS spectra and temperature dependency of the 13C carbonyl chemical shift. A positive correlation between the molecular mobility of SA and its sublimation rate was established. Moreover, the molecular mobility of γ-CD and PEG in the complexes coincided with that of SA, which can be explained by fast guest-driven dynamics. This is the first report on the stability improvement of an API through complexation in polymorphic supramolecular host structures. The relationship between the molecular dynamics and physical properties of encapsulated API will aid in the rational design of drug delivery systems.

Temperature Dependence of Nuclear Quadrupole Resonance and the Observation of Metal-Ligand Covalency in Actinide Complexes: 35Cl in Cs2UO2Cl4.

We report a study of the temperature dependence of 35Cl nuclear quadrupole resonance (NQR) transition energies and spin-lattice relaxation times (T1) for 235U-depleted dicesium uranyl tetrachloride (Cs2UO2Cl4) aimed at elucidating electronic interactions between the uranium center and atoms in the equatorial plane of the UO22+ ion. The transition frequency decreases slowly with temperature below 75 K and with a more rapid linear dependence above this temperature. The spin-lattice relaxation time becomes shorter with temperature, and as temperatures increase, the T1 decrease becomes nearly quadratic. The observed trends are reproduced by a model that assumes phonon-induced fluctuations of the electric field gradient tensor and partial electron delocalization from Cl to U. The fit of the theoretical model to experimental data allows a Debye temperature of 96 K to be estimated. The generalization of this approach to investigations of covalency in actinide-ligand bonding is examined.

Calorimetric measurement of nuclear spin-lattice relaxation rate in metals

The quasiparticle density of states in correlated and quantum-critical metals directly probes the effect of electronic correlations on the Fermi surface. Measurements of the nuclear spin-lattice relaxation rate provide one such experimental probe of quasiparticle mass through the electronic density of states. By far the most common way of accessing the spin-lattice relaxation rate is via nuclear magnetic resonance and nuclear quadrupole resonance experiments, which require resonant excitation of nuclear spin transitions. Here we report non-resonant access to spin-lattice relaxation dynamics in AC-calorimetric measurements. The nuclear spin-lattice relaxation rate is inferred in our measurements from its effect on the frequency dispersion of the thermal response of the calorimeter-sample assembly. We use fast, lithographically-defined nanocalorimeters to access the nuclear spin-lattice relaxation times in metallic indium from 0.3~K to 7~K and in magnetic fields up to 35~T.

Bayesian Approach to T1 Analysis in NMR Spectroscopy with Applications to Solid State Physics

We applied the Bayesian framework to the analysis of nuclear spin–lattice relaxation curves. In the simplest case, nuclear spin–lattice relaxation is described by a single exponential function. However, relaxations to which the exponential function does not fit well are often observed in real NMR experiments. One of the reasons for those relaxations is the sample inhomogeneity. For such cases, it is common practice to analyze the curve by fitting a stretched exponential function exp(−(t/T1)β) to the data, where T1 is the nuclear spin–lattice relaxation time. Another possibility is the coexistence of different relaxation mechanisms. In this situation, the relaxation curves should be fitted by the summation of several relaxation functions. For scientists to interpret relaxation curves, a data-driven method is required to determine which of the two possibilities is more plausible. In this paper, we propose a Bayesian method to select the appropriate relaxation function and even the number of relaxation components. We demonstrate that our method effectively determines the relaxation model on the basis of numerical experiments and the experimental data of nuclear spin–lattice relaxation of the nonmagnetic semiconductor SmS.

