Magnetic Resonance Relaxometry Research Articles

White matter integrity and motor function: a link between cerebral myelination and longitudinal changes in gait speed in aging.

Gait speed is a robust health biomarker in older adults, correlating with the risk of physical and cognitive impairments, including dementia. Myelination plays a crucial role in neurotransmission and consequently affects various functions, yet the connection between myelination and motor functions such as gait speed is not well understood. Understanding this link could offer insights into diagnosing and treating neurodegenerative diseases that impair mobility. This study analyzed 437 longitudinal observations from 138 cognitively unimpaired adults, aged 22 to 94years, to investigate the relationship between myelin content and changes in gait speed over an average of 6.42years. Myelin content was quantified using a novel multicomponent magnetic resonance relaxometry method, and both usual and rapid gait speeds (UGS, RGS) were measured following standard protocols. Adjusting for covariates, we found a significant fixed effect of myelin content on UGS and RGS. Longitudinally, lower myelin content was linked to a greater decline in UGS, particularly in brain regions associated with motor planning. These results suggest that changes in UGS may serve as a reliable marker of neurodegeneration, particularly in cognitively unimpaired adults. Interestingly, the relationship between myelin content and changes in RGS was only observed in a limited number of brain regions, although the reason for such local susceptibility remains unknown. These findings enhance our understanding of the critical role of myelination in gait performance in unimpaired adults and provide evidence of the interconnection between myelin content and motor functionimpairment.

Physically Cross-Linked PVA Hydrogels as Potential Wound Dressings: How Freezing Conditions and Formulation Composition Define Cryogel Structure and Performance

Objectives: Hydrogels produced using the freeze–thaw method have demonstrated significant potential for wound management applications. However, their production requires precise control over critical factors including freezing temperature and the choice of matrix-forming excipients, for which no consensus on the optimal conditions currently exists. This study aimed to address this gap by evaluating the effects of the above-mentioned variables on cryogel performance. Methods: Mechanical properties, absorption capacity, and microstructure were assessed alongside advanced analyses using differential scanning calorimetry (DSC) and low-field nuclear magnetic resonance relaxometry (LF TD NMR). Results: The results demonstrated that fully hydrolyzed polyvinyl alcohol (PVA) with a molecular weight above 61,000 g/mol is essential for producing high-performance cryogels. Among the tested formulations, an 8% (w/w) PVA56–98 solution (Mw~195,000; DH = 98.0–98.8%) with 10% (w/w) propylene glycol (PG) provided the best balance of stretchability, durability, and low adhesion. Notably, while −25 °C is often used for cryogel preparation, freezing the gel precursor at −80 °C yielded superior results, producing materials with more open, interconnected structures and enhanced mechanical strength and elasticity—deviating from conventional practices. Conclusions: The designed cryogel prototypes exhibited functional properties comparable to or even surpassing commercial wound dressings, except for absorption capacity, which remained lower. Despite this, the cryogel prototypes demonstrated potential as wound dressings, particularly for use in dry or minimally exuding wounds. All in all, this study provides a comprehensive analysis of the physicochemical and functional properties of PVA cryogels, establishing a strong foundation for the development of advanced wound dressing systems.

Chert outcrops differentiation by means of low-field NMR relaxometry

Siliceous rocks served as raw materials in the production of stone tools from the Middle Paleolithic onwards. Due to migration, the provenance of archaeological artefacts can differ from their natural outcrop location. The aim of this work was the application of 1D and 2D low-field nuclear magnetic resonance (LF-NMR) relaxometry to distinguish cherts by their original source. Herein, bedded cherts and accompanying nodular cherts coming from three different outcrops of Kraków-Częstochowa Upland were investigated. 1D and 2D (T1-T2) experiments of water-saturated and dry rock sample states delivered T1, T2 times and T1/T2 ratios of distinct hydrogen populations – parameters sensitive to pore size, surface properties, and hydrogen bonding length. In-depth analysis of NMR data showed substantial differences in the porosity, pore surface and pore structure properties of investigated chert samples tested in the three different saturation levels (100% water-saturated, dried and differential). Finally, principal component analysis (PCA) was performed to reduce the number of correlations obtained and highlight the most important NMR properties specific to the particular outcrop localization."Please check captured corresponding author email if correct.""The email is correct"

Investigations on Unconventional Tight Carbonate Rock Cores by Low-Field Nuclear Magnetic Resonance Relaxometry

