Relaxation Time Measurements Research Articles

Characterizing water transfer in compacted soils in the context of energy storage, contribution of magnetic resonance imaging (MRI)

The concept of energy geostructures consists in enhancing existing civil engineering structures from an energy point of view thanks to the insertion of heat exchanger tubes. In order to consider the use of compacted soil embankments for heat storage [1], a good knowledge of water movement is required. Indeed, the increase in temperature of the exchangers leads to a migration of liquid/vapour water to the surface layers [2]. A loss of moisture may alter the thermal capacity of the soil [1] and therefore the system energy efficiency. To determine unsaturated hydraulic properties, the Instantaneous Profile Method (IPM) consists in inducing transient flow in a long cylindrical sample of soil and then measuring the resulting water content and/or pore water pressure profiles at various time intervals [3]. The unsaturated hydraulic conductivity (ku) is then computed using Darcy’s law.
 The direct evaporation technique allows the measurement of the suction profile in a soil column submitted to drying [4] using filter papers whose water retention curve is known. This method is quite reliable but requires long equilibrium time. Thus, the tests need several weeks and do not give accurate results at the early stages of drying, as the soil state is close to saturation. The analysis of the results when the soil retention capacity is low is therefore complicated, especially when the flow is coupled with temperature variations.
 In this study, this classical method was compared to a faster alternate method using nuclear magnetic resonance imaging (MRI) that allows for non-intrusive, continuous and small-scale monitoring of the effect of thermo-hydraulic solicitations on water transfer within the sample. The use of MRI for monitoring the drying/wetting front progression appeared in 1970 [5]. Simpson et al. [6] presented the successive studies that have made it possible to develop a method for monitoring the movement of water within a sample. These measurements can be 1D, 2D and 3D.
 The tests were performed on a sandy lean clay sampled in the Paris region in France. The soil was dried, pulverized, and sieved through a 2 mm sieve before experiments. The compaction state was selected to optimize the heat storage capacity [4] with a water content of 16.3% and a dry density of 1.79 Mg.m-3. Ten cylindrical samples of 70 mm in diameter and 20 mm in height were compacted and superimposed with introducing filter paper disks between them. The regular weighting of each sample and each filter paper during three months allowed the derivation of the ku curve by the IPM method.
 For the MRI method, 9 samples of 36 mm in diameter and 10 mm in height were compacted at the initial state then brought to different degrees of saturation. The measurement of the water proton relaxation time using a Bruker Biospec 24/40 superconducting magnet (100 MHz), allowed the definition of a calibration curve which connects MRI signal to the water content of the samples (Figure 1b). A Single Point Imaging pulse sequence [7] was used to obtain the signal intensity (encoding time 75 µs < t < 200 µs). In an image acquired with the SPI method, the intensity of each voxel (S) is :
 (1) Whereis the magnetization in a pixel and is the transverse relaxation time.
 The calibration curve is shown in Figure 1b. Then, a larger sample of 30mm in height was compacted and exposed to an air flow at 20°C and 30% relative humidity through using a remote humid air generation system. 27 measurements points were monitored with an interval of 1.1 mm along the sample. Four examples of the recorded profiles are shown in Figure 1c. The evolution of the water content inside the sample is then calculated using the calibration curve to interpret the water migration in the samples submitted to humidity- and temperature-controlled air (Figure 1a). The pre-established retention curve of the soil will be used to calculate its matric suction. At each depth, the flow velocity and the hydraulic gradient will be calculated from the water content profiles and suction profiles respectively in order to determine the unsaturated hydraulic conductivity. 
 These experimental developments allow the non-intrusive and continuous quantification of water movement in unsaturated soils during the application of coupled thermo-hydraulic solicitations. The understanding of these fundamental parameters is a key step for studying thermo-hydromechanical behavior of compacted soils considered for heat storage. The results provide insight into the feasibility of these structures in terms of their long-term energy efficiency and stability.

