Fast Motion Regime Research Articles

Thermodynamic and Dynamic Transitions and Interaction Aspects in Reorientation Dynamics of Molecular Probe in Organic Compounds: A Series of 1-alkanols with TEMPO.

The spectral and dynamic properties of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) in a series of 1-alkanols ranging from methanol to 1-decanol over a temperature range 100-300 K were investigated by electron spin resonance (ESR). The main characteristic ESR temperatures connected with slow to fast motion regime transition; T50G 's and TX1fast 's are situated above the corresponding glass temperatures, Tg, and for the shorter members, the T50G 's lie above or close to melting point, Tm, while the longer ones the T50G < Tm relationship indicates that the TEMPO molecules are in the local disordered regions of the crystalline media. The T50G 's and especially TX1fast 's are compared with the dynamic crossover temperatures, TXVISC = 8.72M0.66, as obtained by fitting the viscosity data in the liquid n-alkanols with the empirical power law. In particular, for NC > 6, the TX1fast 's lie rather close to the TXVISC resembling apolar n-alkanes [PCCP 2018,20,11145-11151], while for NC < 6, they are situated in the vicinity of Tm. The absence of a coincidence for lower1-alkanols indicates that the T50G is significantly influenced by the mutual interaction between the polar TEMPO and the protic polar medium due to the increased polarity and proticity destroyed by the larger-scale melting transition.

Bulk and confined alkanols by spin probe ESR: Effects of pore size, pore surface composition and pore topology on n-propanol in a series of mesoporous silica-based matrices

The spectral and dynamic behavior of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) in n-propanol (n-PrOH) as a representative of protic polar guests confined in a series of five silicas differing in pore size, surface and topology using electron spin resonance is presented. The hyperfine splitting constants Azz‘ and AN are higher compared with apolar hydrocarbons and the slow to fast motion regime transition at T50G(bulk) occurs in the liqudi state. Under confinement in the virgin silicas, the relative changes in both quantities with respect to the bulk n-PrOH are smaller and more sensitive to the pore size than those for hydrocarbons due to the preferential interaction of the polar pore wall of the virgin silicas with the polar n-PrOH over that with the polar TEMPO. This is supported by reductions of both quantities for the modified matrix. Finally, the T50G is essentially higher due to the very strong effect of the regular pore topology.

Water dynamics in deuterated gypsum, CaSO4⋅2D2O, investigated by solid state deuterium NMR.

NMR relaxation theory and NMR lineshape calculations were used to characterize the rates of C2 symmetry jumps of deuterium nuclei in partly deuterated gypsum powder. The experimental data consisted of variable temperature deuterium NMR powder line shapes and deuterium T1 relaxation times. All of the Mathematica© notebooks used to simulate the spectra and match the experimental T1 values are included as supplementary material, and are suitable templates for similar calculations on other systems. Our simulations show that the deuterium nuclei of D2O in Gypsum undergo a two-site C2 180° jump about the D-O-D bisector angle of 54.8°. The jump rate stays in the fast motion regime down to about 218 K. Below 193 K the powder lineshapes change, the spectral intensities drop significantly, and the motion slows into the intermediate motion regime. The best fit quadrupole coupling constants (QCC's) vary between 216 kHz at the highest temperatures to 235 kHz at the lowest temperatures. The asymmetry parameters (ɳ) vary between 0.11 at the highest temperatures to 0.15 at the lowest temperatures. Knowledge of the C2 jump rates allowed us to calculate activation parameters for the jumps, namely ΔH‡ = 22 kJ/mol, and ΔS‡ = -10 J/mol·K which indicate a non-spontaneous activation process, an activation energy of Ea = 23 kJ/mol, and a pre-exponential factor of A = 3.6 × 1012. As expected, there was no evidence of quantum tunneling.

