Structure and ion transport properties of organic ionic compounds revealed by NMR

Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such as high ionic conductivity,non-flammability,and plasticity.Various nuclear magnetic resonance(NMR)spectroscopy techniques including solid-state NMR,pulsed-field gradient(PFG)NMR,and magnetic resonance imaging(MRI)etc.,provide us a versatile toolkit to understand the fundamental level structures,molecular dynamics,and ionic interactions in these materials.This article reviews the commonly used NMR methods including solid-and solution-state NMR,PFG-NMR,dynamic nuclear polarization(DNP)and the application of these methods in revealing the microscopic level structures and ion-transport mechanisms in OIPC materials.

Experimental aspects of ^(14)N overtone RESPDOR solid-state NMR spectroscopy under MAS beyond 60 kHz

Nitrogen-14(^(14)N)overtone(OT)spectroscopy under fast magic angle spinning(MAS)conditions(>60 kHz)has emerged as a powerful technique for observing correlations and distances between ^(14)N and ^(1)H,owing to the absence of the first-order quadrupolar broadenings.In addition,^(14)N^(OT) allows selective manipulation of ^(14)N nuclei for each site.Despite extensive theoretical and experimental studies,the spin dynamics of ^(14)N^(OT) remains under debate.In this study,we conducted experimental investigations to assess the spin dynamics of ^(14)N^(OT) using the rotational-echo saturation-pulse double-resonance(RESPDOR)sequence,which monitors population transfer induced by a^(14)N^(OT) pulse.The ^(14)N^(OT) spin dynamics is well represented by a model of a two-energy-level system.Unlike spin-1/2,the maximum excitation efficiency of ^(14)N^(OT) coherences of powdered solids,denoted by p,depends on the radiofrequency field(rf-field)strength due to orientation dependence of effective nutation fields even when pulse lengths are optimized.It is also found that the p factor,contributing to the ^(14)N^(OT) spin dynamics,is nearly independent of the B0 field.Consequently,the filtering efficiency of RESPDOR experiments exhibits negligible dependence on B0 when the ^(14)N^(OT) pulse length is optimized.The study also identifies the optimal experimental conditions for ^(14)N^(OT)/^(1)H RESPDOR correlation experiments.

Qualitative analysis of aromatic compounds via 1D TOCSY techniques

The aromatic compounds,including o-xylene,m-xylene,p-xylene,and ethylbenzene,primarily originate from the catalytic reforming of crude oil,and have a wide variety of applications.However,because of similar physical and chemical properties,these compounds are difficult to be identified by gas chromatography(GC)without standard samples.With the development of modern nuclear magnetic resonance(NMR)techniques,NMR has emerged as a powerful and efficient tool for the rapid analysis of complex and crude mixtures without purification.In this study,the parameters of one-dimensional(1D)total correlation spectroscopy(TOCSY)NMR techniques,including 1D selective gradient TOCSY and 1D chemicalshift-selective filtration(CSSF)with TOCSY,were optimized to obtain comprehensive molecular structure information.The results indicate that the overlapped signals in NMR spectra of nonpolar aromatic compounds(including o-xylene,m-xylene,p-xylene and ethylbenzene),polar aromatic compounds(benzyl alcohol,benzaldehyde,benzoic acid),and aromatic compounds with additional conjugated bonds(styrene)can be resolved in 1D TOCSY.More importantly,full molecular structures can be clearly distinguished by setting appropriate mixing time in 1D TOCSY.This approach simplifies the NMR spectra,provides structural information of entire molecules,and can be applied for the analysis of other structural isomers.

Gradient coil design with enhanced shielding constraint for a cryogen-free superconducting MRI system

The relatively fragile low-temperature stability of cryogen-free superconducting magnetic resonance imaging(MRI)magnets requires the careful management of exogenous heat sources.A strongly shielded gradient magnetic field is important for the optimal operation of cryogen-free MRI systems.In this study,we present an enhanced shielding method incorporating a regionalized stray field constraining strategy.By optimizing the constraint parameters,we could develop engineering-feasible gradient coil schemes without increasing system complexity but with the stray field intensity reduced by half.In real measurement in an integrated MRI system,the developed gradient assembly demonstrated good performance and supported to output images of excellent quality.Our findings suggested that the proposed method could potentially form a useful design paradigm for cryogen-free MRI magnets.