Radicals on the silica surface: probes for studying dynamics by means of fast field cycling relaxometry and dynamic nuclear polarization

Determining the dynamics of adsorbed liquids on nanoporous materials is crucial for a detailed understanding of interactions and processes on the solid-liquid interface in many materials and porous systems. Knowledge of the influence of the presence of paramagnetic species on the surface or within the porous matrices is essential for fundamental studies and industrial processes such as catalysts. Magnetic resonance methods, such as electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR) and dynamic nuclear polarization (DNP), are powerful tools to address these questions and to quantify dynamics, electron-nuclear interaction features and their relation to the physical-chemical parameters of the system. This paper presents an NMR study of the dynamics of polar and nonpolar adsorbed liquids, represented by water, n-decane, deuterated water and nonane-d20, on the native silica surface as well as silica modified with vanadyl porphyrins. The analysis of the frequency dependence of the nuclear spin-lattice relaxation time is carried out by separating the intra- and intermolecular contributions, which were analyzed using reorientations mediated by translational displacements (RMTD) and force-free-hard-sphere (FFHS) models, respectively.

Structural geometry and molecular dynamics of hybrid organic–inorganic [NH3(CH2)6NH3]CdCl4 crystals close to phase transition temperatures

Organic–inorganic hybrid perovskites are highly promising for application in various electrochemical devices, such as batteries and fuel cells. The physical properties of crystals of the organic–inorganic hybrid perovskite [NH3(CH2)6NH3]CdCl4 are important for their future application. Therefore, these crystals were grown and their phase transition temperatures TC1 = 337 K and TC2 = 472 K were determined using powder X-ray diffraction and differential scanning calorimetry. We observed that the crystallographic surroundings of 1H and 13C in the cation near TC1 did not show significant changes, whereas those of 113Cd in the anion changed significantly. The change in the coordination geometry of C1 around Cd near TC1 changed the N–H···Cl bond by connecting with the 1H of NH3. The nuclear magnetic resonance spin-lattice relaxation time T1ρ suggested that the 1H energy transfer processes in phases III and II were easier, whereas the 13C energy transfer processes were easier in phase III than in phase II. The results of the current study for [NH3(CH2)nNH3]CdCl4 (n = 6) were compared with those for n = 2, 3, 4, and 5 obtained from previous studies. The features of the length of CH2 and even–odd number of carbons in the diammonium chain are expected to facilitate potential applications in the future.

Spatially Resolved Spin–Lattice Relaxation Times and Line Widths in Manganese-Grafted Detonation Nanodiamonds

We report on a novel approach that allows determining the spatially resolved nuclear spin–lattice relaxation times and NMR line widths in nanomaterials. The approach was applied to a newly synthesized nanomaterial─detonation nanodiamonds with manganese ions directly grafted to the surface of the nanodiamond particles. The interaction of the carbon nuclear spins with paramagnetic Mn2+ ions results in acceleration of nuclear spin–lattice relaxation and broadening of the 13C resonance line. Using spin dephasing experiments, we were able to determine the layer-by-layer contributions of the paramagnetic Mn2+ions to the spin–lattice relaxation time and line width of the carbon spins positioned at different depths from the diamond surface. Developed for nanodiamonds, this approach is more general and can be successfully applied to study the distribution of nuclear relaxation rates and line broadening and for mapping magnetic interactions inside various nanoparticles, being of practical use in various nanotechnologies.

Measurement of nuclear spin relaxation time in lanthanum aluminate for development of polarized lanthanum target

The nuclear spin–lattice relaxation time (T1) of lanthanum and aluminum nuclei in a single crystal of lanthanum aluminate doped with neodymium ions is studied to estimate the feasibility of the dynamically polarized lanthanum target applicable to beam experiments. The application of our interest is the study of fundamental discrete symmetries in the spin optics of epithermal neutrons. This study requires a highly flexible choice of the applied magnetic field for neutron spin control and favors longer T1 under lower magnetic field and at higher temperature. The T1 of 139La and 27Al was measured under magnetic fields of 0.5–2.5 T and at temperatures of 0.1–1.5 K and found widely distributed up to 100 h. The result suggests that the T1 can be as long as T1∼ 1 h at 0.1 K with a magnetic field of 0.1 T, which partially fulfills the requirement of the neutron beam experiment. Possible improvements to achieve a longer T1 are discussed.