Investigations on Unconventional Tight Carbonate Rock Cores by Low-Field Nuclear Magnetic Resonance Relaxometry

Markers of low field NMR relaxation features of tissues

This work presents an approach to exploiting Nuclear Magnetic Resonance (NMR) relaxometry data (1H spin-lattice relaxation rates covering the frequency range from below 1 kHz to 10 MHz) for the purpose of differentiating between pathological and reference tissues. Characteristic quantities (markers) that can be obtained in a straightforward manner, not resorting to an advanced analysis of 1H spin-lattice relaxation data, have been identified and compared for pathological and reference colon tissues. Moreover, the relaxation data have been parametrised in terms of Lorentzian spectral densities and the possibility of using the obtained dipolar relaxation constants and correlation times as biomarkers to assess the state of tissues has been discussed. It has also been demonstrated that the relaxation data for the reference and the pathological tissues can be attributed to two groups (for each case). The studies are a step towards exploiting the potential of NMR relaxometry for characterisation of pathological changes in tissues.

Molecular Dynamics, Dielectric Properties, and Textures of Protonated and Selectively Deuterated 4'-Pentyl-4-biphenylcarbonitrile Liquid Crystal.

Using liquid crystals in near-infrared applications suffers from effects related to processes like parasitic absorption and high sensitivity to UV-light exposure. One way of managing these disadvantages is to use deuterated systems. The combined 1H and 2H nuclear magnetic resonance relaxometry method (FFC NMR), dielectric spectroscopy (DS), optical microscopy (POM), and differential scanning calorimetry (DSC) approach was applied to investigate the influence of selective deuteration on the molecular dynamics, thermal properties, self-organization, and electric-field responsiveness to a 4'-pentyl-4-biphenylcarbonitrile (5CB) liquid crystal. The NMR relaxation dispersion (NMRD) profiles were analyzed using theoretical models for the description of dynamics processes in different mesophases. Obtained optical textures of selectively deuterated 5CB showed the occurrence of the domain structure close to the I/N phase transition. The dielectric measurements showed a substantial difference in switching fields between fully protonated/deuterated 5CB and selectively deuterated molecules. The DSC thermograms showed a more complex phase transition sequence for partially deuterated 5CB with respect to fully protonated/deuterated molecules.

Determination of the Redox Ratio of Iron in a Diamagnetic Matrix Using Low-Field NMR Relaxometry.

Proton nuclear magnetic resonance (NMR) relaxometry is proposed to determine the iron redox ratio of slag samples. It depends on the paramagnetic effect on bulk water relaxation times. Experiments have been carried out to calibrate the relationship between the concentration of Fe3+ and Fe2+ ions and the measured relaxation times on prepared standard samples. It is shown that Fe2+ ions have very different effects on the relaxation times than Fe3+ ions. For the solid slag samples, digestion in an acid was used to produce solutions with a pH of 1.0. Hydrogen peroxide (H2O2) was then added to the digested samples to oxidize Fe2+ ions to Fe3+ ions. The concentration of Fe2+ and Fe3+ ions in solution can be calculated by measuring the relaxation times before and after oxidation. The Fe3+/∑Fe ratio of slag samples was also investigated by wet chemistry and 57Fe Mössbauer spectroscopy and calculated by FactSage at the equilibrium state. The results obtained from different methods are consistent, indicating that this NMR relaxometry method is reliable.

N-Heterocyclic Carbene-Derived Carbon Disulfide Radical Ligands for Palladium Diradicals.

N-heterocyclic carbenes (NHCs) are recognized for their ability to stabilize various main group radicals; however, NHC-derived, sulfur-based radicals remain rare. In this study, we successfully synthesized and characterized a series of palladium diradical complexes that featured new sulfur-based radical ligands from NHC-carbon disulfide adducts. Spectroscopic and computational characterizations of the palladium complexes confirmed the open-shell singlet ground state, which resulted from the antiferromagnetic coupling of two unpaired electrons on each ligand. Proton nuclear magnetic resonance relaxometry was used to experimentally confirm the presence of these unpaired electrons. Moreover, the redox behavior of the complexes was localized on the ligand center, confirming the redox activity of the ligands. The discovery of this sulfur-based, redox-active radical ligand underscores the versatility and significance of NHC-derived radicals, thereby expanding the repertoire of radical ligands and opening new avenues for advanced material and catalytic systems.