Revealing structure correlation between ionic liquid and metal-organic framework matrix

Solid-state batteries are rising rapidly in response to the fast-increasing energy demand.Metal-organic framework(MOF)loaded with ionic liquids has brought new opportunities for solid-state batteries owing to its good interfacial compatibility and high ionic conductivity.MOF-808 is selected to be filled with Li-contained ionic liquid for structure and ion dynamics investigation using nuclear magnetic resonance(NMR)and X-ray diffraction.This study finds that the introduced ionic liquid would partially soften the matrix of MOF-808 and thus yield amorphous phase.By selective isotope replacement under cycling symmetric 6Li metal cell,Lit ion is observed to mainly go cross ionic liquid in the open channel of matrix under potential polarization.

Multinuclear MR and MRI study of lithium-ion cells using a variable field magnet and a fixed frequency RF probe

An exploratory multinuclear magnetic resonance(MR)and magnetic resonance imaging(MRI)study was performed on lithium-ion battery cells with ^(7)Li,^(19)F,and ^(1)H measurements.A variable field superconducting magnet with a fixed frequency parallel-plate radiofrequency(RF)probe was employed in the study.The magnetic field was changed to set the resonance frequency of each nucleus to the fixed RF probe frequency of 33.7 MHz.Two cartridge-like lithium-ion cells,with graphite anodes and LiNi_(0.5)Mn_(0.3)Co_(0.2)O_(2)(NMC)cathodes,were interrogated.One cell was pristine,and one was charged to a cell voltage of 4.2 V.The results presented demonstrate the great potential of the variable field magnet approach in multinuclear measurement of lithium-ion batteries.These methods open the door for developing faster and simpler methods for detecting,quantifying,and interpreting MR and MRI data from lithium-ion and other batteries.

Rheo-NMR: A versatile hyphenated technique for capturing molecular dynamics and structure under flow

The general development of Rheo-NMR during the last four decades as well as selective hyphenated apparatuses is presented.Based on different magnet types,the current review is divided into two categories,namely low-field and high-field NMR,while the timedomain NMR is normally applied in the former case and the frequency-domain NMR is adopted in the latter one.Depending on different rheometer cells,it can be further divided into tensile and shear mode Rheo-NMR.The combination of various rheometer cells and NMR facility guarantees our acquisition of molecular level structure and dynamics information under flow conditions,which is crucial for our understanding of the molecular origin of complex fluids.A personal perspective is also presented at last to highlight possible development in this direction.

A study on the temperature sensitivity of NMR porosity in porous media based on the intensity of magnetization Dedicated to the special issue “Magnetic Resonance in Porous Media”

The measurement of nuclear magnetic resonance(NMR)porosity is affected by temperature.Without considering the impact of NMR logging tools,this phenomenon is mainly caused by variations in magnetization intensity of the measured system due to temperature fluctuations and difference between the temperature of the porous medium and calibration sample.In this study,the effect of temperature was explained based on the thermodynamic theory,and the rules of NMR porosity responses to temperature changes were identified through core physics experiments.In addition,a method for correcting the influence of temperature on NMR porosity measurement was proposed,and the possible factors that may affect its application were also discussed.

Deep learning for determining pure isotropic proton spectra from solidstate spectra

Recently,an article on ^(1)H solid-state NMR spectra was published,in which the authors proposed a deep learning approach to infer the pure isotropic proton NMR spectra obtained at an infinite magic angle spinning(MAS)rate.This approach even allowed to obtain,by far,the best resolved ^(1)H spectra of molecular solids[1](https://doi.org/10.1002/anie.202216607).Deep learning based artificial intelligence is developing rapidly,and its application is deepening.Currently,there are many applications of deep learning in the field of magnetic resonance,such as the reconstruction of the under-sampled multidimensional spectra[2-4],the deconvolution of two-dimensional NMR spectra[5]and noise suppression and weak peak retrial[6],etc.

