Gradient Spin Echo Research Articles

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.

Test-retest reproducibility of in vivo oscillating gradient and microscopic anisotropy diffusion MRI in mice at 9.4 Tesla.

Microstructure imaging with advanced diffusion MRI (dMRI) techniques have shown increased sensitivity and specificity to microstructural changes in various disease and injury models. Oscillating gradient spin echo (OGSE) dMRI, implemented by varying the oscillating gradient frequency, and microscopic anisotropy (μA) dMRI, implemented via tensor valued diffusion encoding, may provide additional insight by increasing sensitivity to smaller spatial scales and disentangling fiber orientation dispersion from true microstructural changes, respectively. The aims of this study were to characterize the test-retest reproducibility of in vivo OGSE and μA dMRI metrics in the mouse brain at 9.4 Tesla and provide estimates of required sample sizes for future investigations. Twelve adult C57Bl/6 mice were scanned twice (5 days apart). Each imaging session consisted of multifrequency OGSE and μA dMRI protocols. Metrics investigated included μA, linear diffusion kurtosis, isotropic diffusion kurtosis, and the diffusion dispersion rate (Λ), which explores the power-law frequency dependence of mean diffusivity. The dMRI metric maps were analyzed with mean region-of-interest (ROI) and whole brain voxel-wise analysis. Bland-Altman plots and coefficients of variation (CV) were used to assess the reproducibility of OGSE and μA metrics. Furthermore, we estimated sample sizes required to detect a variety of effect sizes. Bland-Altman plots showed negligible biases between test and retest sessions. ROI-based CVs revealed high reproducibility for most metrics (CVs < 15%). Voxel-wise CV maps revealed high reproducibility for μA (CVs ~ 10%), but low reproducibility for OGSE metrics (CVs ~ 50%). Most of the μA dMRI metrics are reproducible in both ROI-based and voxel-wise analysis, while the OGSE dMRI metrics are only reproducible in ROI-based analysis. Given feasible sample sizes (10-15), μA metrics and OGSE metrics may provide sensitivity to subtle microstructural changes (4-8%) and moderate changes (> 6%), respectively.

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.

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.

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.

Molecular self-diffusion in internal magnetic fields of porous medium investigated by NMR MGSE method

Inhomogeneous magnetic fields generated in porous media due to differences in magnetic susceptibility at solid/liquid interfaces and due to intrinsic or artificially doped magnetic impurities can be used to gain insight into the molecular dynamics of fluid in the structure of a porous medium using the concept of NMR modulated gradient spin echo method. We extended the theory of this method to the case of an inhomogeneous magnetic field that cannot be approximated by an uniform gradient, in order to explain the CPMG measurements of self-diffusion in water soaked ceramics, which are doped with magnetic impurities of different contents. The new interpretation provides the spin relaxation times, the average pore size and their distribution, as well as the strength of the internal magnetic gradient fields in the doped ceramics.

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.

Structural and dynamic properties of some aqueous salt solutions.

Aqueous salt solutions are utilized and encountered in wide-ranging technological applications and natural settings. Towards improved understanding of the effect of salts on the dynamic properties of such systems, dilute aqueous salt solutions (up to 1 molar concentration) are investigated here, via experiments and molecular simulations. Four salts are considered: sodium chloride, for which published results are readily available for comparison, ammonium acetate, barium acetate and barium nitrate, for which published data are scarce. In the present work, molecular dynamics (MD) simulations are conducted to quantify viscosity and water self-diffusion coefficients, together with rheometry and Pulsed Field Gradient Spin Echo (PFGSE)-NMR experiments for validation. Simulation predictions are consistent with experimental observations in terms of trend and magnitude of salt-specific effects. Combining insights from the approaches considered, an interpretation of the results is proposed whereby the capacity of salts to influence bulk dynamics arises from their molecular interfacial area and strength of interaction with first hydration-shell water molecules. For the concentration range investigated, the interpretation could be useful in formulating aqueous systems for applications including the manufacturing of advanced catalysts.

