Cycling Nuclear Magnetic Resonance Relaxometry Research Articles

Detecting soil hydrological connectivity in a badland area by fast field cycling nuclear magnetic resonance relaxometry

AbstractThe ‘hydrological connectivity inside the soil’ refers to both the spatial pattern inside the soil (structural component) and the physical–chemical process at a molecular level (functional component). Fast field cycling (FFC) nuclear magnetic resonance (NMR) relaxometry allows for measuring structural and functional connectivity by two suitable indexes named structural connectivity index (SCI) and functional connectivity index (FCI). In this study, FFC NMR relaxometry was applied to soils sampled in a very degraded environment (i.e., a badland area) to detect the capability of the measurement technique to distinguish the hydrological connectivity of these samples having different conditions (layer explored by roots, sparsely‐vegetated and bare soil). The relaxograms measured by the FFC NMR, using Proton Larmor frequencies in the range 0.01–10 MHz, were integrated and the resulting S‐shaped curves were analysed to obtain the connectivity indexes. Results showed that the ‘Sparsely vegetated’ sample is characterized by more small‐sized pores than the ‘Rooted’ one. The comparison between the ‘Sparsely vegetated’ and ‘Bare’ conditions pointed out that the presence of vegetation reduces the measured relaxation times and, as a consequence, the corresponding pore sizes and modifies the structural connectivity. The analysis also revealed that the three samples are characterized by similar values of SCI, which are independent of the proton Larmor frequency, while the FCI values of the ‘Bare’ soil are the lowest. Conversely, samples from soil with vegetation (‘Rooted’ and ‘Sparsely vegetated’) present comparable functional connectivity. Finally, the analysis of the frequency distribution of the ratio of each connectivity index and its mean value (SCI/m(SCI) and FCI/m(FCI)) allowed to establish its normal distribution. For the investigated samples, this result established that FCI and SCI can be represented by their mean value.

Changes in Physicochemical Properties of Biochar after Addition to Soil

It is recognized that biochar undergoes changes when it is applied to soils. However, the mechanisms of biochar alterations are not fully understood yet. To this purpose, the present study is designed to investigate the transformations in the soil of two different biochars obtained from pyrolysis of fir-wood pellets. The production of the biochars differed for the dry and wet quenching procedures used to terminate the pyrolysis. Both biochars were applied to clay soil (26% sand, 6% silt, and 68% clay) placed into lysimeters. After water saturation and 15 days of equilibration, seeds of watercress (Lepidium sativum) were cultivated. After a further 7 weeks, the biochars were manually separated from the systems. A total of four samples were collected. They were analyzed for chemical–physical characteristics by using an innovative technique referred to as fast field cycling nuclear magnetic resonance relaxometry. The results showed that the dry−quenching produced a material that was mainly chemically altered after application to soil compared to the biochar obtained by the wet−quenching. Indeed, the latter was both chemically and physically modified. In particular, results showed that water was better retained in the soil treated with the dry−quenched material. Consequently, we may suggest that crop productivity and environmental remediation may be modulated by applying either the dry−quenched or the wet−quenched biochar.

Broadband NMR relaxometry of electrolytes for energy storage

An increasing use of the fast field cycling nuclear magnetic resonance relaxometry technique to investigate dynamics in electrolytes for energy storage has been evidenced during the last decade. Therefore, this review article describes some of the research studies carried out on electrolytes during the last ten years using this technique. These studies include various types of liquid electrolytes, such as ionic liquids and deep eutectic solvents, semi-solid-state electrolytes, in particular, ionogels and polymer gels, and solid electrolytes such as glasses, glass ceramics, and polymers. An extended description of the different models used to explain the relaxation rate profiles is presented throughout this article.

Measuring hydrological connectivity inside soils with different texture by fast field cycling nuclear magnetic resonance relaxometry

The locution “hydrological connectivity inside the soil” is generally used to disclose how the spatial patterns inside the soil affect the physical–chemical processes at a molecular level to influence water transfer into the soil, the surface runoff and related sediment transport. Fast Field Cycling (FFC) Nuclear Magnetic Resonance (NMR) relaxometry has been used to measure both structural and functional connectivity by two indexes indicated as structural (SCI) and functional (FCI) connectivity index. Here, FFC-NMR relaxometry has been applied to analyze three samples: two non-degraded soils, having different grain-size distribution, and a degraded soil sampled in a badland area. Proton Larmor frequencies (νL) ranging in the 0.015–35 MHz interval were used on water suspended samples. The relaxograms (i.e., the distributions of the longitudinal relaxation times, T1) obtained by the FFC-NMR investigations were integrated. The resulting S-shaped curves were handled to obtain the aforementioned FCI and SCI parameters. Results showed that the empirical frequency distribution of the SCI index is related to soil texture and structure, while soils having similar SCI revealed different functional connectivity values. This approach allowed (i) to distinguish SCI values of degraded soils from those of non-degraded ones and (ii) to verify whether the structural connectivity index is related to soil texture and structure. The analysis also showed that the variation coefficient of SCI and FCI, achieved from the measurements done at different νL values, is minimum in the measurement range 0.015–1 MHz. The frequency of 1 MHz can be considered the optimal value to have accurate measured connectivity indexes. For the investigated samples, the obtained relationship between FCI and SCI allowed to conclude that high structural connectivity values correspond to a better functional connectivity. Finally, the hydrological connectivity inside a soil was defined as the sum of the two components representing structural and functional perspective.