Shrinkage reduction mechanism of low Ca/Si ratio C-A-S-H in cement pastes containing fly ash

Understanding the drying shrinkage of low Ca/Si ratio cement pastes is crucial for promoting the use of low-clinker ratio cementitious materials and reducing the environmental impact of cement production. We prepared well-hydrated cement paste samples with various fly ash replacement and water-to-cement ratios. The long-term drying shrinkage was measured by 1 mm-thick samples. Results showed that fly ash containing samples exhibited lower shrinkage and the irreversible part of drying shrinkage was less compared to those without fly ash. Chemical composition analysis of the calcium aluminate-silicates hydrate (C-A-S-H) was conducted using X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). Additionally, water vapor sorption isotherms and proton nuclear magnetic resonance (1H NMR) relaxometry were used to determine specific surface area and pore structure. By analyzing these results in conjunction with the C-A-S-H model, we attributed the reduced and more reversible drying shrinkage in fly ash cement to lower Ca ion amounts in the interlayer space and fewer trapped larger pores.

Assessing Mechanochemical Properties of Acrylonitrile Butadiene Styrene (ABS) Items in Cultural Heritage Through a Multimodal Spectroscopic Approach.

A multimodal spectroscopic approach is proposed to correlate the mechanical and chemical properties of plastic materials in art and design objects, at both surface and subsurface levels, to obtain information about their conservation state and to monitor their degradation. The approach was used to investigate the photo-oxidation of acrylonitrile butadiene styrene (ABS), a plastic commonly found in many artistic and design applications, using ABS-based LEGO bricks as model samples. The modifications of the chemical and viscoelastic properties of ABS during photoaging were monitored by correlative Brillouin and Raman microspectroscopy (BRaMS), combined with portable and noninvasive broad-range external reflection infrared (IR) spectroscopy and nuclear magnetic resonance (NMR) relaxometry, directly applicable in museums. BRaMS enabled combined measurements of Brillouin light scattering and Raman spectroscopy in a microspectroscopic setup, providing for the coincident probe of the chemical and mechanical changes of ABS at the sample surface. NMR relaxometry allowed for noninvasive measurements of relaxation times and depth profiles which are directly related to the molecular mobility of the material. Complementary chemical information was acquired by external reflection IR spectroscopy. The simultaneous probe of the chemical and mechanical properties by this multimodal spectroscopic approach enabled us to define a decay model of ABS in terms of compositional changes and variation of stiffness and rigidity occurring with photodegradation. The knowledge acquired on LEGO samples has been used to rate the conservation state of ABS design objects noninvasively investigated by external reflection Fourier transform IR spectroscopy and NMR relaxometry offered by the MObile LABoratory (MOLAB) platform of the European Research Infrastructure of Heritage Science.

Moisture sorption behaviour, microstructural changes and macroscopic deformation of hardened cement pastes during the first three drying–resaturation cycles

Moisture sorption and macroscopic deformation of hardened cement pastes (hcps) were studied in the first three drying–resaturation (D–R) cycles using low–field 1H nuclear magnetic resonance relaxometry. Four types of water (interlayer, gel, interhydrate and capillary) were detected in the hcps. In principle, they were sequentially removed from larger to smaller pores during drying with decreasing relative humidity (RH), resulting in shrinkage of the hcps. Unexpected increases in gel and interlayer water contents as well as greater shrinkage during drying from 100 % to 69 % RH were observed, which is believed to originate from the re–arrangement of C–S–H structure. Because of the C–S–H re–arrangement, irreversible shrinkage was detected during D–R cycles. The drying and irreversible shrinkage in each cycle diminished with the D–R number. A lower water–to–cement ratio and higher curing temperature for hcps are beneficial for reducing drying and irreversible shrinkage.

Dual Polyanion Mechanism for Superionic Transport in BH4‐Based Argyrodites

AbstractPolyanion rotations are often linked to cation diffusion, but the study of multiple polyanion systems is scarce due to the complexities in experimentally determining their dynamic interactions. This work focuses on BH4‐based argyrodites, synthesized to achieve a high conductivity of 11 mS cm−1. Advanced tools, including high‐resolution X‐ray diffraction, neutron pair distribution function analysis, and mutinuclear magic‐angle‐spinning nuclear magnetic resonance (NMR) spectroscopy and relaxometry, along with theoretical calculations, are employed to unravel the dynamic intricacies among the dual polyanion lattice and active charge carriers. The findings reveal that the anion sublattice of Li5.07PS4.07(BH4)1.93 affords an even temporal distribution of Li among PS43− and BH4−, suggesting minimal trapping of the charge carriers. Moreover, the NMR relaxometry unveils rapid BH4− rotation on the order of ∼GHz, affecting the slower rotation of neighboring PS43− at ∼100 MHz. The PS43− rotation synchronizes with Li+ motion and drives superionic transport. Thus, the PS43− and BH4− polyanions act as two‐staged dual motors, facilitating rapid Li+ diffusion.