Measuring free radicals with relaxometry: Pioneering steps for measurements in human semen

A possible biological mechanism for unexplained male infertility is due to the effect of oxidative stress (OS), defined by the imbalance of reactive oxygen species (ROS) production, and the capacity of the antioxidant defence system to counteract it. In physiological concentrations, ROS and especially free radicals play an essential role in sperm maturation and fertilization, while an overabundance could lead to OS-induced damage to spermatozoa. To date, there are no direct detection techniques available that can measure the total amount of free radicals real time and identify where and when free radicals are generated. This study applies a quantum sensing technique using fluorescent nanodiamonds (FNDs), called T1 relaxometry, which is uniquely sensitive and specific for free radicals allowing measurements of the current radical load for nanoscale detection in living cells and body fluids. This proof-of-principle study investigates if we can use this technique to detect the free radical generation in human whole and separated, using density gradient centrifugation, semen. This method could be potentially used as new diagnostic measure for unexplained infertility or to track the effect of therapeutic interventions such as lifestyle changes. We adapted the existing relaxometry technique to measure free radicals in semen. The measured relaxation time (T1 time) was correlated to sperm concentration and progressive motility. Additionally, we explored the influence of the oxidative trigger hydrogen peroxide and the antioxidant glutathione on the free radical concentration measured. No significant correlations were found, which indicates that measurements in more proximity of the sperm cell are required to use relaxometry as a potential diagnostic tool for unexplained male infertility.

Enhancing SNSPDs detection efficiency via suspended SiO2 membrane

Superconducting nanowire single-photon detectors (SNSPDs) with high detection efficiency have played significant role in numerous applications for photon detection from visible light to mid-infrared band. However, it is still a challenge to easily promote the sensitivity of SNSPD without compromising its other performance. We report a method to improve the detection sensitivity of devices via suspended SiO2 membrane, and the intrinsic detection efficiency is significantly enhanced from 78% to 100% for a 1550 nm wavelength. The electro-thermal simulation and hotspot relaxation time measurement indicate that a suspended SiO2 membrane can significantly decrease the cooling efficiency between the hotspot and the substrate, and the relaxation time is enlarged twice than before. Meanwhile, we note that the proposed method does not affect other properties of devices, such as dark count rate, detection speed, and timing jitter. Because the thermal dissipation process can be controlled continuously (by varying the size of the suspended area), the proposed method may also help to obtain a deeper understanding of the thermal diffusion and detection process of SNSPDs.

Multi-echo single-shot spectroscopy combined with simultaneous 2D model fitting for fast and accurate measurement of metabolite-specific concentrations and T2 relaxation times.

The purpose of the current study was to develop a novel single-voxel MR spectroscopy acquisition scheme to simultaneously determine metabolite-specific concentrations and transverse relaxation times within realistic clinical scan times. Partly truncated multi-TE data are acquired as an echo train in a single acquisition (multi-echo single-shot [MESS]). A 2D multiparametric model fitting approach combines truncated, low-resolved short TE data with fully sampled, highly resolved, longer TE data to yield concentration and T2 estimates for major brain metabolites simultaneously. Cramer-Rao lower bounds (CRLB) are used as a measure of performance. The novel scheme was compared with traditional multi-echo multi-shot methods. In silico, in vitro, and in vivo experiments support the findings. MESS schemes, requiring only 2 min 12s for the acquisition of three echo times, provide valid concentration and relaxation estimates for multiple metabolites and outperform traditional methods for simultaneous determinations of metabolite-specific T2 s and concentrations, with improvements ranging from 5% to 30% for T2 s and from 10% to 50% for concentrations. However, substantial unsuppressed residual water signals may hamper the method's reproducibility, as observed in an initial experiment setup that prioritizes short TEs with severely truncated acquisition for the benefit of signal-to-noise ratio (SNR). Nevertheless, CRLB have been confirmed to be well suited as design criteria, and within-session repeatability approaches CRLB when residual water is removed in postprocessing by exploiting longer and less truncated data recordings. MESS MRS combined with 2D model fitting promises comparable accuracy, increased precision, or inversely shorter experimental times compared with traditional approaches. However, the optimal design must be investigated as a trade-off between SNR, the truncation factor, and TE batch selections, all of which influence the robustness of estimations.

