Slip/Stick Viscosity Models of Nanoconfined Liquids: Solvent-Dependent Rotation in Metal-Organic Frameworks.

Artificial molecular machines are expected to operate in environments where viscous forces impact molecules significantly. With that, it is well-known that solvent behaviors dramatically change upon confinement into limited spaces as compared to bulk solvents. In this study, we demonstrate the utility of an amphidynamic metal-organic framework with pillars consisting of 2H-labeled dialkynyltriptycene and dialkynylphenylene barrierless rotators that operate as NMR sensors for solvent viscosity. Using line-shape analysis of quadrupolar spin echo spectra we showed that solvents such as dimethylformamide, diethylformamide, 2-octanone, bromobenzene, o-dichlorobenzene, and benzonitrile slow down their Brownian rotational motion (103-106 s-1) to values consistent with confined viscosity values (ca. 100-103 pa s) that are up to 10000 greater than those in the bulk. Magic angle spinning assisted 1H T2 measurements of included solvents revealed relaxation times of approximately 100-1000 ms over the explored temperature ranges, and MAS-assisted 1H T1 measurements of included solvents suggested a much lower activation energy for rotational dynamics as compared to those measured by the rotating pillars using 2H measurements. Finally, translational diffusion measurements of DMF using pulsed-field gradient methods revealed intermediate dynamics for the translational motion of the solvent molecules in MOFs.

7Li intermolecular multiple-quantum coherences in liquids.

We report here evidence for the generation of 7Li multiple-quantum coherences in aqueous solutions outside of regimes where conventional multiple-quantum coherences due to alignment or quadrupolar relaxation could be observed. These coherences are shown to observe nonlinear behavior as a function of concentration, and hence these effects can be identified as arising from intermolecular multiple-quantum coherences. Due to the importance of lithium ion solutions for the study of electrochemical systems, awareness of such coherences is particularly important in the interpretation of experimental results, and new applications using lithium as a probe may become possible on this basis.

Nuclear magnetic resonance spin-lattice relaxation of lithium ions in aqueous solution by NMR and molecular dynamics.

We study the aqueous solvation dynamics of lithium ions using nuclear magnetic resonance spectroscopy, molecular dynamics, and viscosity measurements. Several relaxation mechanisms are examined to explain the strong increases of spin-lattice relaxation toward high concentrations. The use of both 6Li and 7Li isotopes is helpful to identify the quadrupolar contribution to the relaxation rate. In particular, it is found that the quadrupolar interaction constitutes the strongest contribution above a concentration of ∼10 molal. The next-strongest contribution arises from interactions that scale with the square of the gyromagnetic ratio (mostly the dipolar interaction), and the experimental relaxation rates appear to be fully accounted for when these mechanisms are combined over the concentration range up to the saturation concentration. The study of solvation dynamics, particularly at high concentrations, could be of relevance for electrolyte dynamics in aqueous Li-ion rechargeable batteries.

Mapping oscillating magnetic fields around rechargeable batteries.

Power storage devices such as batteries are a crucial part of modern technology. The development and use of batteries has accelerated in the past decades, yet there are only a few techniques that allow gathering vital information from battery cells in a nonivasive fashion. A widely used technique to investigate batteries is electrical impedance spectroscopy (EIS), which provides information on how the impedance of a cell changes as a function of the frequency of applied alternating currents. Building on recent developments of inside-out MRI (ioMRI), a technique is presented here which produces spatially-resolved maps of the oscillating magnetic fields originating from the alternating electrical currents distributed within a cell. The technique works by using an MRI pulse sequence synchronized with a gated alternating current applied to the cell terminals. The approach is benchmarked with a current-carrying wire coil, and demonstrated with commercial and prototype lithium-ion cells. Marked changes in the fields are observed for different cell types.

Nuclear magnetic resonance spectroscopy of rechargeable pouch cell batteries: beating the skin depth by excitation and detection via the casing.

Rechargeable batteries are notoriously difficult to examine nondestructively, and the obscurity of many failure modes provides a strong motivation for developing efficient and detailed diagnostic techniques that can provide information during realistic operating conditions. In-situ NMR spectroscopy has become a powerful technique for the study of electrochemical processes, but has mostly been limited to laboratory cells. One significant challenge to applying this method to commercial cells has been that the radiofrequency, required for NMR excitation and detection, cannot easily penetrate the battery casing due to the skin depth. This complication has limited such studies to special research cell designs or to 'inside-out' measurement approaches. This article demonstrates that it is possible to use the battery cell as a resonator in a tuned circuit, thereby allowing signals to be excited inside the cell, and for them to subsequently be detected via the resonant circuit. Employing this approach, 7Li NMR signals from the electrolyte, as well as from intercalated and plated metallic lithium in a multilayer (rolled) commercial pouch cell battery were obtained. Therefore, it is anticipated that critical nondestructive device characterization can be performed with this technique in realistic and even commercial cell designs.

Selective magnetic resonance signal suppression by colored Frank excitation.