Human islet amyloid polypeptide oligomers stabilized and probed by MAS NMR

The capture and characterization of oligomers are extremely important in the studies of amyloid aggregation of proteins and peptides.Oligomers are critical intermediates that can impact the structures of amyloid fibrils.Moreover,it is widely accepted that oligomers are the most toxic species along the aggregation pathway[1e4].The studies of oligomers are believed to shed light on the molecular mechanism of amyloid fibrillation and probably the medical clues for related diseases.In vitro investigations of amyloid oligomers are challenging due to their transient and polymorphic nature[5].This is particularly evident in the case of human type-2 diabetes-associated islet amyloid polypeptide(hIAPP),which tends to rapidly form polymorphic fibrils within minutes[6].Notably,hIAPP demonstrates a higher propensity for rapid aggregation compared to other amyloid proteins such as a-synuclein[7].

Overview and progress of X-nuclei magnetic resonance imaging in biomedical studies

Proton nuclear(^(1)H)is the observed nucleus on which most magnetic resonance imaging(MRI)applications depend.Most traditional^(1)H MRI can provide structural and functional information about organisms,while various non-proton nuclei(X-nuclei)MRI can provide more metabolic information.However,due to the relatively poor signal-to-noise ratio(SNR)of X-nuclei MRI,their applications are quite rare compared to^(1)H.Benefit from the rapid developments of MRI hardware and software technologies,X-nuclei MRI has recently attracted increasing interests in biomedical research.This review firstly introduces some current methods to improve the SNR of X-nuclei MRI.Secondly,this review describes biomedical applications of X-nuclei MRI,especially focusing on the current use of X-nuclei(^(13)C,^(17)O,^(19)F,^(23)Na and^(31)P)MRI to study related diseases in different organs,including the brain,liver,kidney,heart and bone.Finally,perspectives studies on X-nuclei imaging and its potential applications are described in biomedical research.

Using NMR-detected hydrogen-deuterium exchange to quantify protein stability in cosolutes,under crowded conditions in vitro and in cells

We review the use of nuclear magnetic resonance(NMR)spectroscopy to assess the exchange of amide protons for deuterons(HDX)in efforts to understand how high concentration of cosolutes,especially macromolecules,affect the equilibrium thermodynamics of protein stability.HDX NMR is the only method that can routinely provide such data at the level of individual amino acids.We begin by discussing the properties of the protein systems required to yield equilibrium thermodynamic data and then review publications using osmolytes,sugars,denaturants,synthetic polymers,proteins,cytoplasm and in cells.

Non-invasive assessment for intratumoural distribution of interstitial fluid flow

Interstitial fluid plays a vital role in drug delivery and tumour treatment.However,few non-invasive measurement methods are available for measuring low-velocity biological fluid flow.Therefore,this study aimed to develop a novel technology called interstitial flow velocity-MRI.The interstitial flow velocity-MRI sequence consists of a dual inversion recovery preparation and an improved stimulated echo sequence(ISTE)combined with phase-contrast MRI.A homemade flow phantom was used to assess the feasibility and sensitivity of interstitial flow velocity-MRI.In addition,xenografts of female BALB/c mouse models of 4T1 breast cancer administered losartan(40 mg/kg)or saline(n?6)were subjected to imaging on a 7.0 T scanner to assess the in vivo interstitial fluid flow velocity.The results showed a significant correlation(P<0.001)between the theoretical velocities and velocities measured using the flow phantom.Interstitial flow velocity-MRI could detect a velocity as low as 10.21±2.65 mm/s with a spatial resolution of 0.313 mm.The losartan group had a lower mean interstitial fluid velocity than the control group(85±16 vs 113±24 mm/s).In addition,compared to the saline treatment,losartan treatment reduced the proportion of collagen fibres by 10%and 12%in the Masson and Sirius red staining groups,respectively.Interstitial flow velocity-MRI has the potential to determine interstitial fluid flow velocity non-invasively and exhibits an intuitive velocity map.

