Pulsed Gradient Spin Echo Research Articles

Diffusion Measurements To Understand Dynamics and Structuring in Solutions Involving a Homologous Series of Ionic Liquids.

The self-diffusion coefficients of each of the components in mixtures containing pyridine and each of the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imides in acetonitrile were determined using NMR diffusometry (i. e., Pulsed Gradient Spin Echo). The nature of solvation was found to change significantly with the proportion of salt in the mixtures. Increased diffusion coefficients (when corrected for viscosity) for the molecular components were observed with increasing proportion of ionic liquid and with increasing alkyl chain length on the cation. Comparison of the molecular solvents suggests increased interactions in solution of the pyridine with other components of the mixture, consistent with the proposed interactions shown previously to drive changes in reaction kinetics. Discontinuities were seen in the diffusion data for each species in solution across different ionic liquids between the hexyl and octyl derivatives, suggesting a change in the structuring in solution as the alkyl chain on the cation changes and demonstrating the importance of such when considering homologous series.

Correlation between diffusion tensor indices and fascicular morphometric parameters of peripheral nerve.

Introduction: Diffusion tensor imaging (DTI) is a magnetic resonance imaging (MRI) technique that measures the anisotropy of water diffusion. Clinical magnetic resonance imaging scanners enable visualization of the structural integrity of larger axonal bundles in the central nervous system and smaller structures like peripheral nerves; however, their resolution for the depiction of nerve fascicular morphology is limited. Accordingly, high-field strength MRI and strong magnetic field gradients are needed to depict the fascicular pattern. The study aimed to quantify diffusion tensor indices with high-field strength MRI within different anatomical compartments of the median nerve and determine if they correlate with nerve structure at the fascicular level. Methods: Three-dimensional pulsed gradient spin-echo (PGSE) imaging sequence in 19 different gradient directions and b value 1,150s/mm2 was performed on a 9.4T wide-bore vertical superconducting magnet. Nine-millimeter-long segments of five median nerve samples were obtained from fresh cadavers and acquired in sixteen 0.625mm thick slices. Each nerve sample had the fascicles, perineurium, and interfascicular epineurium segmented. The diffusion tensor was calculated from the region-average diffusion-weighted signals for all diffusion gradient directions. Subsequently, correlations between diffusion tensor indices of segmentations and nerve structure at the fascicular level (number of fascicles, fascicular ratio, and cross-sectional area of fascicles or nerve) were assessed. The acquired diffusion tensor imaging data was employed for display with trajectories and diffusion ellipsoids. Results: The nerve fascicles proved to be the most anisotropic nerve compartment with fractional anisotropy 0.44 ± 0.05. In the interfascicular epineurium, the diffusion was more prominent in orthogonal directions with fractional anisotropy 0.13 ± 0.02. Diffusion tensor indices within the fascicles and perineurium differed significantly between the subjects (p < 0.0001); however, there were no differences within the interfascicular epineurium (p ≥ 0.37). There were no correlations between diffusion tensor indices and nerve structure at the fascicular level (p ≥ 0.29). Conclusion: High-field strength MRI enabled the depiction of the anisotropic diffusion within the fascicles and perineurium. Diffusion tensor indices of the peripheral nerve did not correlate with nerve structure at the fascicular level. Future studies should investigate the relationship between diffusion tensor indices at the fascicular level and axon- and myelin-related parameters.

Investigation of time-dependent diffusion in extra-axial brain tumors using oscillating-gradient spin-echo