Low‐field nuclear magnetic resonance relaxometry: a new approach for monosaccharide identification in sugar solutions

SummaryMonosaccharides such as glucose, fructose, and galactose are the building blocks of oligosaccharides and act as the major energy sources in our body. These three monosaccharides are the most prominent in food processing and widely consumed analytes, found in fruits or milk. Although several analytical methods are available to identify and quantify sugar solutions, their drawbacks urge the search for better possible alternatives. A simple, rapid, and efficient method for identifying monosaccharides (ᴅ‐fructose, ᴅ‐galactose, and ᴅ‐glucose) was investigated using low‐field nuclear magnetic resonance (LF‐NMR), exploring the applicability and reliability of this machine. The transverse (T2) relaxation curve was analysed to distinguish monosaccharides from each other. The increasing monosaccharide concentration in the sugar solution causes leftward shifts in signals, indicating a gradual reduction in the mobility of water molecules. The addition of sugar generated a secondary peak, which assisted in identifying monosaccharides. Notably, fructose exhibited distinct behaviour from that of glucose and galactose. The regression coefficient consistently exceeded 0.98, indicating the reliability of this experiment. LF‐NMR encountered challenges in differentiating stereo‐isomeric glucose and galactose. However, quantification of monosaccharides from known binary mixtures (water and one monosaccharide) is possible by preparing standard curves of different concentrations of sugars. These standard curves can be either T2 or the total surface area of the peaks as a function of sugar concentration. The study concludes that LF‐NMR has potential for the qualitative and quantitative analysis of monosaccharides in pure solutions or powdered samples. It is hoped that the rapid and easy way of monosaccharide identification by simple analysis of peaks obtained from NMR spectra will enhance its accessibility for users. However, it also acknowledges limitations in applying this method to complex systems (mixtures of different sugars in a solution).

Slaughterhouse Wastewater Properties Assessment by Modern and Classic Methods

Advanced 1H Nuclear Magnetic Resonance (NMR) relaxometry and diffusometry methods and VIS-nearIR spectroscopy combined with pH, electrical conductivity (EC) and totally dissolved solids (TDSSs) measurements were used to assess the properties of wastewater collected from a chicken slaughterhouse in each step of the treatment process (wastewater before treatment, biologically treated wastewater, chemically treated wastewater and discharged wastewater) and from sludge. The 1H NMR Carr–Purcell–Meiboom–Gill (CPMG) and Pulsed-Gradient-Stimulated-Echo (PGSE) decay curves recorded for all samples of wastewater were analyzed by inverse Laplace transform (ILT) to obtain the distributions of transverse relaxation times T2 and diffusion coefficient D. The VIS-nearIR total absorbance, T2-values, D-values, pH, EC and TDSS parameters were used for statistical analysis in principal component (PCA). The 1H T2-distributions measured for the slaughterhouse wastewater lie in two main regions reflecting the number of dissolved solids or the distribution of undissolved solids. The PCA analysis successfully differentiates between polluted and less polluted wastewaters and sludge. The wastewater treatment applied by the slaughterhouse is efficient. The recommended methods for wastewater monitoring are the NMR T2- and D-distributions and EC, TDSSs and NMR-D diffusion coefficient. Finally, Machine Learning algorithms are used to provide prediction maps of wastewater treatment stage.

Novel approach to detect encasement failures in the anchorage system of guyed transmission towers by distribution of relaxation times

Anchor rods of guyed transmission towers encapsulated in Portland cement pastes and mortar are usually affected by corrosion processes when buried in soils with chemical aggressiveness. Encasement failures, such as cracks and leaks, cause preferential points of degradation of the inner metal bar, affecting its mechanical integrity over the years and causing, in many cases, the collapse of the transmission tower. However, the nondestructive testing (NDT) used for diagnosis has not shown conclusive results. In this study, a methodology to detect failures in the cement paste encasement was developed using electrochemical impedance spectroscopy (EIS) by evaluating the distribution of relaxation time constants (DRT) to identify different time constants of water in the pore structure of cement paste. These parameters were typically determined by the nuclear magnetic resonance (NMR) relaxometry technique, which was not correctly applied to the field tests. From the results, it was possible to detect the presence of cement paste in soils with electrical resistivities varying from 4.0 to 200.0 Ω.m by identifying their time constant at 0.10 ms, which was attributed to the water present in the hydrated calcium silicate gel (C-S-H) interlayers.