EPR study of spectra transformations of the intrinsic vanadyl-porphyrin complexes in heavy crude oils with temperature to probe the asphaltenes' aggregation

Temperature dependencies of electron paramagnetic resonance spectra of intrinsic paramagnetic vanadyl complexes and dynamical viscosity for two heavy crude oils and asphalt samples are measured. Transitions between the different motional conditions (from the rigid to the fast motion regimes) are observed. The rotational correlation times (in the model of the isotropic diffusion) are extracted. It is shown that the characteristic temperatures for the motional regime transitions are mainly defined by the asphaltenes’ content. From our analysis it follows that the thermal treatment leads to the destruction of the asphaltene complexes onto the 4–5 small pieces. The results indicate that paramagnetic vanadyl complexes are the sensitive intrinsic probes to study qualitatively and quantitatively structural transformations of aspahltenes of heavy crude oils in-situ.

Molecular dynamics simulations of NMR relaxation and diffusion of bulk hydrocarbons and water

Molecular dynamics (MD) simulations are used to investigate 1H nuclear magnetic resonance (NMR) relaxation and diffusion of bulk n-C5H12 to n-C17H36 hydrocarbons and bulk water. The MD simulations of the 1H NMR relaxation times T1,2 in the fast motion regime where T1=T2 agree with measured (de-oxygenated) T2 data at ambient conditions, without any adjustable parameters in the interpretation of the simulation data. Likewise, the translational diffusion DT coefficients calculated using simulation configurations agree with measured diffusion data at ambient conditions. The agreement between the predicted and experimentally measured NMR relaxation times and diffusion coefficient also validate the forcefields used in the simulation. The molecular simulations naturally separate intramolecular from intermolecular dipole-dipole interactions helping bring new insight into the two NMR relaxation mechanisms as a function of molecular chain-length (i.e. carbon number). Comparison of the MD simulation results of the two relaxation mechanisms with traditional hard-sphere models used in interpreting NMR data reveals important limitations in the latter. With increasing chain length, there is substantial deviation in the molecular size inferred on the basis of the radius of gyration from simulation and the fitted hard-sphere radii required to rationalize the relaxation times. This deviation is characteristic of the local nature of the NMR measurement, one that is well-captured by molecular simulations.

On the mutual relationships between spin probe mobility, free volume and relaxation dynamics in organic glass-formers: Glycerol

The rotation dynamics of the spin probe TEMPO in glycerol from ESR is compared with the ortho-positronium (o-Ps) annihilation from PALS and interpreted using the relaxation dynamics from BDS. Rotation time scale within the slow motion regime exhibits two Arrhenius regions with the characteristic ESR temperature, TX1τ, close to the characteristic PALS temperature, Tb1L, which is related to the secondary β process above Tg. Next, a slow to fast motion regime transition at the characteristic ESR temperature, Tcτ, close to the characteristic PALS temperature, Tb2L, followed by non-Arrhenius fast motion regime region is fully coupled with the primary α process.

Low-power suppression of fast-motion spin 3/2 signals

Triple Quantum Filters (TQFs) are frequently used for the selection of bi-exponentially relaxing spin 3/2 nuclei (in particular 23Na) in ordered environments, such as biological tissues. These methods provide an excellent selection of slow-motion spins, but their sensitivity is generally low, and coherence selection requirements may lead to long experiments when applied in vivo. Alternative methods, such as 2P DIM, have demonstrated that the sensitivities of the signals from bi-exponentially relaxing sodium can be significantly increased using strategies other than TQFs. A shortcoming of the 2P DIM method is its strong dependence on B0 inhomogeneities. We describe here a method, which is sensitive to the slow-motion regime, while the signal from spins in the fast-motion regime is suppressed. This method is shown to be more effective than TQFs, requires minimal phase cycling for the suppression of the influence of rf inhomogeneity, and has less dependence on resonance offsets and B0-inhomogeneity than 2P DIM.

2H NMR study of phase transition and hydrogen dynamics in hydrogen bonded organic antiferroelectric 55DMBP-H2ca

Hydrogen dynamics in one-dimensional hydrogen bonded organic antiferroelectric, co-crystal of 5,5’-dimethyl-2,2’-bipyridine (55DMBP) and chloranilic acid (H2ca), was investigated by use of 2H high resolution solid-state NMR. The two types of hydrogen bonds O-H …N and N+-H …O − in the antiferroelectric phase were clearly observed as the splitting of the side band of the 2H MAS NMR spectra of the acid-proton deuterated compound 55DMBP-D 2ca. The temperature dependence of the spin-lattice relaxation time was measured of the N+-H and O-H deuterons, respectively. It was suggested that the motion of the O-H deuteron is already in the antiferroelectric phase in the fast-motion regime in the NMR time scale, while that of the N+-H deuteron is a slow motion. In the high-temperature paraelectric phase, the both deuterons become equivalent and the fast motion of the deuterons in the NMR time scale is taking place with the activation energy of 7.9 kJ mol−1.