Oscillating gradient spin-echo (OGSE) sequences provide access to short diffusion times and may provide insight into micro-scale internal structures of pathologic lesions based on an analysis of changes in diffusivity with differing diffusion times. We hypothesized that changes in diffusivity acquired with a shorter diffusion time may permit elucidation of properties related to the internal structure of extra-axial brain tumors. This study aimed to investigate the utility of changes in diffusivity between short and long diffusion times for characterizing extra-axial brain tumors. In total, 12 patients with meningothelial meningiomas, 13 patients with acoustic neuromas, and 11 patients with pituitary adenomas were scanned with a 3 T magnetic resonance imaging (MRI) scanner with diffusion-weighted imaging (DWI) using OGSE and pulsed gradient spin-echo (PGSE) (effective diffusion times [Δeff]: 6.5 ms and 35.2 ms) with b-values of 0 and 1000 s/mm2. Relative percentage changes between shorter and longer diffusion times were calculated using region-of-interest (ROI) analysis of brain tumors on λ1, λ2, λ3, and mean diffusivity (MD) maps. The diffusivities of PGSE, OGSE, and relative percentage changes were compared among each tumor type using a multiple comparisons Steel-Dwass test. The mean (standard deviation) MD at Δeff of 6.5 ms was 1.07 ± 0.23 10−3 mm2/s, 1.19 ± 0.18 10−3 mm2/s, 1.19 ± 0.21 10−3 mm2/s for meningothelial meningiomas, acoustic neuromas, and pituitary adenomas, respectively. The mean (standard deviation) MD at Δeff of 35.2 ms was 0.93 ± 0.22 10−3 mm2/s, 1.07 ± 0.19 10−3 mm2/s, 0.82 ± 0.21 10−3 mm2/s for meningothelial meningiomas, acoustic neuromas, and pituitary adenomas, respectively. The mean (standard deviation) of the relative percentage change was 15.7 ± 4.4%, 12.4 ± 8.2%, 46.8 ± 11.3% for meningothelial meningiomas, acoustic neuromas, and pituitary adenomas, respectively. Compared to meningiomas and acoustic neuromas, pituitary adenoma exhibited stronger diffusion time-dependence with diffusion times between 6.5 ms and 35.2 ms (P < 0.05). In conclusion, differences in diffusion time-dependence may be attributed to differences in the internal structures of brain tumors. DWI with a short diffusion time may provide additional information on the microstructure of each tumor and contribute to tumor diagnosis.

Better neural images by combining ultrahigh field strength MRI with innovative MRI sequences

Better MRI scanning technologies and protocols can provide insights into neurological disorders. In this review, we describe the basic concepts of MRI and, in the process, we convey to the reader the relevance of MRI as a high-resolution imaging modality of tissue structure and metabolism. We outline the main parameters for improving MRI resolution and sensitivity for the ultimate goal of optimizing the diagnosis of neurological diseases. A key to obtaining high-resolution images by MRI is the strength of the magnet’s external field strength (Bo). The higher the field strength, the better the signal-to-noise (SNR) of acquired signals. Hence, this results in improved sensitivity and resolution of the reconstructed images. This article recapitulates the advancement of MRI technology towards Ultra-High-Field Strength (UHF) apparatus and the consequent benefits in SNR. Other keys towards improving MRI images include deftly modifying the parameters of longitudinal magnetization relaxation time (T1), transverse magnetization relaxation time (T2), repetition times between radiofrequency (RF) pulses (TR), and the time of reading post-pulse (TE). Such parameters can be controlled through acquisition software associated with the MRI machines. The review profiles the cumulative efforts by researchers to complement UHF-MRI hardware with innovative RF pulse sequences protocols such as Diffusion Weighted Imaging (DWI), Pulse Gradient Spin Echo (PGSE), Oscillating Gradient Spin Echo (OGSE), Blood Oxygen Level Dependent (BOLD)-MRI and Arterial Spin Label (ASL)-MRI. Collectively, these advances in both MRI hardware and software have pushed the field to attain a mesoscopic level of resolution. Further enhancements in analyzing MRI images through Artificial Intelligence (AI) algorithms may advance resolutions beyond the mesoscopic stage and perhaps even toward the microscopic resolution of living tissue.

Motion compensated renal diffusion weighted imaging.