Detection of Authenticity and Quality of the Turkish Delights (Lokum) by Means of Conventional and Fast Field Cycling Nuclear Magnetic Resonance Relaxometry.

Turkish delights (lokum) are traditional confectionery products that contain mainly sucrose as the sugar source and starch as the gelling agent. However, manufacturers sometimes might prefer to use corn syrup instead of sucrose to decrease the cost. This jeopardizes the originality of Turkish delights and leads to production of adulterated samples. In this study, Turkish delights were formulated using sucrose (original sample) and different types of corn syrups (SBF10, SCG40, and SCG60). Results clearly indicated that corn-syrup-containing samples had improved textural properties and were less prone to crystallization. However, this case affected authenticity of the products negatively. Both time domain nuclear magnetic resonance (TD NMR) and fast field cycling nuclear magnetic resonance (FFC NMR) techniques were found to be effective to discriminate the original samples from the corn-syrup-containing samples. In addition, quantitative analysis of FFC NMR showed that, apart from the rotational motions, molecules in Turkish delights (mainly water and also sugar molecules) undergo two types of translational dynamics.

Influence of underlying local organisations in typical nematic phase of 6CHBT and induced nematic phase of bicomponent liquid crystalline systems 4DBT–12CB – a Fast Field Cycling NMR investigation

ABSTRACTVariable-temperature proton magnetic relaxation dispersion (PMRD) profiles are collected in the induced nematic phases of the binary liquid crystalline mixtures composed of smectic mesogens: 5-butyl-2-(4-isothiocyanatophenyl)-1,3-dioxane (4DBT) and 4′-dodecyl-4-cyanobiphenyl (12CB) and the low viscous nematogen 4-(trans-4′-n-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT), with a view to assess the influence of local organisations on the power spectrum of director fluctuation modes. Two distinct compositions of the binary mixture i.e. 50 mol% of 12CB (without a smectic phase) and 70 mol% of 12CB (with a smectic phase) are used. Fast Field Cycling nuclear magnetic resonance relaxometry is employed to measure proton spin-lattice relaxation rates (R1) as a function of Larmor frequency (10 kHz–30 MHz). PMRD data analysis with the choice of a suitable model indicated nematic clusters of moderate size (~200 Å) found in the broad nematic region of 50 mol% 12CB, whose size is almost invariant with temperature. On the other hand, cybotactic clusters, i.e. local smectic organisations of relatively larger size (~2000–3000 Å), are observed near the nematic–smectic transition (T > TAN) of 70 mol% 12CB. Interestingly, the shape geometry of such local organisations accessed from PMRD analysis is weakly anisotropic near TAN, while being isotropic near TNI for 70 mol% 12CB.

Molecular Dynamics of Water in Wood Studied by Fast Field Cycling Nuclear Magnetic Resonance Relaxometry

Water plays a very important role in wood and wood products. The molecular motion of water in wood is susceptible to thermal activation. Thermal energy makes water molecules more active and weakens the force between water and wood; therefore, the water molecules dynamic properties are greatly influenced. Molecular dynamics study is important for wood drying; this paper therefore focuses on water molecular dynamics in wood through fast field cycling nuclear magnetic resonance relaxometry techniques. The results show that the spin-lattice relaxation rate decreases with the Larmor frequency. Nuclear magnetic resonance dispersion profiles at different temperatures could separate the relaxation contribution of water in bigger pores and smaller pores. The T1 distribution from wide to narrow at 10 MHz Larmor frequency reflects the shrinkage of pore size with the higher temperature. The dependence of spin-lattice relaxation rate on correlation time for water molecular motion based on BPP (proposed by Bloembergen, Purcell, and Pound) theory shows that water correlation time increases with higher temperature, and its activation energy, calculated using the Arrhenius transformation equation, is 9.06±0.53 kJ/mol.

Determining diffusion coefficients of ionic liquids by means of field cycling nuclear magnetic resonance relaxometry.

Field Cycling Nuclear Magnetic Resonance (FC NMR) relaxation studies are reported for three ionic liquids: 1-ethyl-3- methylimidazolium thiocyanate (EMIM-SCN, 220-258 K), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4, 243-318 K), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6, 258-323 K). The dispersion of (1)H spin-lattice relaxation rate R1(ω) is measured in the frequency range of 10 kHz-20 MHz, and the studies are complemented by (19)F spin-lattice relaxation measurements on BMIM-PF6 in the corresponding frequency range. From the (1)H relaxation results self-diffusion coefficients for the cation in EMIM-SCN, BMIM-BF4, and BMIM-PF6 are determined. This is done by performing an analysis considering all relevant intra- and intermolecular relaxation contributions to the (1)H spin-lattice relaxation as well as by benefiting from the universal low-frequency dispersion law characteristic of Fickian diffusion which yields, at low frequencies, a linear dependence of R1 on square root of frequency. From the (19)F relaxation both anion and cation diffusion coefficients are determined for BMIM-PF6. The diffusion coefficients obtained from FC NMR relaxometry are in good agreement with results reported from pulsed- field-gradient NMR. This shows that NMR relaxometry can be considered as an alternative route of determining diffusion coefficients of both cations and anions in ionic liquids.