Proton conduction in hydronium solvate ionic liquids affected by ligand shape.

We investigated the ligand dependence of the proton conduction of hydronium solvate ionic liquids (ILs), consisting of a hydronium ion (H3O+), polyether ligands, and a bis[(trifluoromethyl)sulfonyl]amide anion (Tf2N-; Tf = CF3SO2). The ligands were changed from previously reported 18-crown-6 (18C6) to other cyclic or acyclic polyethers, namely, dicyclohexano-18-crown-6 (Dh18C6), benzo-18-crown-6 (B18C6) and pentaethylene glycol dimethyl ether (G5). Pulsed-field gradient spin echo nuclear magnetic resonance results revealed that the protons of H3O+ move faster than those of cyclic 18C6-based ligands but as fast as those of acyclic G5 ligands. Based on these results and density functional theory calculations, we propose that the coordination of a cyclic ether ligand to the H3O+ ion is essential for fast proton conduction in hydronium solvate ILs. Our results attract special interest for many electro- and bio-chemical applications such as electrolyte systems for fuel cells and artificial ion channels for biological cells.

Luminescent cyclometalated platinum(ii) complexes with acyclic diaminocarbene ligands: structural, photophysical and biological properties.

Four new cyclometalated Pt(ii) complexes bearing acyclic diaminocarbene (ADC) ligands, [Pt(C^N)Cl{C(NHXyl)(NHR)}] [C^N = 2,6-difluorophenylpyridine (dfppy), phenylquinoline (pq); R = Pr 3a, 4a, CH2Ph 3b, 4b], were prepared by the nucleophilic attack on the isocyanide [Pt(C^N)Cl(CNXyl)] (C^N = dfppy 1, pq 2) by the corresponding amine RNH2 (R = Pr, CH2Ph). Complexes 3 show in their 1H NMR spectra in CDCl3 a notable concentration dependence, with a clear variation of the δH (NHXyl) signal, suggesting an assembling process implying donor-acceptor NHXylCl bonding, also supported by 1D-PGSE (Pulse Field Gradient Spin Echo) and 2D-DOSY (Diffusion Ordered Spectroscopy) NMR experiments in solution and X-ray diffraction studies. The intermolecular interactions in compounds 3a and 3b were studied by using Hirshfeld surface analysis and Non-Covalent Interaction (NCI) methods on their X-ray structures. Their photophysical properties were investigated by absorption and emission spectroscopies and also by TD-DFT calculations performed on 3a and 4b. These complexes show green (3) or orange (4) phosphorescence, attributed to a mixed 3IL/3MLCT excited state. The carbene ligand does not affect the emission maxima but it produces an increase of the quantum yields in relation to the isocyanide in the precursors. In fluid solutions, the emission is not concentration-dependent, but the complexes may show aggregation induced emission as detailed for complexes 3a and 4a. In addition, cytotoxicity studies in the human cell lines A549 (lung carcinoma) and HeLa (cervix carcinoma) showed good activity for these complexes and 3a, 3b and 4a exhibit a strong effect on DNA electrophoretic mobility. To the best of our knowledge, compounds 3 and 4 represent the first examples of cycloplatinated complexes bearing acyclic diamino carbenes with antiproliferative properties.

Synthesis and characterization of bis(amine)palladium(II) carboxylate complexes as precursors of palladium nanoparticles.