Ferrimagnetism in EuFe4As12 revealed by Eu153 NMR and As75 NQR measurements

Filled skutterudite compound EuFe$_4$As$_{12}$ shows the highest magnetic ordering temperature of $T_{\rm C}$ = 154 K among Eu-based skutterudite compounds, but its magnetic ground state has not been determined yet. Here, we performed $^{153}$Eu nuclear magnetic resonance (NMR) and $^{75}$As nuclear quadrupole resonance (NQR) measurements on EuFe$_4$As$_{12}$ to reveal its magnetic ground state as well as the physical properties from a microscopic point of view. From the temperature and magnetic field dependence of $^{153}$Eu NMR spectrum in the magnetically ordered state, we found that the Eu ions are in Eu$^{2+}$ state with a nearly 7 $\mu_{\rm B}$ corresponding to $S$ = 7/2 spins. Combined with the magnetization measurements which show the reduced saturation moments of 4.5 $\mu_{\rm B}$/f.u., we determined the ground magnetic structure in EuFe$_4$As$_{12}$ to be ferrimagnetic where the Eu$^{2+}$ 4$f$ and the Fe 3$d$ ordered moments are ferromagnetically aligned in each sublattice but the moments between the sublattices are antiferromagnetically aligned. We also found the local distortion at the Eu site from the cubic symmetry in the magnetically ordered state. The relationship between the rattling motion of Eu atoms and the local symmetry of the Eu ions is discussed. From the $^{75}$As NQR nuclear spin-lattice relaxation time measurements as well as $^{153}$Eu NMR measurements, we found that the 4$f$ electrons of the Eu ions are well described by the local moment picture in both the magnetic and paramagnetic metallic states.

Kinetic features for nucleation-growth process of magnetic phase transition in La(Fe0.88Si0.12)13 compounds

Non-equilibrium transient features of the nucleation-growth phenomenon were investigated to identify the hysteresis characteristics of a first-order phase transition in La(Fe0.88Si0.12)13 compound. The kinetics in the boundary of the nucleated domains in the matrix of the original phase was investigated in the magnetostatically arrested state at which the domain motion was temporarily arrested by the demagnetizing fields. The response to relatively slow magnetic field changes has a time scale characterized by the dissipation of the locally generated latent heat at the phase boundaries. Applying a faster oscillating field to the arrested boundary results in the appearance of unique responses in which the characteristic time scales are close to the atomic nuclear spin-lattice relaxation time for magnetic elements.

NMR Studies of the Dynamics of 1D $$^3\hbox {He}$$ in $$^4\hbox {He}$$ Plated MCM-41

Pulsed NMR techniques have been used to study the dynamics of $$^3\hbox {He}$$ confined to the interior of the hexagonal nanochannels of MCM-41 for which the walls were coated with a monolayer of $$^4\hbox {He}$$ as determined by isotherm measurements. The $$^3\hbox {He}$$ was added afterward to form a 1D $$^3\hbox {He}$$ line density of about 0.1 $$\hbox {A}^{-1}$$ , corresponding to a Fermi temperature of $$T_{\mathrm{F}} \sim$$ 120 mK. A distinct and appreciable departure from the Curie law was observed for the nuclear spin magnetization below 0.5 K. The temperature dependence of the nuclear spin–lattice relaxation times, $$T_1$$ , for temperatures $$0.05<T<2.5$$ K, followed the expected linear behavior at low temperatures, and a peak was observed at $$T\sim 2T_{\mathrm{F}}$$ consistent with the Luttinger liquid theory as predicted by Polini et al. (Phys Rev Lett 98:266403, 2007). The observed temperature dependence of the nuclear spin–spin relaxation times, $$T_2$$ , differed considerably from that observed for $$T_1$$ , with a minimum at $$T= 0.8$$ K, similar to the tendency reported by Matsushita and colleagues.

