Alexej Jerschow

Assessment of glycosaminoglycan concentration in vivo by chemical exchange-dependent saturation transfer (gagCEST).

Glycosaminogycans (GAGs) are involved in numerous vital functions in the human body. Mapping the GAG concentration in vivo is desirable for the diagnosis and monitoring of a number of diseases such as osteoarthritis, which affects millions of individuals. GAG loss in cartilage is typically an initiating event in osteoarthritis. Another widespread pathology related to GAG is intervertebral disk degeneration. Currently existing techniques for GAG monitoring, such as delayed gadolinium-enhanced MRI contrast (dGEMRIC), T1ρ, and 23Na MRI, have some practical limitations. We show that by exploiting the exchangeable protons of GAG one may directly measure the localized GAG concentration in vivo with high sensitivity and therefore obtain a powerful diagnostic MRI method.

7Li MRI of Li batteries reveals location of microstructural lithium

There is an ever-increasing need for advanced batteries for portable electronics, to power electric vehicles and to facilitate the distribution and storage of energy derived from renewable energy sources. The increasing demands on batteries and other electrochemical devices have spurred research into the development of new electrode materials that could lead to better performance and lower cost (increased capacity, stability and cycle life, and safety). These developments have, in turn, given rise to a vigorous search for the development of robust and reliable diagnostic tools to monitor and analyse battery performance, where possible, in situ. Yet, a proven, convenient and non-invasive technology, with an ability to image in three dimensions the chemical changes that occur inside a full battery as it cycles, has yet to emerge. Here we demonstrate techniques based on magnetic resonance imaging, which enable a completely non-invasive visualization and characterization of the changes that occur on battery electrodes and in the electrolyte. The current application focuses on lithium-metal batteries and the observation of electrode microstructure build-up as a result of charging. The methods developed here will be highly valuable in the quest for enhanced battery performance and in the evaluation of other electrochemical devices.

Solid-state NMR spectroscopic methods in chemistry

Over the last decades, NMR spectroscopy has grown into an indispensable tool for chemical analysis, structure determination, and the study of dynamics in organic, inorganic, and biological systems. It is commonly used for a wide range of applications from the characterization of synthetic products to the study of molecular structures of systems such as catalysts, polymers, and proteins. Although most NMR experiments are performed on liquid-state samples, solid-state NMR is rapidly emerging as a powerful method for the study of solid samples and materials. This Review outlines some of the developments of solid-state NMR spectroscopy, including techniques such as cross-polarization, magic-angle spinning, multiple-pulse sequences, homo- and heteronuclear decoupling and recoupling techniques, multiple-quantum spectroscopy, and dynamic angle spinning, as well as their applications to structure determination. Modern solid-state NMR spectroscopic techniques not only produce spectra with a resolution close to that of liquid-state spectra, but also capitalize on anisotropic interactions, which are often unavailable for liquid samples. With this background, the future of solid-state NMR spectroscopy in chemistry appears to be promising, indeed.

Rapid Isotropic 3D-Sodium MRI of the Knee Joint In-vivo at 7T

To demonstrate the feasibility of acquiring high‐resolution, isotropic 3D‐sodium magnetic resonance (MR) images of the whole knee joint in vivo at ultrahigh field strength (7.0T) via a 3D‐radial acquisition with ultrashort echo times and clinically acceptable acquisition times.

Isolating chemical exchange saturation transfer contrast from magnetization transfer asymmetry under two-frequency rf irradiation.

Chemical exchange saturation transfer (CEST), arising from mobile groups, and magnetization transfer (MT) contrast arising from immobile protons, have enjoyed wide popularity recently in MRI applications. It is often difficult to separate genuine CEST signatures from MT effects, which are asymmetric with respect to the water resonance. A two-pool model for magnetization transfer (MT) is established based on Provotorovs theory of saturation, and then extended to the situation of simultaneous two-frequency rf irradiation. Numerical simulations and experimental results demonstrate that two-frequency rf irradiation can flatten out MT asymmetry when both frequency components lie within the spectrum of an MT pool. Based on this result, we propose a strategy to isolate chemical exchange saturation transfer (CEST) contrast from MT asymmetry contrast by using the two-frequency rf irradiation technique.