The synthesis and characterization of the adducts of n-alkyl amine and palladium n-alkyl carboxylate, [Pd(R2NH2)2(R1COO)2] (R1 = 1, 7, and 11; R2 = 8, 12, and 16), as precursors for the synthesis of palladium nanoparticles (PdNPs) was carried out via differential scanning calorimetry, FT-IR, Raman and UV-Vis spectroscopy, NMR spectroscopy (1H, 13C pulsed field gradient spin-echo (PGSE), and 13C CP-MAS), and powder X-ray diffraction. Pd n-alkyl carboxylates were obtained by a ligand exchange reaction from palladium acetate and the appropriate aliphatic carboxylic acid. It is proposed that carboxyl moieties in the presence of amine ligands are bound to palladium ions via monodentate bonding as opposed to bridging bidentate coordination of pure palladium carboxylate which exists in the form of polymer aggregates. All the studied palladium carboxylate/amine complexes form bilayer lamellar structures and exhibit first-order melting transitions. The evidence presented in this study shows that the phase behavior of bivalent metal carboxylates is mainly controlled by the type of coordination of carboxylate head groups. For n-alkyl carboxylates, linear chain type aggregates replace the trimeric units of Pd acetate. In solution, in the presence of amine, palladium salt aggregates disintegrate and the Pd complex is isolated and stabilized by amine molecules. Using bis(amine) palladium carboxylate adducts as precursors, palladium nanoparticles were fabricated. During high temperature thermolysis, the bis(amine) Pd carboxylate complex decomposes to form small sized Pd nanoparticles. Combining NMR techniques with FTIR spectroscopy, it was possible to follow an original stabilization mechanism. PdNPs are stabilized by weakly interacting long chain aliphatic amide and carboxylic acid derived from the palladium precursor.

Effects of phase regression on high-resolution functional MRI of the primary visual cortex

High-resolution functional MRI studies have become a powerful tool to non-invasively probe the sub-millimeter functional organization of the human cortex. Advances in MR hardware, imaging techniques and sophisticated post-processing methods have allowed high resolution fMRI to be used in both the clinical and academic neurosciences. However, consensus within the community regarding the use of gradient echo (GE) or spin echo (SE) based acquisition remains largely divided. On one hand, GE provides a high temporal signal-to-noise ratio (tSNR) technique sensitive to both the macro- and micro-vascular signal while SE based methods are more specific to microvasculature but suffer from lower tSNR and specific absorption rate limitations, especially at high field and with short repetition times.Fortunately, the phase of the GE-EPI signal is sensitive to vessel size and this provides a potential avenue to reduce the macrovascular weighting of the signal (phase regression, Menon 2002). In order to determine the efficacy of this technique at high-resolution, phase regression was applied to GE-EPI timeseries and compared to SE-EPI to determine if GE-EPI's specificity to the microvascular compartment improved. To do this, functional data was collected from seven subjects on a neuro-optimized 7 T system at 800 μm isotropic resolution with both GE-EPI and SE-EPI while observing an 8 Hz contrast reversing checkerboard. Phase data from the GE-EPI was used to create a microvasculature-weighted time series (GE-EPI-PR). Anatomical imaging (MP2RAGE) was also collected to allow for surface segmentation so that the functional results could be projected onto a surface. A multi-echo gradient echo sequence was collected and used to identify venous vasculature.The GE-EPI-PR surface activation maps showed a high qualitative similarity with SE-EPI and also produced laminar activity profiles similar to SE-EPI. When the GE-EPI and GE-EPI-PR distributions were compared to SE-EPI it was shown that GE-EPI-PR had similar distribution characteristics to SE-EPI (p < 0.05) across the top 60% of cortex. Furthermore, it was shown that GE-EPI-PR has a higher contrast-to-noise ratio (0.5 ± 0.2, mean ± std. dev. across layers) than SE-EPI (0.27 ± 0.07) demonstrating the technique has higher sensitivity than SE-EPI. Taken together this evidence suggests phase regression is a useful method in low SNR studies such as high-resolution fMRI.