Temperature and Size-Dependence of Membrane Molecular Dynamics in Unilamellar Vesicles by Fast Field-Cycling NMR Relaxometry

New methods to study dynamics in lipid bilayers are of interest particularly where they may bridge the gap between conventional experimental techniques and molecular dynamics simulations. Fast field cycling nuclear magnetic resonance relaxometry can provide valuable information as it is sensitive to dynamic processes that occur over a broad time scale. By analysis of data recorded for large unilamellar liposomes composed of 1,2-dimyristoyl-sn-glycero-3-posphocholine (DMPC) or 1,2-dioleoyl-sn-glycero-3-posphocholine (DOPC) at different temperatures and sizes, we validate an evidence-based approach to studying dynamics by relaxometry. Specifically, the number and form of the spectral density contributions from a range of dynamic processes are determined. This success of the approach strongly suggests its general applicability for the study of dynamics in membranes of more complex composition and for parameterizing molecular dynamics simulations.

Surface effects on liquid crystals constrained in nanoscaled pores investigated by field cycling NMR relaxometry and Monte Carlo simulations

Proton relaxation rates of nematic liquid crystals confined in nanoporous cavities were measured in a broad frequency range with the help of field cycling nuclear magnetic resonance relaxometry. The shape of relaxation dispersion curves in confined materials strongly deviates from the behavior in bulk, both above and below the bulk isotropization temperature. A strong increase in relaxation rates, exceeding by two orders of magnitude that of the bulk sample, is observed in the range of a few kilohertz. Relaxation rates in bigger pores decreased. Experimental findings are interpreted in terms of surface-induced orientational order and diffusion between sites with different orientations of local directors. With the aid of Monte Carlo simulations, two processes affecting low-frequency relaxation could be identified: (a) exchange losses of molecules from the surface-ordered phase to the bulk-like phase, and (b) Reorientations Mediated by Translational Displacements, which dominate the long-time scale and account for the recovery of correlation in molecular orientations as molecules probe different surface sites. It is shown that the width of the oriented layer may strongly affect the slope of dispersion curves and that cross-over between plateau and power law dispersion regimes shifts towards lower frequencies for bigger pores.

Investigations of polymer dynamics in nanoporous media by field cycling NMR relaxometry and the dipolar correlation effect

The chain dynamics of short-chain perfluoropolyether melts confined in Vycor nanoporous media has been characterized by field cycling nuclear magnetic resonance relaxometry and the dipolar correlation effect. The slowdown of motions under confinement, leading to larger residual dipolar couplings, has been probed by looking at the quotient of stimulated and primary echoes. Using field cycling relaxometry, it has been shown that there is strong evidence of reptation-like motion, even for such short-chain polymers as shown by the frequency and molecular weight dependences of the spin-lattice relaxation time.

Nuclear magnetic resonance proton-spin relaxation study of the local director fluctuations in the lyotropic liquid crystal: Potassium laurate/1-decanol/water

Field cycling nuclear magnetic resonance relaxometry was used to study the slow molecular dynamics in the nematics and isotropic phases and polyphasic region of the phase diagram in the thernary mixture: potassium laurate/1-decanol/water. The experiment has been performed over a broad range of Larmor frequencies (2×103−6.6×106 Hz). The first experimental evidence of director fluctuations in a micellar lyotropic nematic liquid crystal, studied by H1 spin-lattice relaxation rate, is reported. The results evidence that in the nematic mesophases, director fluctuations are responsible for the spin-lattice relaxation dispersion in the low Larmor frequency range (≲105 Hz). By increasing the intermicellar water content, a crossover was found between a quasi-isotropic three-dimensional (3D) director fluctuation behavior and a two-dimensional (2D) pseudo-lamellar undulation fluctuation. In spite of the fact that no menatic phases of this micellar complex fluid are isotropic with respect to light scattering, they present spin-lattice relaxation profiles as driven by local director fluctuations. The polyphasic region, at lower temperatures, shows a quasinematic 3D director fluctuation behavior; meanwhile, the isotropic phase, at higher temperatures, presents 2D pseudo-lamellar undulation fluctuation modes. We conclude that the micelles, in the isotropic phase, preserve the pseudo-lamellar structure, already found in the nematic phases but forming nematic domains with the directors randomly oriented. In order to explain the higher frequency range (≳105 Hz), two relaxation mechanisms are assigned: (i) molecular reorientation by translational diffusion on the micellar surface and (ii) molecular exchange between the micelle and the bulk.