Hypertrophy of the right ventricle by pulmonary artery banding in rats: a study of structural, functional, and transcriptomics alterations in the right and left ventricles.

Introduction: Right ventricular remodeling with subsequent functional impairment can occur in some clinical conditions in adults and children. The triggering factors, molecular mechanisms, and, especially, the evolution over time are still not well known. Left ventricular (LV) changes associated with right ventricular (RV) remodeling are also poorly understood. Objectives: The study aimed to evaluate RV morphological, functional, and gene expression parameters in rats submitted to pulmonary artery banding compared to control rats, with the temporal evolution of these parameters, and to analyze the influence of RV remodeling by pulmonary artery banding in rats and their controls over time on LV geometry, histology, gene expression, and functional performance. Methods: Healthy 6-week-old male Wistar-EPM rats weighing 170-200g were included. One day after the echocardiogram, depending on the animals undergoing the pulmonary artery banding (PAB) procedure or not (control group), they were then randomly divided into subgroups according to the follow-up time: 72h, or 2, 4, 6, or 8weeks. In each subgroup, the following were conducted: a new echocardiogram, a hemodynamic study, the collection of material for morphological analysis (hypertrophy and fibrosis), and molecular biology (gene expression). The results were presented as the mean ± standard deviation of the mean. A two-way ANOVA and Tukey post-test compared the variables of the subgroups and evolution follow-up times. The adopted significance level was 5%. Results: There was no significant difference among the subgroups in the percentage of water in both the lungs and the liver (the percentage of water in the lungs ranged from 76% to 78% and that of the liver ranged from 67% to 71%). The weight of the right chambers was significantly higher in PAB animals in all subgroups (RV PAB weighed from 0.34 to 0.48g, and control subjects, from 0.17 to 0.20g; right atrium (RA) with PAB from 0.09 to 0.14g; and control subjects from 0.02 to 0.03g). In the RV of PAB animals, there was a significant increase in myocyte nuclear volume (97μm3-183.6μm3) compared to control subjects (34.2μm3-57.2μm3), which was more intense in subgroups with shorter PAB follow-up time, and the fibrosis percentage (5.9%-10.4% vs. 0.96%-1.18%) was higher as the PAB follow-up time was longer. In the echocardiography result, there was a significant increase in myocardial thickness in all PAB groups (0.09-0.11cm compared to control subjects-0.04-0.05cm), but there was no variation in RV diastolic diameter. From 2 to 8weeks of PAB, the S-wave (S') (0.031cm/s and 0.040cm/s), and fractional area change (FAC) (51%-56%), RV systolic function parameters were significantly lower than those of the respective control subjects (0.040cm/s to 0.050cm/s and 61%-67%). Furthermore, higher expression of genes related to hypertrophy and extracellular matrix in the initial subgroups and apoptosis genes in the longer follow-up PAB subgroups were observed in RV. On the other hand, LV weight was not different between animals with and without PAB. The nuclear volume of the PAB animals was greater than that of the control subjects (74μm3-136μm3; 40.8μm3-46.9μm3), and the percentage of fibrosis was significantly higher in the 4- and 8-week PAB groups (1.2% and 2.2%) compared to the control subjects (0.4% and 0.7%). Echocardiography showed that the diastolic diameter and LV myocardial thickness were not different between PAB animals and control subjects. Measurements of isovolumetric relaxation time and E-wave deceleration time at the echocardiography were different between PAB animals and control subjects in all subgroups, but there were no changes in diastolic function in the hemodynamic study. There was also increased expression of genes related to various functions, particularly hypertrophy. Conclusion: 1) Rats submitted to pulmonary artery banding presented RV remodeling compatible with hypertrophy. Such alterations were mediated by increased gene expression and functional alterations, which coincide with the onset of fibrosis. 2) Structural changes of the RV, such as weight, myocardial thickness, myocyte nuclear volume, and degree of fibrosis, were modified according to the time of exposure to pulmonary artery banding and related to variations in gene expression, highlighting the change from an alpha to a beta pattern from early to late follow-up times. 3) The study suggests that the left ventricle developed histological alterations accompanied by gene expression modifications simultaneously with the alterations found in the right ventricle.