Dual-Cation Electrolyte System Using Quaternary Ammonium Salts and Ionic Liquid for High Power and High Energy Li4Ti5O12//AC Hybrid Capacitor System

[Introduction] The Use of thick electrodes (> 100 µm) is a simple approach to increase the energy density of electrochemical energy storage devices. However, the high ionic resistance in thick electrodes limits the high-power applications of such devices. “Dual-cation” electrolytes for thick-electrode hybrid capacitor systems, typically composed of Li4Ti5O12 (LTO, 200 µm) and activated carbon (AC, 400 µm) electrodes, have been developed[1]. A dual-cation electrolyte is composed of lithium tetrafluoroborate (LiBF4) and spiro-(1,1')-bipyrrolidinium tetrafluoroborate (SBPBF4) dissolved in propylene carbonate (PC). An SBP-based dual-cation electrolyte, comprising 1 M LiBF4 + 2 M SBPBF4 / PC, exhibits a higher total ionic conductivity (7.67 S cm-1) than the single-cation electrolyte (3.40 S cm-1), consisting of 1 M LiBF4 / PC, while Li+ conductivity decreases with an increase of SBPBF4 concentration. Our interesting finding was that the presence of SBP+, despite the low Li+ transport in the electrolyte bulk, reduces overvoltage associated with migration limitation in the thick LTO electrode, and thus enhances power density in LTO//AC hybrid capacitor systems.In this study, we propose another dual-cation electrolyte using a 1-ethyl-3-methylimidazolium (EMI) cation in place of the SBP cation, which further enhances the power performance of LTO//AC hybrid capacitor systems. It has been shown that an EMI-based electrolyte exhibits a higher total ionic conductivity (10.9 S cm-1) than the SBP-based electrolyte. Herein we provide a detailed account of factors that improve the discharge properties of the EMI-based dual-cation electrolyte by using electrochemical and spectroscopic methods.[Experimental] The dual-cation electrolytes were prepared by dissolving 1 M LiBF4 and x M SBPBF4 (0 < x < 3) or x' M EMIBF4 (0 < x' < 4), in PC. The ionic conductivity of the prepared electrolytes was measured using a conductivity meter. The LTO(200 μm)//AC(400 μm) hybrid capacitor system assumed a coin type cell assembly; charge-discharge measurements were conducted at 1 mA cm-2 (at the charge) and 1 to 200 mA cm-2 (at the discharge). Pulsed Gradient Spin Echo (PGSE) NMR analysis was conducted to determine the self-diffusion coefficients of the Li(7Li), SBP (1H), and EMI (1H) cations and the BF4 (19F) anion in the electrolytes.. Electrochemical impedance spectroscopy (EIS) was performed to evaluate the resistance of the LTO electrode using LTO//LTO symmetric cells designed at both the delithiated (SOC of LTO = 0%) and lithiated (SOC of LTO = 25%) states.[Results and discussion]The results of the ionic conductivity for all electrolytes are shown in Figure 1. The EMI-based dual-cation electrolyte exhibited higher ionic conductivity than the SBP-based electrolyte. The results of the charge-discharge test (Figure 2) showed that the EMI-based dual-cation electrolyte exhibits optimal discharge properties among the electrolytes. Moreover, the PGSE NMR analysis results indicated that the self-diffusion coefficient for all ions including Li+ decreased with an increase in EMIBF4 concentration. In contrast, the ionic resistance (R ion) of the LTO negative electrode calculated from the EIS results at the delithiated state (SOC of LTO = 0%) yielded lower values for the EMI-based dual-cation electrolyte (11.1 Ω cm2) than that for the SBP-based (14.0 Ω cm2) and single-cation (27.1 Ω cm2) electrolytes. We also evaluated the charge-transfer resistance (R ct) from the EIS results using LTO//LTO symmetric cells at the lithiated state (SOC of LTO = 25%). The R ct was found to be lower in the EMI-based dual-cation electrolyte (1.71 Ω cm2) than that in the SBP-based (2.28 Ω cm2) and single-cation (3.57 Ω cm2) electrolytes. These results showed that charge-transfer reactions at the LTO electrodes occur more readily in the dual-cation electrolyte.The results indicated that a reduction in R ct occurs because ion potential suppression occurs owing to the accelerated ion transport in the electrode, as well as in our previous study[1]. The suppression of the ionic potential increased the Li+ concentration and reaction current at the collector side, which decreased the R ct. This is because the advantage of an increase in total ionic conductivity is effective even when the transport ofLi+ is reduced in a thick-electrode system. This study confirms that the use of the EMI-based electrolyte, which has a higher total ionic conductivity than the SBP-based electrolyte, exhibits a remarkable suppression of R ion and R ct. The use of thick electrodes, therefore, facilitates an increase in total ionic conductivity, which has a more desirable effect than that of high Li+ conductivity, especially in the EMI-based dual-cation electrolyte, wherein the power density of the thick-electrode LTO//AC hybrid capacitor systems was significantly improved.[1] Y. Chikaoka et al., J. Phys. Chem. C, in press(doi.org/10.1021/acs.jpcc.0c01916). Figure 1