The parallel-plate resonator:An RF probe for MR and MRI studies over a wide frequency range

We explore the use of the parallel-plate resonator for the study of thin cuboid samples over a wide range of magnetic resonance frequencies.The parallel-plate resonator functions at frequencies from tens to hundreds of MHz.Seven parallel-plate resonators are presented and discussed in a frequency range from 8 to 500 MHz.Magnetic resonance experiments were performed on both horizontal and vertical bore magnet systems with lithium and hydrogen nuclei.Parallel-plate radiofrequency(RF)probes are easy to build and easy to optimize.Experiments and simulations showed good sensitivity of the parallel-plate RF probe geometry with a small decrease in sensitivity at higher frequencies.

^(1)H and ^(13)C NMR spectral assignments for low-concentration bile acids in biological samples

Bile acids are the main body of enterohepatic circulation in vivo.They have essential functions such as emulsifying fat,bacteriostasis and regulating multiple metabolic pathways as signal molecules.However,the assignments of NMR signals for some lowconcentration bile acids are still needed.This study combined 1D nuclear magnetic resonance(NMR)and 2D NMR techniques including 1He1H correlation spectroscopy(COSY),1He1H total correlation spectroscopy(TOCSY),1H J-resolved spectroscopy(J-Res),1He13C heteronuclear single quantum coherence spectroscopy(HSQC),and 1He13C heteronuclear multiple bond correlation spectroscopy(HMBC)to assign the 1H and 13C signals of six bile acids in aqueous solution at physiological pH(~7.4)and nine bile acids in methanol.These data are of importance to the NMR-based studies on lipid digestion,absorption,and metabolism.

Probing microstructure of solid-state synthesized LiCoO_(2)with MAS NMR spectroscopy

LiCoO_(2)is an important category of active cathode materials in lithium-ion batteries due to its high compacted electrode density,good thermal stability,and stable voltage platform.Recent works on LiCoO_(2)have focused on the realization of higher charging voltages to fully utilize its high theoretical capacity.However,an unambiguous atomic-level local probe is essential for the understanding of structure-function correlation.Here we employ highresolution solid-state nuclear magnetic resonance(NMR)spectroscopy to study the local atomic environments in LiCoO_(2)synthesized with three common sintering methods.While one-dimensional 7Li NMR shows distinct linewidth and subtle dependence on lithium over-stoichiometry,both 7Li and 59Co relaxation times are highly dependent on the sintering method.We prove that the two-step sintering method favors the elimination of unreacted Co3O4,thereby enabling the best discharge capacity in all-solid-state lithium batteries assembled with LiCoO_(2)/LGPS/LiIn,which is in accordance with its narrowest 7Li linewidth and the longest 7Li/59Co T1.

The NMR core analyzing tomograph:a multi-functional tool for non-destructive testing of building materials

NMR is becoming increasingly popular for the investigation of building materials as it is a non-invasive technology that does not require any sample preparation nor causes damage to the material.Depending on the specific application it can offer insights into properties like porosity and spatial saturation degree as well as pore structure.Moreover it enables the determination of moisture transport properties and the(re-)distribution of internal moisture into different reservoirs or chemical phases upon damage and curing.However,as yet most investigations were carried out using devices originally either designed for geophysical applications or the analysis of rather homogeneous small scale(<10 mL)samples.This paper describes the capabilities of an NMR tomograph,which has been specifically optimized for the investigation of larger,heterogeneous building material samples(diameters of up to 72 mm,length of up to 700 mm)with a high flexibility due to interchangeable coils allowing for a high SNR and short echo times(50-80 ms).