To assess the effect of respiratory motion and cardiac driven pulsation in renal DWI and to examine asymmetrical velocity-compensated diffusion encoding waveforms for robust ADC mapping in the kidneys. The standard monopolar Stejskal-Tanner pulsed gradient spin echo (pgse) and the asymmetric bipolar velocity-compensated (asym-vc) diffusion encoding waveforms were used for coronal renal DWI at 3T. The robustness of the ADC quantification in the kidneys was tested with the aforementioned waveforms in respiratory-triggered and breath-held cardiac-triggered scans at different trigger delays in 10 healthy subjects. The pgse waveform showed higher ADC values in the right kidney at short trigger delays in comparison to longer trigger delays in the respiratory triggered scans when the diffusion gradient was applied in the feet-head (FH) direction. The coefficient of variation over all respiratory trigger delays, averaged over all subjects was 0.15 for the pgse waveform in the right kidney when diffusion was measured in the FH direction; the corresponding coefficient of variation for the asym-vc waveform was 0.06. The effect of cardiac driven pulsation was found to be small in comparison to the effect of respiratory motion. Short trigger delays in respiratory-triggered scans can cause higher ADC values in comparison to longer trigger delays in renal DWI, especially in the right kidney when diffusion is measured in the FH direction. The asym-vc waveform can reduce ADC variation due to respiratory motion in respiratory-triggered scans at the cost of reduced SNR compared to the pgse waveform.

Impact of tissue properties on time-dependent alterations in apparent diffusion coefficient: a phantom study using oscillating-gradient spin-echo and pulsed-gradient spin-echo sequences

PurposeThe purpose of this study was to investigate whether the changes in apparent diffusion coefficients (ADCs) due to differences in diffusion time reflect tissue properties in actual measurements of phantoms.Materials and methodsVarious n-alkane phantoms and sucrose/collagen phantoms with various collagen densities were set up with and without polyvinyl alcohol (PVA) foam with an average pore diameter of 300 μm. Thus, n-alkanes or sucrose/collagen represented substrate viscosity and the presence of PVA foam represented tissue structure with septum. Diffusion-weighted images with various diffusion times (7.71–60 ms) were acquired using pulsed-gradient spin-echo (PGSE) and oscillating-gradient spin-echo (OGSE) sequences. The ADCs of the phantoms with and without PVA foam were calculated.ResultsThe ADCs of some of the phantoms without PVA decreased with diffusion times decreased. In the n-alkane phantoms, only C8H18 showed significantly different ADCs depending on the use of PVA foam in the OGSE sequence. On the other hand, sucrose/collagen phantoms showed significant differences according to diffusion time. The ADCs of the phantoms decreased as the molecular size of the n-alkanes or collagen density of the sucrose/collagen phantom increased. Compared to phantoms without PVA foam, the ADC of the phantoms with PVA foam decreased as the diffusion time increased.ConclusionChanges in ADCs due to differences in diffusion time reflect tissue properties in actual measurements of phantoms. These changes in ADCs can be used for tissue characterization in vivo.

A novel male Japanese quail structural connectivity atlas using ultra-high field diffusion MRI at 11.7 T

The structural connectivity of animal brains can be revealed using post-mortem diffusion-weighted magnetic resonance imaging (MRI). Despite the existence of several structural atlases of avian brains, few of them address the bird’s structural connectivity. In this study, a novel atlas of the structural connectivity is proposed for the male Japanese quail (Coturnix japonica), aiming at investigating two lines divergent on their emotionality trait: the short tonic immobility (STI) and the long tonic immobility (LTI) lines. The STI line presents a low emotionality trait, while the LTI line expresses a high emotionality trait. 21 male Japanese quail brains from both lines were scanned post-mortem for this study, using a preclinical Bruker 11.7 T MRI scanner. Diffusion-weighted MRI was performed using a 3D segmented echo planar imaging (EPI) pulsed gradient spin-echo (PGSE) sequence with a 200 upmum isotropic resolution, 75 diffusion-encoding directions and a b-value fixed at 4500 s/mm2. Anatomical MRI was likewise performed using a 2D anatomical T2-weighted spin-echo (SE) sequence with a 150 upmum isotropic resolution. This very first anatomical connectivity atlas of the male Japanese quail reveals 34 labeled fiber tracts and the existence of structural differences between the connectivity patterns characterizing the two lines. Thus, the link between the male Japanese quail’s connectivity and its underlying anatomical structures has reached a better understanding.

Validation of cardiac diffusion tensor imaging sequences: A multicentre test-retest phantom study.