35Cl NQR Relaxation of the Molecular Ferroelectric 5,6-Dichloro-2-Methylbenzimidazole with Hydrogen-Bonded Molecular Chain

The 35Cl nuclear quadruple resonance (NQR) frequencies and spin-lattice relaxation times were measured in the temperature range of 4.2–420 K, of the above-room-temperature ferroelectric 5,6-dichloro-2-methylbenzimidazole, the ferroelectricity of which is thought to arise from the positional ordering of protons along chain of N-H...N hydrogen bonds. The first-order phase transition was clearly detected at around 400 K, as a discontinuity in the temperature dependence of NQR frequencies. The two NQR lines observed showed a much more significant difference in frequency in the high-temperature phase. This is consistent with the recently reported symmetry-lowering of crystal structure on warming. The relaxation mechanism in the low-temperature phase is discussed.

Motional freedom of dimethylammonium ions in a cyanoelpasolite, [(CH3)2NH2]2KCo(CN)6, which exhibits phase transition associated with a distinct change in dielectric property.

The temperature dependence of the 1H nuclear magnetic resonance spin-lattice relaxation time T1 of [(CH3)2NH2]2KCo(CN)6 and the partially deuterated analogue [(CD3)2NH2]2KCo(CN)6 has been reported. A change in the molecular motion of organic cations through the first-order phase transition at Tc = 246 K has been discussed. Although this first-order transition has been reported as an isosymmetric transition, in which the space group of the crystal does not change, the number of the 14N nuclear quadrupole resonance line changed from three in the high-temperature phase to twelve in the low-temperature phase indicating the lowering of crystal symmetry.

NMR studies of the dynamics of HD adsorbed in MCM-41

Abstract The motion of hydrogen deuteride molecules adsorbed on MCM-41 at monolayer coverages has been explored using NMR techniques. The nuclear spin-spin and nuclear spin-lattice relaxation times show an abrupt change at 8.8 K, consistent with the formation of small clusters below that temperature. The molecular tunneling times deduced from the NMR measurements are consistent with the values determined by neutron scattering [Coulomb et al., Micro Meso Matls 101,270 (2007)].

Pump-probe nuclear spin relaxation study of the quantum Hall ferromagnet at filling factor ν = 2

The nuclear spin-lattice relaxation time T1 of the ν = 2 quantum Hall ferromagnet (QHF) formed in a gate-controlled InSb two-dimensional electron gas has been characterized using a pump-probe technique. In contrast to a long T1 of quantum Hall states around ν = 1 that possesses a Korringa-type temperature dependence, the temperature-independent short T1 of the ν = 2 QHF suggests the presence of low energy collective spin excitations in a domain wall. Furthermore, T1 of this ferromagnetic state is also found to be filling- and current-independent. The interpretation of these results as compared to the T1 properties of other QHFs is discussed in terms of the domain wall skyrmion, which will lead to a better understanding of the QHF.

Investigating the Internal Processes of Thermo-Electrochemical Cells Using in-Situ Magnetic Resonance Imaging

Thermo-electrochemical cells are emerging as a promising and efficient method to convert waste heat to electricity. In addition to developing novel redox electrolyte materials to increase the energy densities, it is crucial for future developments to understand the internal chemical and thermodynamical processes happening inside the thermo-electrochemical cell while it is under operating conditions. Although the temperature and concentration distributions between the electrodes and the variations of the convection currents with cell orientation have been modelled mathematically, it has been a challenge to study these internal processes using experimental techniques. Magnetic resonance imaging (MRI) is a non-invasive and well-established diagnosis technique in medical research to investigate physiology, but it also has the capability to study spatial properties of materials, chemical and thermodynamic processes in energy storage devices using different image contrast options including spin density, relaxation time and velocity [1]. The goals of this study are to develop an MRI method to study the internal chemical and thermodynamic processes within a functioning thermo-electrochemical cell, and understanding how these are affected by the electrolyte, the cell geometry and the orientation of the thermal gradient. A cobalt redox couple based electrolyte, which has been shown to be a promising candidate for thermo-electrochemical cells [2], was used for the in-situ experiments inside specialised cells custom built for MRI experiments, and temperature and concentration dependent 1H nuclear magnetic resonance spin-lattice relaxation time (T1) measurements were used to interpret the 1H T1 weighted MRI images of the working cells.