Development of Ultra-Low Field Magnetic Resonance Imaging System at 1 mT

Ultra-low field (ULF) magnetic resonance imaging (MRI) is considered an innovative MRI technique that can be combined with magnetoencephalography (MEG). In this study, a 1-mT ULF-MRI system without a pre-polarization technique aiming at combining an MEG system is developed. The intensity of the static magnetic field B0 is decided considered to be 1 mT because of the limitation of the magnetic field exposed to our MEG sensor made of superconducting quantum interference devices (SQUIDs). A square-shaped (750 mm × 750 mm) B0-coil based on a Merritt-type configuration is fabricated. The inhomogeneity of B0 is less than 0.07 % in the ±125 mm area. Further, an induction coil is employed to detect the magnetic resonance signal instead of the SQUID sensors of the MEG to confirm the feasibility of realizing MRI measurement at 1 mT without the pre-polarization technique. Relaxation time measurements and MR imaging of a phantom made of a CuSO4 aqueous solution are performed. Reasonable longitudinal and transverse relaxation times are obtained, and clear shapes of the phantom are obtained using the gradient- and spin-echo pulse sequences with this ULF-MRI system. These results indicate the potential of the proposed 1-mT ULF-MRI to effectively integrate ULF-MRI and MEG systems without pre-polarization.

Ion transport in non-aqueous electrolyte mixtures of zinc chloride deep eutectic solvent (DES) and molecular solvents

The ion dynamics of null solvents 1ZnCl2:4EtG and 1ChCl:1ZnCl2:6EtG incorporating 1M water, propylene carbonate (PC) or acetonitrile (AcN) were investigated using 1H NMR spectra and spin-lattice relaxation time (T1) measurements combined with ionic conductivity, density, and viscosity, all as a function of temperature. Results show that the inclusion of all co-solvents increased the available free volume of the mixtures and followed the trend H2O ≤ PC < AcN. 1H NMR spectra and T1 inferred the presence of multiple ionic species with varying rates of mobilities. These dynamic heterogeneities were displayed by the broad T1 minima – especially for the 1ZnCl2:4EtG mixtures – and asymmetrically broadened linewidths. T1 results also revealed selective interaction sites between the hydrogen bond donors and acceptors, as well as with the co-solvents.

3D T1 relaxation time measurements in an equine model of subtle post-traumatic osteoarthritis using MB-SWIFT.

The aim of this study is to assess whether articular cartilage changes in an equine model of post-traumatic osteoarthritis (PTOA), induced by surgical creation of standard (blunt) grooves, and very subtle sharp grooves, could be detected with ex vivo T1 relaxation time mapping utilizing three-dimensional (3D) readout sequence with zero echo time. Grooves were made on the articular surfaces of the middle carpal and radiocarpal joints of nine mature Shetland ponies and osteochondral samples were harvested at 39 weeks after being euthanized under respective ethical permissions. T1 relaxation times of the samples (n = 8 + 8 for experimental and n = 12 for contralateral controls) were measured with a variable flip angle 3D multiband-sweep imaging with Fourier transform sequence. Equilibrium and instantaneous Young's moduli and proteoglycan (PG) content from OD of Safranin-O-stained histological sections were measured and utilized as reference parameters for the T1 relaxation times. T1 relaxation time was significantly (p < 0.05) increased in both groove areas, particularly in the blunt grooves, compared with control samples, with the largest changes observed in the superficial half of the cartilage. T1 relaxation times correlated weakly (Rs ≈ 0.33) with equilibrium modulus and PG content (Rs ≈ 0.21). T1 relaxation time in the superficial articular cartilage is sensitive to changes induced by the blunt grooves but not to the much subtler sharp grooves, at the 39-week timepoint post-injury. These findings support that T1 relaxation time has potential in detection of mild PTOA, albeit the most subtle changes could not be detected.