Cardiac diffusion tensor imaging (DTI) is an emerging technique for the in vivo characterisation of myocardial microstructure, and there is a growing need for its validation and standardisation. We sought to establish the accuracy, precision, repeatability and reproducibility of state‐of‐the‐art pulse sequences for cardiac DTI among 10 centres internationally. Phantoms comprising 0%–20% polyvinylpyrrolidone (PVP) were scanned with DTI using a product pulsed gradient spin echo (PGSE; N = 10 sites) sequence, and a custom motion‐compensated spin echo (SE; N = 5) or stimulated echo acquisition mode (STEAM; N = 5) sequence suitable for cardiac DTI in vivo. A second identical scan was performed 1–9 days later, and the data were analysed centrally. The average mean diffusivities (MDs) in 0% PVP were (1.124, 1.130, 1.113) x 10−3 mm2/s for PGSE, SE and STEAM, respectively, and accurate to within 1.5% of reference data from the literature. The coefficients of variation in MDs across sites were 2.6%, 3.1% and 2.1% for PGSE, SE and STEAM, respectively, and were similar to previous studies using only PGSE. Reproducibility in MD was excellent, with mean differences in PGSE, SE and STEAM of (0.3 ± 2.3, 0.24 ± 0.95, 0.52 ± 0.58) x 10−5 mm2/s (mean ± 1.96 SD). We show that custom sequences for cardiac DTI provide accurate, precise, repeatable and reproducible measurements. Further work in anisotropic and/or deforming phantoms is warranted.

Characterization and correction of time-varying eddy currents for diffusion MRI.

To develop and test a method for reducing artifacts due to time-varying eddy currents in oscillating gradient spin-echo (OGSE) diffusion images. An in-house algorithm (TVEDDY), that for the first time retrospectively models eddy current decay, was tested on pulsed gradient spin echo and OGSE brain images acquired at 7 T. Image pairs were acquired using opposite polarity diffusion gradients. A three-parameter exponential decay model (two amplitudes and a time constant) was used to characterize and correct eddy current distortions by minimizing the intensity difference between image pairs. Correction performance was compared with conventional correction methods by evaluating the mean squared error (MSE) between diffusion-weighted images acquired with opposite polarity diffusion gradients. As a ground-truth comparison, images were corrected using field dynamics up to third order in space, measured using a field monitoring system. Time-varying eddy currents were observed for OGSE, which introduced blurring that was not reduced using the traditional approach but was diminished considerably with TVEDDY and field monitoring-informed model-based reconstruction. No MSE difference was observed between the conventional approach and TVEDDY for pulsed gradient spin echo, but for OGSE TVEDDY resulted in significantly lower MSE than the conventional approach. The field-monitoring reconstruction had the lowest MSE for both pulsed gradient spin echo and OGSE. This work establishes that it is possible to estimate time-varying eddy currents from the actual diffusion data, which provides substantial image-quality improvements for gradient-intensive diffusion MRI acquisitions like OGSE.

Gradient nonlinearity correction in liver DWI using motion-compensated diffusion encoding waveforms

Objective To experimentally characterize the effectiveness of a gradient nonlinearity correction method in removing ADC bias for different motion-compensated diffusion encoding waveforms.MethodsThe diffusion encoding waveforms used were the standard monopolar Stejskal–Tanner pulsed gradient spin echo (pgse) waveform, the symmetric bipolar velocity-compensated waveform (sym-vc), the asymmetric bipolar velocity-compensated waveform (asym-vc) and the asymmetric bipolar partial velocity-compensated waveform (asym-pvc). The effectiveness of the gradient nonlinearity correction method using the spherical harmonic expansion of the gradient coil field was tested with the aforementioned waveforms in a phantom and in four healthy subjects.ResultsThe gradient nonlinearity correction method reduced the ADC bias in the phantom experiments for all used waveforms. The range of the ADC values over a distance of ± 67.2 mm from isocenter reduced from 1.29 × 10–4 to 0.32 × 10–4 mm2/s for pgse, 1.04 × 10–4 to 0.22 × 10–4 mm2/s for sym-vc, 1.22 × 10–4 to 0.24 × 10–4 mm2/s for asym-vc and 1.07 × 10–4 to 0.11 × 10–4 mm2/s for asym-pvc. The in vivo results showed that ADC overestimation due to motion or bright vessels can be increased even further by the gradient nonlinearity correction.ConclusionThe investigated gradient nonlinearity correction method can be used effectively with various motion-compensated diffusion encoding waveforms. In coronal liver DWI, ADC errors caused by motion and residual vessel signal can be increased even further by the gradient nonlinearity correction.