Temperature Determination by EPR at 275 GHz and the Detection of Temperature Jumps in Aqueous Samples.

Second-moment analysis along two dimensions of continuous-wave EPR spectra of nitroxides enables EPR thermometry in a broad temperature range. Simulations show that the temperature can be derived in both the slow-motion and the fast-motion regime, which is experimentally verified at 275 GHz for H2O/glycerol (50/50% by volume) and pure water. We demonstrate that this tool allows the calibration of temperature jumps induced by infrared laser irradiation of a submicroliter sample in the single-mode cavity of a 275 GHz spectrometer, which prepares for kinetic studies of processes involving paramagnetic species.

19F spin–lattice relaxation of perfluoropolyethers: Dependence on temperature and magnetic field strength (7.0–14.1 T)

Fluorine (19F) MRI of perfluorocarbon-labeled cells has become a powerful technique to track the migration and accumulation of cells in living organisms. It is common to label cells for 19F MRI with nanoemulsions of perfluoropolyethers that contain a large number of chemically equivalent fluorine atoms. Understanding the mechanisms of 19F nuclear relaxation, and in particular the spin–lattice relaxation of these molecules, is critical to improving experimental sensitivity. To date, the temperature and magnetic field strength dependence of spin–lattice relaxation rate constant (R1) for perfluoropolyethers has not been described in detail. In this study, we evaluated the R1 of linear perfluoropolyether (PFPE) and cyclic perfluoro-15-crown-5 ether (PCE) at three magnetic field strengths (7.0, 9.4, and 14.1T) and at temperatures ranging from 256–323K. Our results show that R1 of perfluoropolyethers is dominated by dipole–dipole interactions and chemical shift anisotropy. R1 increased with magnetic field strength for both PCE and PFPE. In the temperature range studied, PCE was in the fast motion regime (ωτc<1) at all field strengths, but for PFPE, R1 passed through a maximum, from which the rotational correlation time was estimated. The importance of these measurements for the rational design of new 19F MRI agents and methods is discussed.

Mathematical Properties of the Moments of Truncated Dynamic Magnetic Resonance Spectra and Their Potential Application

AbstractThe moments of truncated dynamic magnetic resonance spectra, Mn(L), are expanded in terms of power series of the integration range −L to +L. The expansion consists of three contributions: 1) an L‐independent term that, for the first three moments (n=1 to 3), is independent of the motion and equals the corresponding moment, Mn, of the rigid powder spectrum; 2) a limited number of (positive) terms, diverging as Lk (k&lt;n, odd), reflecting the broadening effect due to motion; these terms vanish for the first three moments and become nonzero, with motion‐dependent coefficients, only from the fourth moment on; and 3) an infinite series of converging (negative) terms, in powers of 1/Lk (k is odd), reflecting the reduction of the moments due to the truncation of the spectra; these terms are motion dependent for all moments. The convergence properties of this series are discussed and expressions for the lower (truncated) moments in the slow and fast motion limits of a secular Hamiltonian are derived. For the slow motion limit, it is shown how the L‐dependence of the moments can be used to estimate the magnetic and dynamic parameters. The procedure is demonstrated using computer‐simulated spectra. In the fast motion regime, closed expressions are obtained in a similar form to those of the relaxation equations. The effect of natural line width and strong‐collision dynamics on the various moments as well as that of nonsecular terms in the Hamiltonian are also briefly discussed.