Diffusivity-limited q-space trajectory imaging

Q-space trajectory imaging(QTI)allows non-invasive estimation of microstructural features of heterogeneous porous media via diffusion magnetic resonance imaging performed with generalised gradient waveforms.A recently proposed constrained estimation framework,called QTI+,improved QTI's resilience to noise and data sparsity,thus increasing the reliability of the method by enforcing relevant positivity constraints.In this work we consider expanding the set of constraints to be applied during the fitting of the QTI model.We show that the additional conditions,which introduce an upper bound on the diffusivity values,further improve the retrieved parameters on a publicly available human brain dataset as well as on data acquired from healthy volunteers using a scanner-ready protocol.

Low-field, high-gradient NMR shows diffusion contrast consistent with localization or motional averaging of water near surfaces

Nuclear magnetic resonance(NMR)measurements of water diffusion have been extensively used to probe microstructure in porous materials,such as biological tissue,however primarily using pulsed gradient spin echo(PGSE)methods.Low-field single-sided NMR systems have built-in static gradients(SG)much stronger than typical PGSE maximum gradient strengths,which allows for the signal attenuation at extremely high b-values to be explored.Here,we perform SG spin echo(SGSE)and SG stimulated echo(SGSTE)diffusion measurements on biological cells,tissues,and gels.Measurements on fixed and live neonatal mouse spinal cord,lobster ventral nerve cord,and starved yeast cells all show multiexponential signal attenuation on a scale of b with significant signal fractions observed at b×Do>1 with b as high as 400 ms/um2.These persistent signal fractions trend with surface-to-volume ratios for these systems,as expected from porous media theory.An exception found for the case of fixed vs.live spinal cords was attributed to faster exchange or permeability in live spinal cords than in fixed spinal cords on the millisecond timescale.Data suggests the existence of multiple exchange processes in neural tissue,which may be relevant to the modeling of time-dependent diffusion in gray matter.The observed multi-exponential attenuation is from protons on water and not macromolecules because it remains proportional to the normalized signal when a specimen is washed with D20.The signal that persists to b×Do>1 is also drastically reduced after delipidation,indicating that it originates from lipid membranes that restrict water diffusion.The multiexponential or stretched exponential character of the signal attenuation at b×Do>1 appears mono-exponential when viewed on a scale of(b×Do)/3,suggesting it may originate from localization or motional averaging of water near membranes on sub-micron length scales.To try to disambiguate these two contributions,signal attenuation curves were compared at varying temperatures.While the curves align when normalizing them using the localization length scale,they separate on a motional averaging length scale.This supports localization as the source of non-Gaussian displacements,but this interpretation is still provisional due to the possible confounds of heterogeneity,exchange,and relaxation.Measurements on two types of gel phantoms designed to mimic extracellular matrix.one with charged functional groups synthesized from polyacrylic acid(PAC)and another with uncharged functional groups synthesized from polyacrylamide(PAM),both exhibit signal at b×Do>1,potentially due to water interacting with macromolecules.These preliminary finding motivate future research into contrast and attenuation mechanisms in tissue with low-field,high-gradient NMR。

Dipolar NMR relaxation of adsorbates on surfaces of controlled wettability

In reservoir rocks,the term“ageing”refers to extended exposition to crude oil;a typically water-wet sandstone will then gradually become oil-wet as a consequence of the deposition of insoluble fractions of oil onto the surface grains.Rocks have been aged artificially by subjecting them to a bitumen solution at elevated temperature in order to achieve comparable surface properties for three different types of rock:Bentheimer,Berea Buff and Liege Chalk.Using saturated and aromatic model compounds as proxies for crude oil,the nuclear magnetic resonance(NMR)relaxation dispersion in native and aged rocks was compared and correlated to the properties of paramagnetic impurities in these rock types.Perfluorated liquids were found to follow the same trend as deuterated and naturally occurring oil components,suggesting they can be used as suitable tracers for wettability studies since the ^(19)F nucleus is absent in natural sources.By combining electron paramagnetic resonance(EPR)and dynamic nuclear polarization(DNP)it becomes possible to identify and quantify the origin of the dominating relaxation processes between native and aged rocks,providing an alternative approach to assess wettability in natural rocks.