Water Dynamics in Dextran-Based Hydrogel Micro/Nanoparticles Studied by NMR Diffusometry and Relaxometry.

Water dynamics in mesoporous dextran hydrogel micro/nanoparticles was investigated by means of nuclear magnetic resonance (NMR) techniques. High-resolution 1H NMR spectra and pulsed field gradient (PFG) NMR diffusometry measurements obtained on swollen state dextran micro/nanogel revealed the existence of different fractions of water molecules based on their interaction with the gel matrix. In addition to the translational diffusion of bulk water, two more diffusion processes characterized with self-diffusion coefficients 1 and 2 orders of magnitude smaller than that of bulk water were identified. 1H spin-lattice relaxation dispersion profiles obtained for a broad range of Larmor frequencies using fast field cycling (FFC) and conventional NMR relaxometry techniques allowed us to further clarify the mechanisms of molecular motion. According to the water proton pool fractions and associated self-diffusion coefficients, it is shown that the relaxation contribution associated with reorientation-mediated translational motions (RMTDs) dominates the relaxation dispersion observed at intermediate frequencies. At very low frequencies, the spin-lattice relaxation rate is dominated by the slow solid-gel dynamics probed by the water molecules interacting with the pores' surface hydroxyl groups due to the rapid chemical exchange between surface hydroxyl groups and free water. The correlation time for the thumbling-like motion of the dextran gel was found to be in the submillisecond range. The values of the self-diffusion and coherence lengths associated with motion of water molecules interacting with the solid-gel particles are consistent with the particle size and pore size distributions obtained for the studied dextran gels.

Observing short-range orientational order in small-molecule liquids.

Local molecular ordering in liquids has attracted a lot of interest from researchers investigating crystallization, but is still poorly understood on the molecular scale. Classical nucleation theory (CNT), a macroscopic thermodynamic description of condensation, has shortcomings when dealing with clusters consisting of tens of molecules. Cluster formation and local order fluctuations in liquid media are difficult to study due to the limited spatial resolution of electron- and photon-imaging methods. We used NMR relaxometry to demonstrate the existence of dynamic clusters with short-range orientational order in nominally isotropic liquids consisting of elongated molecules. We observed clusters in liquids where the local ordering is driven by polar, steric, and hydrogen-bond interactions between the molecules. In the case of a liquid crystal, measuring the local orientational order fluctuations allowed us to observe the size of these clusters diverging when approaching the phase transition from the isotropic to the nematic phase. These fluctuations are described in terms of rotational elasticity as a consequence of the correlated reorientations of the neighbouring molecules. Our quantitative observations of the dynamic clusters in liquids, numbering about ten or fewer molecules, indicate that this is a general phenomenon in various types of liquids.

Water Molecular Dynamics in the Porous Structures of Ultrafiltration/Nanofiltration Asymmetric Cellulose Acetate-Silica Membranes.

This study presents the characterization of water dynamics in cellulose acetate-silica asymmetric membranes with very different pore structures that are associated with a wide range of selective transport properties of ultrafiltration (UF) and nanofiltration (NF). By combining 1H NMR spectroscopy, diffusometry and relaxometry and considering that the spin-lattice relaxation rate of the studied systems is mainly determined by translational diffusion, individual rotations and rotations mediated by translational displacements, it was possible to assess the influence of the porous matrix's confinement on the degree of water ordering and dynamics and to correlate this with UF/NF permeation characteristics. In fact, the less permeable membranes, CA/SiO2-22, characterized by smaller pores induce significant orientational order to the water molecules close to/interacting with the membrane matrix's interface. Conversely, the model fitting analysis of the relaxometry results obtained for the more permeable sets of membranes, CA/SiO2-30 and CA/SiO2-34, did not evidence surface-induced orientational order, which might be explained by the reduced surface-to-volume ratio of the pores and consequent loss of sensitivity to the signal of surface-bound water. Comparing the findings with those of previous studies, it is clear that the fraction of more confined water molecules in the CA/SiO2-22-G20, CA/SiO2-30-G20 and CA/SiO2-34-G20 membranes of 0.83, 0.24 and 0.35, respectively, is in agreement with the obtained diffusion coefficients as well as with the pore sizes and hydraulic permeabilities of 3.5, 38 and 81 kg h-1 m-2 bar-1, respectively, reported in the literature. It was also possible to conclude that the post-treatment of the membranes with Triton X-100 surfactants produced no significant structural changes but increased the hydrophobic character of the surface, leading to higher diffusion coefficients, especially for systems associated with average smaller pore dimensions. Altogether, these findings evidence the potential of combining complementary NMR techniques to indirectly study hydrated asymmetric porous media, assess the influence of drying post-treatments on hybrid CA/SiO2 membrane' surface characteristics and discriminate between ultra- and nano-filtration membrane systems.