Correlating Microstructural Lithium Metal Growth with Electrolyte Salt Depletion in Lithium Batteries Using 7Li MRI

Lithium dendrite growth in lithium ion and lithium rechargeable batteries is associated with severe safety concerns. To overcome these problems, a fundamental understanding of the growth mechanism of dendrites under working conditions is needed. In this work, in situ (7)Li magnetic resonance (MRI) is performed on both the electrolyte and lithium metal electrodes in symmetric lithium cells, allowing the behavior of the electrolyte concentration gradient to be studied and correlated with the type and rate of microstructure growth on the Li metal electrode. For this purpose, chemical shift (CS) imaging of the metal electrodes is a particularly sensitive diagnostic method, enabling a clear distinction to be made between different types of microstructural growth occurring at the electrode surface and the eventual dendrite growth between the electrodes. The CS imaging shows that mossy types of microstructure grow close to the surface of the anode from the beginning of charge in every cell studied, while dendritic growth is triggered much later. Simple metrics have been developed to interpret the MRI data sets and to compare results from a series of cells charged at different current densities. The results show that at high charge rates, there is a strong correlation between the onset time of dendrite growth and the local depletion of the electrolyte at the surface of the electrode observed both experimentally and predicted theoretical (via the Sands time model). A separate mechanism of dendrite growth is observed at low currents, which is not governed by salt depletion in the bulk liquid electrolyte. The MRI approach presented here allows the rate and nature of a process that occurs in the solid electrode to be correlated with the concentrations of components in the electrolyte.

Sodium inversion recovery MRI of the knee joint in vivo at 7T.

The loss of proteoglycans (PG) in the articular cartilage is an early signature of osteoarthritis (OA). The ensuing changes in the fixed charge density in the cartilage can be directly linked to sodium concentration via charge balance. Sodium ions in the knee joint appear in two pools: in the synovial fluids or joint effusion where the ions are in free motion and bound within the cartilage tissue where the Na(+) ions have a restricted motion. The ions in these two compartments have therefore different T₁ and T₂ relaxation times. The purpose of this study is to demonstrate the feasibility of a fluid-suppressed 3D ultrashort TE radial sodium sequence by implementing an inversion recovery (IR) preparation of the magnetization at 7T. This method could allow a more accurate and more sensitive quantification of loss of PG in patients with OA. It is shown that adiabatic pulses offer significantly improved performance in terms of robustness to B₁ and B₀ inhomogeneities when compared to the hard pulse sequence. Power deposition considerations further pose a limit to the RF inversion power, and we demonstrate in simulations and experiments how a practical compromise can be struck between clean suppression of fluid signals and power deposition levels. Two IR sequences with different types of inversion pulses (a rectangular pulse and an adiabatic pulse) were tested on a liquid phantom, ex vivo on a human knee cadaver and then in vivo on five healthy volunteers, with a (Nyquist) resolution of ∼3.6 mm and a signal-to-noise ratio of ∼30 in cartilage without IR and ∼20 with IR. Due to specific absorption rate limitations, the total acquisition time was ∼17 min for the 3D radial sequence without inversion or with the rectangular IR, and 24:30 min for the adiabatic IR sequence. It is shown that the adiabatic IR sequence generates a more uniform fluid suppression over the whole sample than the rectangular IR sequence.

Assessment of glycosaminoglycan concentration changes in the intervertebral disc via chemical exchange saturation transfer.

In this study, it is shown that the chemical exchange saturation transfer (CEST) method for hydroxyl protons can be used to detect changes in glycosaminoglycan (GAG) concentration in the intervertebral disc. The method, termed gagCEST, was demonstrated ex vivo by correlating the CEST effect with the fixed charge density (FCD) of the nucleus pulposus (NP), as well as by correlating tissue CEST images with their corresponding 23Na images. Incubation of five NP samples with trypsin produced samples with varying GAG content (n = 19). A good correlation was found between the –OH CEST effect and FCD, as well as with the N‐acetyl signal amplitude. gagCEST images in vitro further illustrated the amount of detail obtainable from this contrast mechanism when compared with conventional imaging. The large concentration of GAG and the relatively long T1 of water in NP make the method sensitive, in particular, for the assessment of GAG depletion in this tissue. It is the loss of GAG in NP that indicates the early stage of disc degeneration. Copyright

Compressed Sensing Sodium MRI of Cartilage at 7T: Preliminary Study

Sodium MRI has been shown to be highly specific for glycosaminoglycan (GAG) content in articular cartilage, the loss of which is an early sign of osteoarthritis (OA). Quantitative sodium MRI techniques are therefore under development in order to detect and assess early biochemical degradation of cartilage, but due to low sodium NMR sensitivity and its low concentration, sodium images need long acquisition times (15-25 min) even at high magnetic fields and are typically of low resolution. In this preliminary study, we show that compressed sensing can be applied to reduce the acquisition time by a factor of 2 at 7 T without losing sodium quantification accuracy. Alternatively, the nonlinear reconstruction technique can be used to denoise fully-sampled images. We expect to even further reduce this acquisition time by using parallel imaging techniques combined with SNR-improved 3D sequences at 3T and 7 T.

Sodium MRI: Methods and applications

Sodium NMR spectroscopy and MRI have become popular in recent years through the increased availability of high-field MRI scanners, advanced scanner hardware and improved methodology. Sodium MRI is being evaluated for stroke and tumor detection, for breast cancer studies, and for the assessment of osteoarthritis and muscle and kidney functions, to name just a few. In this article, we aim to present an up-to-date review of the theoretical background, the methodology, the challenges, limitations, and current and potential new applications of sodium MRI.