Dynamics of pH-sensitive nitroxide radicals in water adsorbed in ordered mesoporous molecular sieves by EPR Spectroscopy

A spin pH probe technique was used to study the influence of the channel diameter on the EPR spectra of pH-sensitive nitroxide radicals (NR) located in the channels of the mesoporous molecular sieves MCM-41 and SBA-15 with diameters ranging from 2.3 to 8.1nm. From EPR spectra analysis and the results of the NR retention by the mesoporous molecular sieves upon washing with an aqueous KCl solution, the regularities of NR molecular location inside the channels were studied. The obtained dependence of the fraction of the radical molecules in the fast motional regime (with the rotational correlation times, τc=2×10−11s–9×10−11s) in the channels of the mesoporous molecular sieves as a function of pH indicates that both NR in the fast and slow motional regime (with τc=8×10−9s–7×10−10s) may be used for estimation of the solution acidity inside the channels and of the near-surface electrical potential.

2H–13C HETCOR MAS NMR for indirect detection of 2H quadrupole patterns and spin–lattice relaxation rates

Two-dimensional (2D) cross-polarization magic angle spinning (CP-MAS) 2H–13C heteronuclear correlation (HETCOR) experiments were utilized to indirectly detect site-specific deuterium MAS powder patterns. The 2H–13C cross-polarization efficiency is orientation-dependent and non-uniform for all crystallites. This leads to difficulty in extracting the correct 2H MAS quadrupole powder patterns. In order to obtain accurate deuterium line shapes, 13C spin lock rf field, spin lock rf ramp and CP contact time were carefully calibrated with the assistance of theoretical simulations. The extracted quadrupole patterns for U-[2H/13C/15N]-alanine indicate that the methyl deuterium undergoes classic, three-site jumping in the fast motion regime (10−8–10−12s) and the methine deuterium has a rigid deuterium powder pattern. For U-[2H/13C/15N]-phenylalanine, indirectly detected deuterium line shapes illustrate that the aromatic ring undergoes 180° flips in the fast motion regime while 2Hβ and 2Hα are completely rigid. The experimental deuterium line shapes for U-[2H/13C/15N]-proline reflect that 2Hβ, 2Hγ and 2Hδ are subjected to fast, two-site reorientations at an angle of (15±5)°, (30±5)° and (25±10)° respectively. In addition, an approach that combines a composite inversion pulse with 2H–13C CP-MAS is applied to measure 2H spin–lattice relaxation times in a site-specific, 13C-detected fashion.

Horizon-absorbed energy flux in circularized, nonspinning black-hole binaries, and its effective-one-body representation

We propose, within the effective one body (EOB) approach, a new, resummed, analytical representation of the gravitational wave energy flux absorbed by a system of two circularized (nonspinning) black holes. This expression is such to be well-behaved in the strong-field, fast motion regime, notably up to the EOB-defined last unstable orbit. Building conceptually upon the procedure adopted to resum the multipolar asymptotic energy flux, we introduce a {\it multiplicative} decomposition of the multipolar absorbed flux made by three factors: (i) the leading-order contribution, (ii) an "effective source" and (iii) a new residual amplitude correction $(\tilde{\rho}_\lm^H)^{2\ell}$. In the test-mass limit, we use a frequency-domain perturbative approach to accurately compute numerically the horizon-absorbed fluxes along a sequence of stable and unstable circular orbits and we extract from them the functions $\tilde{\rho}_\lm^H$. These quantities are then fitted via rational functions. The resulting analytically represented test-mass knowledge is then suitably {\it hybridized} with lower-order analytical information that is valid for any mass ratio. This yields a resummed representation of the absorbed flux for a generic, circularized, nonspinning black-hole binary. Our result adds new information to the state-of-the-art calculation of the absorbed flux at fractional 5 post-Newtonian order [S. Taylor and E. Poisson, Phys. Rev. D {\bf 78} 084016 (2008)], that is recovered in the weak-field limit approximation by construction.