Tailoring the Selective Permeation Properties of Asymmetric Cellulose Acetate/Silica Hybrid Membranes and Characterisation of Water Dynamics in Hydrated Membranes by Deuterium Nuclear Magnetic Resonance.

In this work, the water order and dynamics in hydrated films of flat asymmetric cellulose acetate (CA)/silica, CA/SiO2, and hybrid membranes, covering a wide range of nanofiltration (NF) and ultrafiltration (UF) permeation properties, were characterised by deuterium nuclear magnetic resonance (DNMR) relaxation. The range of NF/UF characteristics was attained by subjecting three CA/SiO2 membranes, prepared from casting solutions with different acetone/formamide ratios to drying post-treatments of solvent exchange and conditioning with surfactant mixtures. Post-treated and pristine CA/SiO2 membranes were characterised in terms of hydraulic permeability, selective permeation properties and molecular weight cut-off. These results were correlated with the DNMR relaxation findings. It was found that the post-treatment by solvent exchange caused membrane shrinkage that led to very different permeation characteristics and a significant enhancement of the DNMR relaxation observables. In contrast, conditioning with surfactant solutions exhibited a weaker effect over those properties. Scanning electron microscopy (SEM) images were obtained for the membranes post-treated with solvent exchange to confirm their asymmetric nature. This work provides an essential indication that DNMR relaxometry is a reliable tool to characterise the asymmetric porous structures of the NF/UF CA/SiO2 hybrid membranes.

Characterization of Pectin-Based Gels: A 1H Nuclear Magnetic Resonance Relaxometry Study.

Rare sugars are monosaccharides and their derivatives that are not commonly found in nature. d-Allulose is a rare sugar that is C-3 epimer of fructose and presents an alternative to sucrose with potential health benefits. In this study, different amounts of sucrose, d-allulose, and soy protein isolate (SPI) were used to prepare a set of pectin gels. The effect of these ingredients on the gels was studied at both a molecular level, by 1H nuclear magnetic resonance (NMR) relaxometry, and a macroscopic level, through the assessment of viscoelastic properties as well as hardness and moisture content measurements. The NMR dispersion profiles were analyzed considering relaxation mechanisms associated with rotational and translational diffusion motions of mono- and disaccharides as well as bound water molecules. Significant variations of the local diffusion coefficient for the studied formulations were evidenced by the model fitting analysis. The viscosity trends observed within each group of samples having the same amount of SPI were mostly in agreement with the diffusion coefficients obtained from the NMR relaxometry. The observed discrepancies could be explained considering hardness and moisture content results, which put into evidence the fact that decreasing the moisture (mainly free water) affects the macroscopic properties of the systems, such as hardness and viscosity, but not the local diffusion processes probed by NMR relaxometry. These findings show the importance of combining both micro- and macroscopic information to analyze the different properties of food products.

A differential equations model-fitting analysis of COVID-19 epidemiological data to explain multi-wave dynamics.