Comparing CT and MR Properties of Artificial Thrombi According to Their Composition.

This study aims to determine whether and to what extent the structure and composition of thrombi can be assessed using NMR and CT measurements. Seven different thrombus models, namely, six RBC thrombi with hematocrit levels (HTs) of 0%, 20%, 40%, 60%, 80% and 100% and one platelet thrombus model, were analyzed using proton NMR at 100 MHz and 400 MHz, with measurements of T1 and T2 NMR relaxation times and measurements of the apparent diffusion coefficient (ADC). In addition, the thrombus models were CT-scanned in a dual-energy mode (80 kV and 140 kV) and in a single-energy mode (80 kV) to measure their CT numbers. The results confirmed that RBC thrombi can be distinguished from platelet thrombi by using ADC and CT number measurements in all three settings, while they cannot be distinguished by using T1 and T2 measurements. All measured parameters allowed for the differentiation of RBC thrombi according to their HT values, but the best sensitivity to HT was obtained with ADC and single-energy CT measurements. The importance of this study also lies in the potential application of its results for the characterization of actual thrombi in vivo.

Magnetic functionalization of ZnO nanoparticles surfaces via optically generated methyl radicals.

The combination of nuclear and electron magnetic resonance techniques, in pulse and continuous wave regimes, is used to unravel the nature and features of the light-induced magnetic state arising at the surface of chemically prepared zinc oxide nanoparticles (NPs) occurring under 120K when subjected to a sub-bandgap (405nm) laser excitation. It is shown that the four-line structure observed around g ∼ 2.00 in the as-grown samples (beside the usual core-defect signal at g ∼ 1.96) arises from surface-located methyl radicals (•CH3), originating from the acetate capped ZnO molecules. By functionalizing the as-grown zinc oxide NPs with deuterated sodium acetate, the •CH3 electron paramagnetic resonance (EPR) signal is replaced by trideuteromethyl (•CD3). For •CH3, •CD3, and core-defect signals, an electron spin echo is detected below ∼100K, allowing for the spin-lattice and spin-spin relaxation-time measurements for each of them. Advanced pulse-EPR techniques reveal the proton or deuteron spin-echo modulation for both radicals and give access to small unresolved superhyperfine couplings between adjacent •CH3. In addition, electron double resonance techniques show that some correlations exist between the different EPR transitions of •CH3. These correlations are discussed as possibly arising from cross-relaxation phenomena between different rotational states of radicals.

Multinuclear solid state nuclear magnetic resonance for studying CsPbBr3 nanocubes

Abstract Cesium lead bromide perovskite (CsPbBr3) nanocrystals have raised impressive interest as efficient and stable optoelectronic materials. Size and morphology play important roles in the final performances of these materials and advanced characterization studies are needed to elucidate structural and surface properties. In this work, CsPbBr3 cubic nanocrystals were obtained by colloidal synthesis and characterized by multinuclear Solid State NMR (SSNMR), complemented by X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and optical spectroscopy. The multinuclear NMR approach allowed the different components of the nanocubes to be separately observed. In particular, the surface ligands and their interactions with the nanocubes surface were investigated by 1H and 13C NMR experiments, while the structural investigation of the perovskite nanocubes was addressed by exploiting 207Pb and 133Cs spectral properties in comparison with bulk CsPbBr3. Static 207Pb NMR spectra indicated a possible contribution of chemical shift anisotropy from the 207Pb nuclei of the outer layer. The 133Cs NMR spectra showed signals with different chemical shifts for cesium atoms in at least three regions of the nanocubes, from the inner core to the surface, which were interpreted in terms of cubic layers with different distances from the surface using a simple geometrical model. This interpretation was also supported by 133Cs longitudinal relaxation time measurements.