Prediction of dMRI signals with neural architecture search

BackgroundThere is growing interest in the neuroscience community in estimating and mapping microscopic properties of brain tissue non-invasively using magnetic resonance measurements. Machine learning methods are actively investigated to predict the signals measured in diffusion magnetic resonance imaging (dMRI). New methodWe applied the neural architecture search (NAS) to train a recurrent neural network to generate a multilayer perceptron to predict the dMRI data of unknown signals based on the different acquisition parameters and training data. The search space of NAS is the number of neurons in each layer of the multilayer perceptron network. To our best knowledge, this is the first time to apply NAS to solve the dMRI signal prediction problem. ResultsThe experimental results demonstrate that the proposed NAS method can achieve fast training and predict dMRI signals accurately. For dMRI signals with four acquisition strategies of double diffusion encoding (DDE), double oscillating diffusion encoding (DODE), multi-shell and DSI-like pulsed gradient spin-echo (PGSE), the mean squared errors of the multilayer perceptron network designed by NAS are 0.0043, 0.0034, 0.0147 and 0.0199, respectively. Comparison with existing method(s)We also compared NAS with other machine learning prediction methods, such as support vector regression (SVR), decision tree (DT) and random forest (RF), k-nearest neighbors (KNN), adaboost regressor (AR), gradient boosting regressor (GBR) and extra-trees regressor (ET). NAS achieved the better prediction performance in most cases. ConclusionIn this study, NAS was developed for the prediction of dMRI signals and could become an effective prediction tool.

Axon diameter inferences in the human corpus callosum using oscillating gradient spin echo sequences

Previous methods used to infer axon diameter distributions using magnetic resonance imaging (MRI) primarily use single diffusion encoding sequences such as pulsed gradient spin echo (PGSE) and are thus sensitive to axons of diameters >5 μm. We applied oscillating gradient spin echo (OGSE) sequences to study human axons in the 1–2 μm range in the corpus callosum, which include the majority of axons constituting cortical connections. The ActiveAx model was applied to calculate the fitted mean effective diameter for axons (AxD) and was compared with values found using histology. Axon diameters from histological data were calculated using three different datasets; true diameters (minimum diameter), a combination of minimum and maximum diameters, and diameters measured across a consistent diffusion direction. The AxD estimates from MRI were 1.8 ± 0.1 μm to 2.34 ± 0.04 μm with an average of 2.0 ± 0.2 μm for the ActiveAx model. The histology AxD values were 1.43 ± 0.02 μm when using the true minimum axon diameters, 5.52 ± 0.02 μm when using the combination of minimum and maximum axon diameters, and 2.20 ± 0.02 μm when collecting measurements across a consistent diffusion direction. This experiment demonstrates the first known usage of OGSE to calculate axon diameters in the human corpus callosum on a 1–2 μm scale. The importance for the model to account for axonal orientation dispersion is indicated by histological results which more closely match the MRI model results depending on the direction of axon diameter measurements. These initial steps using this non-invasive imaging method can be applied to future methodology to develop in vivo axon diameter measurements in human brain tissue.

Xenon Diffusion in Ionic Liquids with Blurred Nanodomain Separation.

The dynamics of xenon gas, loaded in a series of 1-alkyl-3-methylimidazolium based ionic liquids, probes the formation of increasingly blurred polar/apolar nanodomains as a function of the anion type and the cation chain length. Exploiting 129 Xe NMR spectroscopy techniques, like Pulse Gradient Spin Echo (PGSE) and inversion recovery (IR), the diffusion motion and relaxation times are determined for 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Cn C1 im][TFSI]. A correlation between the ILs nano-structure and both xenon diffusivity and relaxation times, as well as chemical shifts, is outlined. Interestingly, comparison with previous results of the same properties in the homologous imidazolium chlorides and hexafluorophospate shows an opposite trend with the alkyl chain length. Classical molecular dynamics (MD) simulations are used to calculate the xenon and cation and anion diffusion coefficients in the same systems, including imidazolium cations with longer chains (n=4, 6, 8 … 20). An almost quantitative agreement with the experiments validates the MD simulations and, at the same time, provides the necessary structural and dynamic microscopic insights on the nano-segregation and diffusion of xenon in bistriflimide, chloride and hexafluorphosphate salts allowing to observe and rationalize the shaping effect of the cation in the nanostructure.