A comprehensive and comparative study of the internal structure and dynamics of natural [formula omitted]keratin and regenerated[formula omitted]keratin by solid state NMR spectroscopy

Structure and dynamics of natural and regenerated chicken feather β-keratin were investigated by 13C cross-polarization (CP) magic angle spinning (MAS) solid state nuclear magnetic resonance (SSNMR) spectral analysis, 13C and 1H spin-lattice relaxation time measurements, and 13C two dimensional phase adjusted spinning sidebands (2DPASS) MAS SSNMR measurements. Chemical shift anisotropy (CSA) parameters of both natural and regenerated chicken feather β-keratin were extracted by using 2DPASS MAS SSNMR experiment. The beauty of 2DPASS MAS SSNMR experiment is it can correlate the isotropic and anisotropic dimension with the help of shearing transformation and two dimensional Fourier Transformation. Molecular correlation time at each and every magnetically inequivalent carbon site of both natural and regenerated chicken feather β-keratin were also determined. The change in molecular dynamics of structural protein after pretreatment was monitored by 2DPASS MAS SSNMR and 13C relaxation measurement. This type of comprehensive study will provide the information about the interrelation between the structure and dynamics of structural protein and will also shed light in the way of developing methods for conversion of animal by-products to novel product.

Nuclear spin-lattice relaxation time in TaP and the Knight shift of Weyl semimetals

We first analyze the recent experimental data on the nuclear spin-lattice relaxation rate of the Weyl semimetal TaP. We argue that its non-monotonic temperature dependence is explained by the temperature dependent chemical potential of Weyl fermions. We also develop the theory of the Knight shift in Weyl semimetals, which contains two counteracting terms. The diamagnetic term follows $-\ln[W/\max(|\mu|,k_BT)]$ with $W$, $\mu$ and $T$ being the high energy cutoff, chemical potential and temperature, respectively, and is always negative. The paramagnetic term scales with $\mu$ and changes sign depending on the doping level. Altogether, the Knight shift is predicted to vanish or even change sign upon changing the doping or the temperature, making it a sensitive tool to identify Weyl points. We also calculate the Korringa relation for Weyl semimetals which shows an unusual energy dependence rather than being constant as expected for a non-interacting Fermi system.

Nuclear spin dynamics in [001] AlAs quantum well in the regime of integer and fractional quantum Hall effect

Relaxation of nuclear spins located in the vicinity of 2D electron system confined in a 16 nm [001] AlAs/AlGaAs quantum well was studied with the aid of electron spin resonance (ESR) in the regime of integer and fractional quantum Hall effect. Nuclear spin-lattice relaxation time τ was measured from the time decay of the Overhauser shift near different filling factors of the electron system. The resultant dependence of τ on filling factor turned out to be nontrivial. At the temperature 1.5 K τ reached its maximal value at the exact filling ν = 1 and decreased when ν was altered, yet this maximum vanished when the system was cooled down to 0.5 K. The fractional quantum Hall effect state at the filling of 2∕3 was formed at the temperature of 0.5 K, and the development of this state was accompanied by the slowing of the nuclear spin relaxation. This observation suggests the enhancement of energy gap in the spin excitation spectrum of two-dimensional electrons at 2/3 state.

Nuclear Spin Relaxometry of $$^3$$He Atoms Confined in Mesoporous MCM-41

MCM-41 is a unique mesoporous material with cylindrical-like pores that provide an ideal platform to study 1D properties of adsorbed atoms (Boninsegni and Moroni in J Low Temp Phys 118(1):1, 2000). In this research, we use pulsed NMR to measure the nuclear spin-lattice relaxation times ( $$T_1$$ ) of $$^3$$ He adsorbed onto $$^4$$ He-preplated MCM-41 over a wide range of temperatures for a line density that would lead to a Fermi temperature of 200 mK. The temperature dependence of the nuclear spin-lattice relaxation time for $$ 0.025<T< 3.5 $$ K exhibited a pronounced peak at 195 mK, qualitatively similar to that calculated for the spin relaxation of 1D Fermi systems.