Elucidation of Liquid Structures and Transport Properties of Highly Concentrated LiN(SO2F)2/Ethylene Carbonate Electrolytes

The Li+ conduction mechanism in highly concentrated ethylene carbonate (EC) solution of lithium bis(fluorosulfonyl)amide (LiFSA) was studied based on the measurements of thermal properties, density, viscosity, ionic conductivity, self-diffusion coefficients, Raman spectra, and proton nuclear magnetic resonance relaxation time. The compositions of EC and LiFSA were varied from dilute to concentrated states ([EC]/[LiFSA] = 9.2–0.80). For compositions of [EC]/[LiFSA] ≤ 1.5, the free solvents decrease, and contact ion pairs and aggregates become dominant, causing a significant change in the transport properties. Faster diffusion of Li+ compared with solvent (Li+ hopping conduction) was observed when the molar composition of [EC]/[LiFSA] ≤ 1.0 as in the case of sulfolane.

Combined estimation of B1 and T1 for dynamic contrast-enhanced MRI by accounting for incomplete spoiling of transverse magnetization

Objective. The variable flip angle (VFA) method for longitudinal relaxation time (T 1) measurement is inherently sensitive to inaccuracies in the radiofRequency transmit field (B 1) and incomplete spoiling of transverse magnetization. The objective of this study is to devise a computational method that addresses the problems of incomplete spoiling and B 1 inhomogeneity in the estimation of T 1 using VFA method. Approach. Using an analytical expression of the gradient echo signal with account of incomplete spoiling, we first showed that ill-posedness in the simultaneous estimation of B 1 and T 1 can be lifted with the use of flip angles larger than the Ernst angle. We then devised a nonlinear optimization method based on this signal model of incomplete spoiling for simultaneous estimation of B 1 and T 1. Main results. We evaluated the proposed method on a graded-concentration phantom to show that the derived T 1 estimates offers an improvement over the regular VFA method and compares well with reference values measured by inversion recovery. Reduction of the number of flip angles from 17 to 5 yielded consistent results indicating that the proposed method is numerically stable. T 1 estimates derived from in-vivo brain imaging were consistent with literature values for gray and white matter tissues. Significance. Contrary to the common notion that B 1 correction in the VFA method for T 1 mapping should be performed separately, we show that combined estimation of B 1 and T 1 is feasible by the proposed method simply with the acquisition of 5 flip angles, as demonstrated on both phantom and in-vivo imaging data.

Comparison of Algorithms to Compute Relaxation Time Maps in Magnetic Resonance Imaging

Magnetic resonance imaging (MRI) is a valuable diagnostic tool that provides detailed information about the structure and function of tissues in the human body. In particular, measuring relaxation times, such as T1 and T2, can provide important insights into the composition and properties of different tissues. Accurate relaxation time mapping is therefore critical for clinical diagnosis and treatment planning, as it can help to identify and characterize pathological conditions, monitor disease progression, and guide interventions. However, the computation of relaxation time maps in MRI is a complex and challenging task that requires sophisticated mathematical algorithms. Thus, there is a need for robust and accurate algorithms that can reliably extract the desired information from MRI data. This article compares the performance of the Reduced Dimension Nonlinear Least Squares (RD-NLS) algorithm versus several widely used algorithms to compute relaxation times in MRI, such as Levenberg-Marquardt and Nelder-Mead. RD-NLS simplifies the search space for the optimum fit by leveraging the partial linear relationship between signal intensity and model parameters. The comparison was performed on several datasets and signal models, resulting in T1 and T2 maps. The algorithms were evaluated based on their fit error, with the RD-NLS algorithm showing a lower error than other fit-ting algorithms. The improvement was particularly notable in T1 maps, with less of a difference in T2 maps. Additionally, the average T1 values computed with different algorithms differed by up to 14 ms, indicating the importance of algorithm selection. These results suggest that the RD-NLS algorithm outperforms other commonly used algorithms for computing relaxation times in MRI.