Diffusion in Sephadex Gel Structures: Time Dependency Revealed by Multi-Sequence Acquisition over a Broad Diffusion Time Range.

It has been increasingly reported that in biological tissues diffusion-weighted MRI signal attenuation deviates from mono-exponential decay, especially at high b-values. A number of diffusion models have been proposed to characterize this non-Gaussian diffusion behavior. One of these models is the continuous-time random-walk (CTRW) model, which introduces two new parameters: a fractional order time derivative α and a fractional order spatial derivative β. These new parameters have been linked to intravoxel diffusion heterogeneities in time and space, respectively, and are believed to depend on diffusion times. Studies on this time dependency are limited, largely because the diffusion time cannot vary over a board range in a conventional spin-echo echo-planar imaging sequence due to the accompanying T2 decays. In this study, we investigated the time-dependency of the CTRW model in Sephadex gel phantoms across a broad diffusion time range by employing oscillating-gradient spin-echo, pulsed-gradient spin-echo, and pulsed-gradient stimulated echo sequences. We also performed Monte Carlo simulations to help understand our experimental results. It was observed that the diffusion process fell into the Gaussian regime at extremely short diffusion times whereas it exhibited a strong time dependency in the CTRW parameters at longer diffusion times.

MESMERISED: Super-accelerating T1 relaxometry and diffusion MRI with STEAM at 7 T for quantitative multi-contrast and diffusion imaging

There is an increasing interest in quantitative imaging of T1, T2 and diffusion contrast in the brain due to greater robustness against bias fields and artifacts, as well as better biophysical interpretability in terms of microstructure. However, acquisition time constraints are a challenge, particularly when multiple quantitative contrasts are desired and when extensive sampling of diffusion directions, high b-values or long diffusion times are needed for multi-compartment microstructure modeling. Although ultra-high fields of 7 T and above have desirable properties for many MR modalities, the shortening T2 and the high specific absorption rate (SAR) of inversion and refocusing pulses bring great challenges to quantitative T1, T2 and diffusion imaging. Here, we present the MESMERISED sequence (Multiplexed Echo Shifted Multiband Excited and Recalled Imaging of STEAM Encoded Diffusion). MESMERISED removes the dead time in Stimulated Echo Acquisition Mode (STEAM) imaging by an echo-shifting mechanism. The echo-shift (ES) factor is independent of multiband (MB) acceleration and allows for very high multiplicative (ESxMB) acceleration factors, particularly under moderate and long mixing times. This results in super-acceleration and high time efficiency at 7 T for quantitative T1 and diffusion imaging, while also retaining the capacity to perform quantitative T2 and B1 mapping. We demonstrate the super-acceleration of MESMERISED for whole-brain T1 relaxometry with total acceleration factors up to 36 at 1.8 mm isotropic resolution, and up to 54 at 1.25 mm resolution qT1 imaging, corresponding to a 6x and 9x speedup, respectively, compared to MB-only accelerated acquisitions. We then demonstrate highly efficient diffusion MRI with high b-values and long diffusion times in two separate cases. First, we show that super-accelerated multi-shell diffusion acquisitions with 370 whole-brain diffusion volumes over 8 b-value shells up to b = 7000 s/mm2 can be generated at 2 mm isotropic in under 8 minutes, a data rate of almost a volume per second, or at 1.8 mm isotropic in under 11 minutes, achieving up to 3.4x speedup compared to MB-only. A comparison of b = 7000 s/mm2 MESMERISED against standard MB pulsed gradient spin echo (PGSE) diffusion imaging shows 70% higher SNR efficiency and greater effectiveness in supporting complex diffusion signal modeling. Second, we demonstrate time-efficient sampling of different diffusion times with 1.8 mm isotropic diffusion data acquired at four diffusion times up to 290 ms, which supports both Diffusion Tensor Imaging (DTI) and Diffusion Kurtosis Imaging (DKI) at each diffusion time. Finally, we demonstrate how adding quantitative T2 and B1+ mapping to super-accelerated qT1 and diffusion imaging enables efficient quantitative multi-contrast mapping with the same MESMERISED sequence and the same readout train. MESMERISED extends possibilities to efficiently probe T1, T2 and diffusion contrast for multi-component modeling of tissue microstructure.