Inspired by the growing interest in miniaturized NMR devices and their applications in material science as well as in chemical and biological research, low power rf excitation is explored. 1H NMR spectra have been measured with low power Frank excitation and are compared to spectra obtained by single-pulse excitation. Frank excitation consists of a large number of phase-modulated, constant-amplitude rf-pulses. A Frank sequence is divided into packages of discrete phase wavelets that correspond to a scan across a spectral frequency range. The largely coherent excitation is found experimentally to require less power than white noise excitation. The package structure suggests that individual wavelets can be omitted to skip individual frequency regions in the excitation, converting the white Frank excitation into colored Frank excitation. This work explores different approaches of colored, selective Frank excitation for spectroscopy and imaging. It is motivated by the aim to eliminate the rf amplifier from the NMR spectrometer so as to enable further miniaturization of NMR instruments. Colored Frank excitation bears promise as a low-power modality for solvent signal suppression in spectroscopy and motion tagging in magnetic resonance imaging.

In-situ MRI velocimetry of the magnetohydrodynamic effect in electrochemical cells.

Electrochemical reactions have become increasingly important in a large number of processes and applications. The use of NMR (Nuclear Magnetic Resonance) techniques to follow in situ electrochemistry processes has been gaining increasing attention from the scientific community because they allow the identification and quantification of the products and reagents, whereas electrochemistry measurements alone are not able to do so. However, when an electrochemical reaction is performed in situ the reaction rate can be increased by action of the Lorentz force, which is equal to the cross product between the current density and the magnetic field applied. This phenomenon is called the magnetohydrodynamic (MHD) effect. Although this process is beneficial because it accelerates the reaction, it needs to be well understood and taken into account during the in situ electrochemical measurements. The MHD effect is based on increased mass transfer, which is shown by in situ MRI velocimetry here. Images had to be acquired in a rapid manner since current was not pulsed. Significant velocities in a plane parallel to the electrodes alongside with complex flow patterns were detected.

Elucidating the ionic liquid distribution in monolithic SILP hydroformylation catalysts by magnetic resonance imaging.

Monolithic silicon carbide supported ionic liquid-phase (SILP) Rh-catalysts have very recently been introduced for gas-phase hydroformylation as an important step toward industrial upscaling. This study investigates the monolithic catalyst system in combination with different impregnation procedures with non-invasive magnetic resonance imaging (MRI). The findings were supported by X-ray microtomography (micro-CT) data of the monolithic pore structure and a catalytic performance test of the catalyst system for 1-butene gas-phase hydroformylation. MRI confirmed a homogeneous impregnation of the liquid phase throughout the full cross-section of the cylindrical monoliths. Consistent impregnations from one side to the other of the monoliths were achieved with a stabilizer in the system that helped preventing inhomogeneous rim formation. External influences relevant for industrial application, such as long-term storage and temperature exposure, did not affect the homogeneous liquid-phase distribution of the catalyst. The work elucidates important parameters to improve liquid-phase catalyst impregnation to obtain efficient monolithic catalysts for industrial exploitation in gas-phase hydroformylation as well as other important industrial processes.

Imaging of copper oxygenation reactions in a bubble flow.

Reactions of gases with liquids play a crucial role in the production of many bulk chemicals. Often, the gas is bubbled into the chosen reactor. Most of the processes at the gas-liquid interface of the bubbles and in their tails are not fully understood and warrant further investigation. For this purpose, NMR imaging or Magnetic Resonance Imaging has been applied to visualize some of the processes in the bubble tail. To generate sufficient contrast, a magnetogenic gas-liquid reaction associated with a change of magnetic state, from diamagnetic to paramagnetic, was employed. In this work, a copper(I)-based compound was oxidized to copper(II) to exploit relaxation contrast. To match the speed of the rising bubbles to the acquisition time of the spin-echo imaging sequence, polyethylene glycol was added to increase the viscosity of the reacting solution. Images of the oxygen ingress into a static solution as well as of oxygen bubbles rising in the solution are presented. In both cases, changes in magnetism were observed, which reported the hydrodynamic processes.

Miniaturized multi-coil arrays for functional planar imaging with a single-sided NMR sensor.

Nowadays most low-field NMR sensors, such as the single-sided Profile NMR-MOUSE®, still suffer from poor sensitivity, either resulting from low magnetic field strengths and correspondingly low NMR frequencies, or lack of sensitivity. Generally, micro-coils can improve sensitivity, but due to their small size, and thus small inductance, they are mainly used for high-field NMR. Their main application field is parallel imaging, where those coils are typically assembled to receive-only coil-arrays and increase the field-of-view. Prominent signal combination techniques such as GRAPPA and SENSE are used to combine the spatially independent NMR signals to images in order to increase acquisition speed. A decisive disadvantage of today's single-sided NMR probes is the limited accessibility for NMR imaging. Although it is possible to use flat gradient coils on top of the NMR-MOUSE® to apply imaging techniques, such images can only be recorded with very long acquisition times, excluding the NMR-MOUSE® for lateral imaging of time-dependent processes. In this study sensitivity improved micro-structured RF coils, optimized for low frequencies, and correspondingly arrays of these coils, were employed to improve sensitivity and gave access to lateral spatial resolution within the sensitive plane at several observation points at the same time. Recently developed three- and four-coil arrays were combined with a Profile NMR-MOUSE® and characterized in terms of coil coupling, noise correlation and signal combination. The three-coil array was used for lateral imaging of moisture transport in travertine rock samples and to study the one-dimensional drying of paint.