Applicability of solid state fast field cycling NMR relaxometry in understanding relaxation properties of leaves and leaf-litters

Inversion recovery high field solid state (SS) 1H NMR spectroscopy and fast field cycling (FFC) NMR relaxometry have been applied on dried leaves and leaf-litters from a reafforestated area in central Sicily (Italy) in order to evaluate relaxation properties in both slow ( 1 ≪ ω 0 2 τ C 2 ) and fast ( 1 ≫ ω 0 2 τ C 2 ) motion regimes. Namely, SS 1H NMR spectroscopy (i.e. slow motion regime conditions) revealed that two relaxation components (a fast and a slow one) can be identified in all the leaves and leaf-litter samples. The fast component was assigned to small sized plant metabolites, whereas the slow one was attributed to slowly tumbling macropolymeric molecules. FFC NMR relaxometry (i.e. fast motion regime conditions) indicated that intra- and inter-segmental motional contributions to plant relaxation occur, depending on the nature of the plant sample under investigation. The present study represents the first example of a combination of high and low resolution NMR techniques for the understanding of the dynamics properties of environmentally relevant soft matter such as leaves and leaf-litters. These materials are considered among the main contributors for the synthesis of natural organic matter. For this reason, a comprehension of their basic molecular dynamics properties is a crucial point to evaluate their effect on, e.g., carbon cycle, fate of organic and inorganic pollutants, and microbial biomass grow.

Fast motion in molecular solids at low temperatures: Evidence from a pulsed electron paramagnetic resonance study of nitroxyl radical relaxation

We have investigated the electron phase-memory relaxation time of the nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl at temperatures between 5 and 80 K in crystalline and glassy states of ethanol using pulsed X-band electron paramagnetic resonance spectroscopy. The results indicate that the transition from the slow to fast motion regimes of the paramagnetic center occurs upon further cooling of the sample below ∼20 K. We provide experimental evidence that this phenomenon cannot be ascribed to the impact of hyperfine interactions with methyl protons in the system, but it can be instead a signature of the coupling of the electron spin with the boson peak excitations of the lattice.

Comparison of the liquid-ordered bilayer phases containing cholesterol or 7-dehydrocholesterol in modeling Smith-Lemli-Opitz syndrome

The phase behavior of egg sphingomyelin (ESM) mixtures with cholesterol or 7-dehydrocholesterol (7-DHC) has been investigated by independent methods: fluorescence microscopy, X-ray diffraction, and electron spin resonance spectroscopy. In giant vesicles, cholesterol-enriched domains appeared as large and clearly delineated domains assigned to a liquid-ordered (Lo) phase. The domains containing 7-DHC were smaller and had more diffuse boundaries. Separation of a gel phase assigned by X-ray examination to pure sphingomyelin domains coexisting with sterol-enriched domains was observed at temperatures less than 38 degrees C in binary mixtures containing 10-mol% sterol. At higher sterol concentrations, the coexistence of liquid-ordered and liquid-disordered phases was evidenced in the temperature range 20 degrees -50 degrees C. Calculated electron density profiles indicated the location of 7-DHC was more loosely defined than cholesterol, which is localized precisely at a particular depth along the bilayer normal. ESR spectra of spin-labeled fatty acid partitioned in the liquid-ordered component showed a similar, high degree of order for both sterols in the center of the bilayer, but it was higher in the coexisting disordered phase for 7-DHC. The differences detected in the models of the lipid membrane matrix are said to initiate the deleterious consequences of the Smith-Lemli-Opitz syndrome.

Simulation of electron spin resonance spectroscopy in diverse environments: An integrated approach

We discuss in this work a new software tool, named E-SpiReS (Electron Spin Resonance Simulations), aimed at the interpretation of dynamical properties of molecules in fluids from electron spin resonance (ESR) measurements. The code implements an integrated computational approach (ICA) for the calculation of relevant molecular properties that are needed in order to obtain spectral lines. The protocol encompasses information from atomistic level (quantum mechanical) to coarse grained level (hydrodynamical), and evaluates ESR spectra for rigid or flexible single or multi-labeled paramagnetic molecules in isotropic and ordered phases, based on a numerical solution of a stochastic Liouville equation. E-SpiReS automatically interfaces all the computational methodologies scheduled in the ICA in a way completely transparent for the user, who controls the whole calculation flow via a graphical interface. Parallelized algorithms are employed in order to allow running on calculation clusters, and a web applet Java has been developed with which it is possible to work from any operating system, avoiding the problems of recompilation. E-SpiReS has been used in the study of a number of different systems and two relevant cases are reported to underline the promising applicability of the ICA to complex systems and the importance of similar software tools in handling a laborious protocol. Program summary Program title: E-SpiReS Catalogue identifier: AEEM_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AEEM_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GPL v2.0 No. of lines in distributed program, including test data, etc.: 311 761 No. of bytes in distributed program, including test data, etc.: 10 039 531 Distribution format: tar.gz Programming language: C (core programs) and Java (graphical interface) Computer: PC and Macintosh Operating system: Unix and Windows Has the code been vectorized or parallelized?: Yes RAM: 2 048 000 000 Classification: 7.2 External routines: Babel-1.1, CLAPACK, BLAS, CBLAS, SPARSEBLAS, CQUADPACK, LEVMAR Nature of problem: Ab initio simulation of cw-ESR spectra of radicals in solution Solution method: E-SpiReS uses an hydrodynamic approach to calculate the diffusion tensor of the molecule, DFT methodologies to evaluate magnetic tensors and linear algebra techniques to solve numerically the stochastic Liouville equation to obtain an ESR spectrum. Running time: Variable depending on the task. It takes seconds for small molecules in the fast motional regime to hours for big molecules in viscous and/or ordered media.