Cellular 1H MR Relaxation Times in Healthy and Cancer Three-Dimensional (3D) Breast Cell Culture.

Noninvasive measurements of 1H Magnetic Resonance Imaging (MR) relaxation times in a three-dimensional (3D) cell culture construct are presented. Trastuzumab was used as a pharmacological component delivered to the cells in vitro. The purpose of this study was to evaluate the Trastuzumab delivery by relaxation times in 3D cell cultures. The bioreactor has been designed and used for 3D cell cultures. Four bioreactors were prepared, two with normal cells and two with breast cancer cells. The relaxation times of HTB-125 and CRL 2314 cell cultures were determined. An immunohistochemistry (IHC) test was performed before MRI measurements to confirm the amount of HER2 protein in the CRL-2314 cancer cells. The results showed that the relaxation time of CRL2314 cells is lower than normal HTB-125 cells in both cases, before and after treatment. An analysis of the results showed that 3D culture studies have potential in evaluating treatment efficacy using relaxation times measurements with a field of 1.5 Tesla. The use 1H MRI relaxation times allows for the visualization of cell viability in response to treatment.

Surface and bulk relaxation of vapor-deposited polystyrene glasses.

We have studied the liquid-like response of the surface of vapor-deposited glassy films of polystyrene to the introduction of gold nanoparticles on the surface. The build-up of polymer material was measured as a function of time and temperature for both as-deposited films, as well as films that have been rejuvenated to become normal glasses cooled from the equilibrium liquid. The temporal evolution of the surface profile is well described by the characteristic power law of capillary-driven surface flows. In all cases, the surface evolution of the as-deposited films and the rejuvenated films is enhanced compared to bulk and is not easily distinguishable from each other. The temperature dependence of the measured relaxation times determined from the surface evolution is found to be quantitatively comparable to similar studies for high molecular weight spincast polystyrene. Comparisons to numerical solutions of the glassy thin film equation provide quantitative estimates of the surface mobility. For temperatures sufficiently close to the glass-transition temperature, particle embedding is also measured and used as a probe of bulk dynamics, and, in particular, bulk viscosity.

Investigation of Cu Adsorption and Migration with Spectral Induced Polarization in Activated Carbon.

In this paper, the adsorption process of copper ions on activated carbon (AC) was simulated in a column test. It was deduced that it is consistent with the pseudo-second-order model. Cation exchange was observed to be the major mechanism of Cu-AC interactions through scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) measurements. Adsorption isotherms were fitted well using the Freundlich model. Adsorption thermodynamics at 298, 308, 318 K demonstrated that the adsorption process is spontaneous and endothermic. Spectral induced polarization (SIP) technique was used to monitor the adsorption process, and the double Cole-Cole model was used to analyze the SIP results. The normalized chargeability was proportional to the adsorbed copper content. Two measured relaxation times from the SIP testing were converted into the average pore sizes of 2, 0.8, 0.6, 100-110, 80-90, and 53-60 µm by the Schwartz equation, which are consistent with the measured pore sizes from both mercury intrusion porosimetry and scanning electron microscopy (SEM). The reduction in the pore sizes by SIP during the flow-through tests suggested that the adsorbed Cu2+ gradually migrated into small pores as with continued permeation of the influent. These results showcased the feasibility of using SIP technique in engineering practice involving the monitoring of copper contamination in land near a mine waste dump or in adjacent permeable reactive barriers.

Tunable Superconducting Flux Qubits with Long Coherence Times

In this work, we study a series of tunable flux qubits inductively coupled to a coplanar waveguide resonator fabricated on a sapphire substrate. Each qubit includes an asymmetric superconducting quantum interference device which is controlled by the application of an external magnetic field and acts as a tunable Josephson junction. The tunability of the qubits is typically $\pm 3.5$ GHz around their central gap frequency. The measured relaxation times are limited by dielectric losses in the substrate and can attain $T_{1}\sim 8 \mu s$. The echo dephasing times are limited by flux noise even at optimal points and reach $T_{2E}\sim 4 \mu s$, almost an order of magnitude longer than state of the art for tunable flux qubits.