Water and Ion Dynamics in Confined Media: A Multi-Scale Study of the Clay/Water Interface

This review details a large panel of experimental studies (Inelastic Neutron Scattering, Quasi-Elastic Neutron Scattering, Nuclear Magnetic Resonance relaxometry, Pulsed-Gradient Spin-Echo attenuation, Nuclear Magnetic Resonance Imaging, macroscopic diffusion experiments) used recently to probe, over a large distribution of characteristic times (from pico-second up to days), the dynamical properties of water molecules and neutralizing cations diffusing within clay/water interfacial media. The purpose of this review is not to describe these various experimental methods in detail but, rather, to investigate the specific dynamical information obtained by each of them concerning these clay/water interfacial media. In addition, this review also illustrates the various numerical methods (quantum Density Functional Theory, classical Molecular Dynamics, Brownian Dynamics, macroscopic differential equations) used to interpret these various experimental data by analyzing the corresponding multi-scale dynamical processes. The purpose of this multi-scale study is to perform a bottom-up analysis of the dynamical properties of confined ions and water molecules, by using complementary experimental and numerical studies covering a broad range of diffusion times (between pico-seconds up to days) and corresponding diffusion lengths (between Angstroms and centimeters). In the context of such a bottom-up approach, the numerical modeling of the dynamical properties of the diffusing probes is based on experimental or numerical investigations performed on a smaller scale, thus avoiding the use of empirical or fitted parameters.

Role of interlayer porosity and particle organization in the diffusion of water in swelling clays

This study focuses on the role played by the interparticle and interlayer porosities, and the preferred orientation of the particles on water diffusion in dual-porosity clayey media (i.e., swelling clay minerals). For this purpose, we use Na-vermiculite, a swelling clay that does not exhibit osmotic swelling and therefore allows a clear discrimination between the interparticle and interlayer porosities. Two samples were prepared with an equal proportion of interparticle and interlayer porosities (i.e., 0.25 each) but different degree of preferred particle orientation (i.e., isotropic vs anisotropic). Through-diffusion and pulsed gradient spin echo attenuation measurements by nuclear magnetic resonance of protons techniques were used to probe water mobility, while the orientation of the particles was quantified by X-ray scattering analysis. Experimental water diffusion results obtained with these two Na-vermiculite samples were compared to those with samples made of Na-kaolinite particles (non-swelling clay mineral) having only interparticle porosities equal to 0.25 and 0.5, corresponding respectively to the interparticle and the total porosity of the Na-vermiculite samples. In addition, these experimental results were compared to simulated data using Brownian dynamics with virtual porous media representative of the real samples. For the range of porosities investigated, a good agreement was observed between measured and simulated water mobilities. The obtained results confirmed the important role played by the preferential orientation of the particles on water dynamics in clayey media, through an important reduction of overall water mobility between the isotropic and anisotropic Na-vermiculite samples. These results also showed that for the same total porosity, the presence of interlayer porosity and associated nano-confinement led to a logical reduction in the pore diffusion coefficient of water in Na-vermiculite in comparison to Na-kaolinite. Moreover, in comparison with Na-kaolinite having the same interparticle porosity, results showed that the contribution of the interlayer volume on the traversing flux was small compared to the interparticle volume. Finally, the computed results revealed that the anisotropy in water diffusion can be directly predicted based on the degree of particles preferred orientation, irrespective of the total or the distribution of the different porosity types.

Studying the "Rigid-Flexible" Properties of Polymeric Micelle Core-Forming Segments with a Hydrophobic Phthalocyanine Probe Using NMR and UV Spectroscopy.