Motional heterogeneity in single-site silica-supported species revealed by deuteron NMR

The molecular dynamics of [-SiDMe(2)] grafted on two amorphous silica materials, mesoporous SBA and non-porous Aerosil, was investigated by deuteron ((2)H) solid-state NMR spectroscopy. Quadrupole echo (QE), quadrupole Carr-Purcell-Meiboom-Gill (QCPMG) and magic angle spinning (MAS) spectra were recorded as a function of temperature. These were analyzed to determine the rates and trajectories of molecular motion of the surface species. The dynamics were modelled as a composite two frame motion with independent rotations around the two Si-O bonds. In the first frame there are fast three-site jumps of the -SiDMe(2) group described by a single rate (k(1)) and unequal populations of the tetrahedral sites, such that the ratio D : Me : Me is around 1 : 4 : 4. In the second frame, the Si-O axis makes small step, nearest-neighbour jumps at a rate k(2) along an arc defined by the rim of a cone with a fixed half-angle. Both rates were found to be in the fast motional regime (k(1,2) > 10(10) s(-1)) throughout the experimentally accessible temperature range, 190-350 K. The experimental data are compatible only with models that include a distribution of arc lengths, lambda, in the second frame. The best fit of the simulations to the experimental data yields the distributions of the arc length. The results unequivocally demonstrate that even though the sites all have the same average environment, as reported by the isotropic chemical shifts, the dynamics of the grafted species are microscopically spatially heterogeneous with different molecules on the surface having different ranges of motional trajectories and populations. Furthermore, a clear difference in dynamic behavior is observed between the two silica supports, the motion being more constrained on the mesoporous SBA. This differential mobility is possibly due to differences in surface roughness and to the pore structure of SBA compared with the smoother surface of Aerosil.

NMR study of diffusive processes in novel liquid crystalline phases

Various deuterium one- and two-dimensional (2D) NMR techniques are used in the present study to characterize molecular self-diffusive processes in some novel mesophases. Both aligned and powder samples of liquid crystals (LC) are chosen to investigate rotational and/or translational jump diffusions. It is demonstrated that rotation of aligned LC samples in a NMR goniometer probe can be helpful in obtaining dynamic and structural information. Both spectral simulations and/or pulse separation ( τ) dependences of the quadrupole echo intensity are successfully employed. Deuteron spin-lattice relaxation times and angle dependent spectra are measured in a columnar phase of a monomeric discotogen to illustrate both the fast and intermediate motion regimes. Jump diffusions of chiral rodlike molecules in various smectic C⁎ (SmC⁎) phases and twist grain boundary A⁎ (TGBA⁎) phase are studied. In the LC 10B1M7, the jump rate (or diffusion constant) is determined as a function of temperature in the ferro-, ferri- and antiferro-electric chiral C⁎ phases. 2D deuterium exchange NMR is used to monitor the dynamic processes (self-diffusion) in the ferroelectric SmC⁎ and TGBA⁎ phases. Moreover, packing information of the phase can also be obtained in the two ferrielectric subphases and TGBA⁎ phase, which can be compared with results obtained by X-rays measurements.