Imaging gas-exchange lung function and brain tissue uptake of hyperpolarized 129 Xe using sampling density-weighted MRSI.

Imaging of the different resonances of hyperpolarized 129 Xe in the brain and lungs was performed using a 3D sampling density-weighted MRSI technique in healthy volunteers. Four volunteers underwent dissolved-phase hyperpolarized 129 Xe imaging in the lung with the MRSI technique, which was designed to improve the point-spread function while preserving SNR (1799 phase-encoding steps, 14-s breath hold, 2.1-cm isotropic resolution). A frequency-tailored RF excitation pulse was implemented to reliably excite both the 129 Xe gas and dissolved phase (tissue/blood signal) with 0.1° and 10° flip angles, respectively. Images of xenon gas in the lung airspaces and xenon dissolved in lung tissue/blood were used to generate quantitative signal ratio maps. The method was also optimized and used for imaging dissolved resonances of 129 Xe in the brain in 2 additional volunteers. High-quality regional spectra of hyperpolarized 129 Xe were achieved in both the lung and the brain. Ratio maps of the different xenon resonances were obtained in the lung with sufficient SNR (> 10) at both 1.5 T and 3T, making a triple Lorentzian fit possible and enabling the measurement of relaxation times and xenon frequency shifts on a voxel-wise basis. The imaging technique was successfully adapted for brain imaging, resulting in the first demonstration of 3D xenon brain images with a 2-cm isotropic resolution. Density-weighted MRSI is an SNR and encoding-efficient way to image 129 Xe resonances in the lung and the brain, providing a valuable tool to quantify regional spectroscopic information.

Creating Solid Solutions of Metallocenes: Migration of Nickelocene into the Ferrocene Crystal Lattice in the Absence of a Solvent

Ferrocene and nickelocene do not react with each other in solution; however, the large impact of the paramagnetic component on the ferrocene 1H NMR signal linewidth and relaxation times has been quantified. Co-crystallization of ferrocene and nickelocene at any ratio from a solvent can be explained with both pure substances crystallizing in the same space group P21/n. As a new phenomenon, when a ferrocene single crystal is exposed to polycrystalline nickelocene in the absence of a solvent, the nickelocene migrates into the ferrocene crystal lattice and a mixed crystal is formed that retains its macroscopic shape. This process has been proven visually by cutting the single crystal. Mixing polycrystalline ferrocene with polycrystalline nickelocene at different molar ratios with a mortar and pestle leads to crystalline solid solutions with the corresponding molar ratios of both components. This migration of one organometallic component into an existing crystal lattice of another at ambient temperature in the absence of a solvent has not been described previously. Paramagnetic 1H solid-state NMR spectroscopy of static and rotating samples of dry ferrocene/nickelocene mixtures at varying ratios is used to prove and quantify the mixing of both metallocenes at the molecular level. A single-crystal X-ray structure of a 50/50 mixed crystal corroborates the NMR results that nickelocene and ferrocene are randomly distributed in the lattice and that the space group P21/n is retained. All ferrocene molecules in the mixed crystal lattice show a broadening of their 1H wideline signals and residual magic-angle spinning (MAS) lines at ambient temperature. The broadening of the ferrocene signals correlates with the nickelocene content. 1H T1 relaxation time measurements for the signals of ferrocene in samples with different amounts of nickelocene corroborate the assumption that the signal broadening is due to paramagnetic dipole–dipole relaxation of ferrocene molecules in the vicinity of nickelocene. Spatially separated ferrocene and nickelocene powders in one rotor show the solid-state NMR characteristics of the individual polycrystalline metallocenes. The described formation of solid solutions of metallocenes in the absence of a solvent will open new pathways to homogeneously mixed nanoparticles with desired metal ratios and dual-atom catalysts.