How Does the Solvent Composition Influence the Transport Properties of Electrolyte Solutions?

The electrolyte solutions used in lithium ion batteries have been optimized based on the empirical knowledge and concept. Yet the ion transport phenomena in the electrolyte solution, which composed of mixed solvent with salt concentration of about 1 mol kg−1, are complicated and significantly different from those in dilute solutions. In the present study, the characteristics of the electrolyte solutions are reanalyzed by using physical and spectroscopic data for the electrolyte solutions, which were obtained from our experiment, and by referring to recent theoretical studies 1,2) and the experimentally determined diffusion coefficient in previous studies 3,4).We experimentally measured the viscosity η and ionic conductivity σ of the electrolyte solutions of 1 mol kg−1 of LiPF6 and lithium bis(fluorosulfonyl)imide (LiFSA) dissolved in the binary mixture solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) in the temperature range of 288 ≤ T/K ≤ 328 with varying the EC content from 0 to 60 vol.%, which translates into the molar fraction of EC in 0 ≤ x EC ≤ 0.6 and the solute to solvent ratio constant (total ca. 11 solvent molecules are present per solute in the system). The diffusion coefficients D of each species, Li+, PF6, FSA−, EC and DMC, were determined by pulse gradient spin echo NMR. The state of molecules around Li+ was examined by the Raman spectra of the solvents and anions.With the increase in x EC, DMC solvating Li+ is replaced by EC, resulting in the increase in the total number of solvents around Li+. Reanalysis of Raman spectra based on Borodin's calculations 2) reassessed the solvation numbers and confirmed that the preferential coordination of EC to Li+, but the extent of the preference was not as strong as previously conceived. The addition of EC, more viscous fluid than DMC, into the system leads to the increase in η, which should be responsible for the monotonous decrease in D of all the species with x EC. On the other hand, σ initially increases until marking the maximum at x EC = ~0.3. The opposite trend between D and σ, i.e., dD/dx EC < 0 while dσ/dx EC > 0, at low x EC suggests that the Nernst-Einstein relation does not hold as it ignores the inter-ionic correlations. The analysis of the Stokes radii r St based on η and D obtained in the present study implies that the increase in x EC results in the decrease in r St for all the species, among which the anions are most influenced. Although only an equivocal picture on the cation-anion correlation, such as the ion pair formation, was obtained from the Raman spectroscopy, the present study is consistent with the view that the highly Li+-solvating EC, with its higher dielectric shielding effect than DMC, liberates the anions from the attraction from Li+, enhancing the cation-anion anti-correlation, which positively contributes to the ionic conductivity until the viscosity prevails at high x EC. The Einstein-Stokes formula and van der Waals radius are certainly "classical" concepts; nonetheless, if properly formulated, they can be consistent with the solvation number obtained from Raman spectra not only qualitatively but also semi-quantitatively. References Borodin, G. V. Zhuang, P. N. Ross and K. Xu, Phys. Chem. C, 117, 7433 – 7444 (2013).Borodin, M. Olguin, P. Ganesh, P. R. C. Kent, J. L. Allen and W. A. Henderson, Chem. Chem. Phys., 18, 164 – 175 (2016).Hayamizu, Y. Aihara, S. Arai, C. Garcia-Martinez, J. Phys. Chem. B, 103, 519 – 524 (1999).Hayamizu, J. Chem. Eng. Data, 57, 2012 – 2017 (2012). Figure 1

T1, T2, and Fat Fraction Cardiac MR Fingerprinting: Preliminary Clinical Evaluation.