Compartmental epidemiological models are, by far, the most popular in the study of dynamics related with infectious diseases. It is, therefore, not surprising that they are frequently used to study the current COVID-19 pandemic. Taking advantage of the real-time availability of COVID-19 related data, we perform a compartmental model fitting analysis of the portuguese case, using an online open-access platform with the integrated capability of solving systems of differential equations. This analysis enabled the data-driven validation of the used model and was the basis for robust projections of different future scenarios, namely, increasing the detected infected population, reopening schools at different moments, allowing Easter celebrations to take place and population vaccination. The method presented in this work can easily be used to perform the non-trivial task of simultaneously fitting differential equation solutions to different epidemiological data sets, regardless of the model or country that might be considered in the analysis.

Tuning the 1H NMR Paramagnetic Relaxation Enhancement and Local Order of [Aliquat]+-Based Systems Mixed with DMSO.

Understanding the behavior of a chemical compound at a molecular level is fundamental, not only to explain its macroscopic properties, but also to enable the control and optimization of these properties. The present work aims to characterize a set of systems based on the ionic liquids [Aliquat][Cl] and [Aliquat][FeCl4] and on mixtures of these with different concentrations of DMSO by means of 1H NMR relaxometry, diffusometry and X-ray diffractometry. Without DMSO, the compounds reveal locally ordered domains, which are large enough to induce order fluctuation as a significant relaxation pathway, and present paramagnetic relaxation enhancement for the [Aliquat][Cl] and [Aliquat][FeCl4] mixture. The addition of DMSO provides a way of tuning both the local order of these systems and the relaxation enhancement produced by the tetrachloroferrate anion. Very small DMSO volume concentrations (at least up to 1%) lead to enhanced paramagnetic relaxation without compromising the locally ordered domains. Larger DMSO concentrations gradually destroy these domains and reduce the effect of paramagnetic relaxation, while solvating the ions present in the mixtures. The paramagnetic relaxation was explained as a correlated combination of inner and outer-sphere mechanisms, in line with the size and structure differences between cation and anion. This study presents a robust method of characterizing paramagnetic ionic systems and obtaining a consistent analysis for a large set of samples having different co-solvent concentrations.

Dynamics of binary mixtures of an ionic liquid and ethanol by NMR.

A study of molecular dynamics of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulphonyl)imide ([Emim][Tf2N]) in solution with deuterated ethanol at different molar concentration and temperatures is presented. The study was performed using 1 H and 2 H nuclear magnetic relaxation and 2 H 1D spectroscopy. The temperature dependence of the spin-lattice relaxation time T1 of the cations allows the evaluation of the activation energies of the rotational degree of freedom of these molecules. The viscosity in the binary system increases with the concentration of ionic liquid. However, the activation energy in the cation molecules decreases when the concentration of the ionic liquid increases, indicating that the rotational dynamics is facilitated. This behavior is explained from the fact that the presence of the ionic liquid in the system disrupts the degree of intermediate range order expected in the alcohol system. Copyright © 2017 John Wiley & Sons, Ltd.

1H NMR Relaxometry and Diffusometry Study of Magnetic and Nonmagnetic Ionic Liquid-Based Solutions: Cosolvent and Temperature Effects.

In this work, 1H NMR relaxometry and diffusometry as well as viscometry experiments were carried out as a means to study the molecular dynamics of magnetic and nonmagnetic ionic liquid-based systems. In order to evaluate the effect of a cosolvent on the superparamagnetic properties observed for Aliquat-iron-based magnetic ionic liquids, mixtures comprising different concentrations, 1% and 10% (v/v), of DMSO-d6 were prepared and studied. The results for both magnetic and nonmagnetic systems were consistently analyzed an suggest that, when at low concentrations, DMSO-d6 promotes more structured ionic arrangements, thus enhancing these superparamagnetic properties. Furthermore, the analysis of temperature and water concentration effects allowed to conclude that neither one of these variables significantly affected the superparamagnetic properties of the studied magnetic ionic liquids.