The aim of the performed studies was to thoroughly examine the internal structure of self-assembled nanocarriers (i.e., polymeric micelles—PMs) by means of a hydrophobic phthalocyanine probe in order to identify the crucial features that are required to enhance the photoactive probe stability and reactivity. PMs of hydrophilic poly(ethylene glycol) and hydrophobic poly(ε-caprolactone) (PCL) or poly(d,l-lactide) (PDLLA) were fabricated and loaded with tetra tert-butyl zinc(II) phthalocyanine (ZnPc-t-but4), a multifunctional spectroscopic probe with a profound ability to generate singlet oxygen upon irradiation. The presence of subdomains, comprising “rigid” and “flexible” regions, in the studied block copolymers’ micelles as well as their interactions with the probe molecules, were assessed by various high-resolution NMR measurements [e.g., through-space magnetic interactions by the 1D NOE effect, pulsed field gradient spin-echo, and spin–lattice relaxation time (T1) techniques]. The studies of the impact of the core-type microenvironment on the ZnPc-t-but4 photochemical performance also included photobleaching and reactive oxygen species measurements. ZnPc-t-but4 molecules were found to exhibit spatial proximity effects with both (PCL and PDLLA) hydrophobic polymer chains and interact with both subdomains, which are characterized by different rigidities. It was deduced that the interfaces between particular subdomains constitute an optimal host space for probe molecules, especially in the context of photochemical stability, photoactivity (i.e., for significant enhancement of singlet oxygen generation rates), and aggregation prevention. The present contribution proves that the combination of an appropriate probe, high-resolution NMR techniques, and UV–vis spectroscopy enables one to gain complex information about the subtle structure of PMs essential for their application as nanocarriers for photoactive compounds, for example, in photodynamic therapy, nanotheranostics, combination therapy, or photocatalysis, where the micelles constitute the optimal microenvironment for the desired photoreactions.

Using NMR to Test Molecular Mobility during a Chemical Reaction.

We evaluate critically the use of pulsed gradient spin-echo nuclear magnetic resonance to measure molecular mobility during chemical reactions. With raw NMR spectra available in a public depository, we confirm the boosted mobility during the click chemical reaction (Wang et al. Science 2020 369, 537-541) regardless of the order of magnetic field gradient (linearly increasing, linearly decreasing, random sequence). We also confirm boosted mobility for the Diels-Alder chemical reaction. The conceptual advantage of the former chemical system is that a constant reaction rate implies a constant catalyst concentration, whereas that of the latter is the absence of a paramagnetic catalyst, precluding paramagnetism as an objection to the measurements. The data and discussion in this paper show the reliability of experiments when one avoids convection, allows decay of nuclear spin magnetization between successive pulses and recovery of its intensity between gradients, and satisfies quasi-steady state during the time window to acquire each datum. Especially important is to make comparisons on the time scale of the actual chemical reaction kinetics. We discuss possible sources of mistaken conclusions that are desirable to avoid.

Diffusion Tensor Imaging of Skeletal Muscle Contraction Using Oscillating Gradient Spin Echo.

Diffusion tensor imaging (DTI) measures water diffusion in skeletal muscle tissue and allows for muscle assessment in a broad range of neuromuscular diseases. However, current DTI measurements, typically performed using pulsed gradient spin echo (PGSE) diffusion encoding, are limited to the assessment of non-contracted musculature, therefore providing limited insight into muscle contraction mechanisms and contraction abnormalities. In this study, we propose the use of an oscillating gradient spin echo (OGSE) diffusion encoding strategy for DTI measurements to mitigate the effect of signal voids in contracted muscle and to obtain reliable diffusivity values. Two OGSE sequences with encoding frequencies of 25 and 50 Hz were tested in the lower leg of five healthy volunteers with relaxed musculature and during active dorsiflexion and plantarflexion, and compared with a conventional PGSE approach. A significant reduction of areas of signal voids using OGSE compared with PGSE was observed in the tibialis anterior for the scans obtained in active dorsiflexion and in the soleus during active plantarflexion. The use of PGSE sequences led to unrealistically elevated axial diffusivity values in the tibialis anterior during dorsiflexion and in the soleus during plantarflexion, while the corresponding values obtained using the OGSE sequences were significantly reduced. Similar findings were seen for radial diffusivity, with significantly higher diffusivity measured in plantarflexion in the soleus muscle using the PGSE sequence. Our preliminary results indicate that DTI with OGSE diffusion encoding is feasible in human musculature and allows to quantitatively assess diffusion properties in actively contracting skeletal muscle. OGSE holds great potential to assess microstructural changes occurring in the skeletal muscle during contraction, and for non-invasive assessment of contraction abnormalities in patients with muscle diseases.