Dixon cardiac magnetic resonance fingerprinting (MRF) has been recently introduced to simultaneously provide water T1 , water T2 , and fat fraction (FF) maps. To assess Dixon cardiac MRF repeatability in healthy subjects and its clinical feasibility in a cohort of patients with cardiovascular disease. T1MES phantom, water-fat phantom, 11 healthy subjects and 19 patients with suspected cardiovascular disease. Prospective. 1.5T, inversion recovery spin echo (IRSE), multiecho spin echo (MESE), modified Look-Locker inversion recovery (MOLLI), T2 gradient spin echo (T2 -GRASE), 6-echo gradient rewound echo (GRE), and Dixon cardiac MRF. Dixon cardiac MRF precision was assessed through repeated scans against conventional MOLLI, T2 -GRASE, and PDFF in phantom and 11 healthy subjects. Dixon cardiac MRF native T1 , T2 , FF, postcontrast T1 and synthetic extracellular volume (ECV) maps were assessed in 19 patients in comparison to conventional sequences. Measurements in patients were performed in the septum and in late gadolinium enhanced (LGE) areas and assessed using mean value distributions, correlation, and Bland-Altman plots. Image quality and diagnostic confidence were assessed by three experts using 5-point scoring scales. Paired Wilcoxon rank signed test and paired t-tests were applied. Statistical significance was indicated by *(P < 0.05). Dixon cardiac MRF showed good overall precision in phantom and in vivo. Septal average repeatability was ~23 msec for T1 , ~2.2 msec for T2 , and ~1% for FF. Biases in healthy subjects/patients were measured at +37 msec*/+60 msec* and -8.8 msec*/-8 msec* when compared to MOLLI and T2 -GRASE, respectively. No statistically significant differences in postcontrast T1 (P = 0.17) and synthetic ECV (P = 0.19) measurements were observed in patients. Dixon cardiac MRF attained good overall precision in phantom and healthy subjects, while providing coregistered T1 , T2 , and fat fraction maps in a single breath-hold scan with similar or better image quality than conventional methods in patients. 2. 2.

Improved gradient waveforms for oscillating gradient spin-echo (OGSE) diffusion tensor imaging.

The dependence of the diffusion tensor on frequency is of great interest in studies of tissue microstructure because it reveals restrictions to the Brownian motion of water molecules caused by cell membranes. Oscillating gradient spin-echo (OGSE) sequences can sample this dependence with gradient shapes for which the power spectrum of the zeroth moment is focused at a target frequency. In order to maintain the total spectral power (ie the b-value), oscillating gradient amplitudes must grow with the frequency squared. For this reason, OGSE applications on clinical MRI scanners are limited to low frequencies, for which it is difficult to obtain a narrow frequency bandwidth of the gradient moment in a useful echo time. In particular, the commonly used pair of single-period trapezoidal-cosine pulses separated by a half-period produces significant side lobes away from the target frequency. To mitigate this effect, improved OGSE waveforms are proposed, which reduce the gap between the two gradient pulses to the minimum duration required for the refocusing RF pulse. Additionally, a slight deviation from the periodicity of the waveforms is proposed in order to permit using the maximum slew rate of the gradient system for all lobes of trapezoidal waveforms while maintaining advantageous spectral properties, which is not the case for the currently used OGSE sequences. Numerical calculations validate these changes, showing that both modifications significantly narrow the gradient moment power spectrum and increase the contribution of its main lobe to the b-value, thus improving the specificity of the measurement. The utility of the new shapes is demonstrated by diffusion tensor measurements of human white matter in vivo over the range of 30-75 Hz with a b-value of nearly 1000 s/mm2 , using a high-performance gradient insert. However, the improvement should increase the sampling precision of OGSE experiments for all gradient systems.