Lyotropic Aqueous 2-Picolinium Ionic Liquid Crystals and Their Shear-Induced Foams.

1-Dodecyl-2-methylpyridinium bromide ([C12-2-Pic][Br]) and 1-hexadecyl-2-methylpyridinium bromide ([C16-2-Pic][Br]) are two ionic liquid crystals presenting thermotropic smectic phases above 80 °C. Aiming to take advantage of the liquid crystalline properties at lower temperatures, lyotropic aqueous systems were prepared from these two organic salts. Both systems were characterized by polarized optical microscopy (POM), X-ray powder diffraction (XRD), and fast field cycling nuclear magnetic resonance (FFC-NMR) relaxometry to assess their texture, phase structure, and molecular dynamics, respectively. The mesomorphic behavior was induced at room temperature. Moreover, the lyotropic [C12-2-Pic][Br]aq revealed a smectic phase with higher separation between layers, different from the lamellar phases found in the thermotropic system (S1 and SA), which is thermally stable up to 50 °C. Furthermore, the surfactant nature of the ionic liquids diluted solutions investigated in this work allowed the formation of foams. It was found that the precursor solutions of the lyotropic dilutions with the longest alkyl chain ([C16-2-Pic][Br]aq) originated liquid foams with more stable structures than those of [C12-2-Pic][Br]aq.

Accelerated proton dissociation in an excited state induces superacidic microenvironments around graphene quantum dots

Investigating proton transport at the interface in an excited state facilitates the mechanistic investigation and utilization of nanomaterials. However, there is a lack of suitable tools for in-situ and interfacial analysis. Here we addresses this gap by in-situ observing the proton transport of graphene quantum dots (GQDs) in an excited state through reduction of magnetic resonance relaxation time. Experimental results, utilizing 0.1 mT ultra-low-field nuclear magnetic resonance relaxometry compatible with a light source, reveal the light-induced proton dissociation and acidity of GQDs’ microenvironment in the excited state (Hammett acidity function: –13.40). Theoretical calculations demonstrate significant acidity enhancement in –OH functionalized GQDs with light induction (pKa*\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\mathrm{p}}}{K}_{{\ ext{a}}}^{*}$$\\end{document} = –4.62, stronger than that of H2SO4). Simulations highlight the contributions of edge and phenolic –OH groups to proton dissociation. The light-induced superacidic microenvironment of GQDs benefits functionalization and improves the catalytic performances of GQDs. Importantly, this work advances the understanding of interfacial properties of light-induced sp2–sp3 carbon nanostructure and provides a valuable tool for exploring catalyst interfaces in photocatalysis.

3D Printed Drug Delivery Systems in Action-Magnetic Resonance Imaging and Relaxometry for Monitoring Mass Transport Phenomena.

The hypothesis of the study was that (1) 3D printed drug delivery systems (DDS) could be characterized in situ during drug release using NMR/MRI techniques in terms of mass transport phenomena description (interfacial phenomena), particularly for systems dealing with two mobile phases (e.g., water and low molecular weight liquid polymer); (2) consequently, it could be possible to deduce how these interfacial mass transport phenomena influence functional properties of 3D printed DDS. Matrix drug delivery systems, prepared using masked stereolithography (MSLA), containing poly(ethylene glycol) diacrylate (PEGDA) and low molecular weight polyethylene glycol (PEG) with ropinirole hydrochloride (RH) were studied as example formulations. The PEGDA to PEG (mobile phase) concentration ratio influenced drug release. It was reflected in spatiotemporal changes in parametric T2 relaxation time (T2) and amplitude (A) images obtained using magnetic resonance imaging (MRI) and T1-T2 relaxation time correlations obtained using low-field time-domain nuclear magnetic resonance (LF TD NMR) relaxometry during incubation in water. For most of the tested formulations, two signal components related to PEG and water were assessed in the hydrated matrices by MRI relaxometry (parametric T2/A images). The PEG component faded out due to outward PEG diffusion and was gradually replaced by the water component. Both components spatially and temporally changed their parameters, reflecting evolving water-polymer interactions. The study shows that dynamic phenomena related to bidirectional mass transport can be quantified in situ using NMR and MRI techniques to gain insight into drug release mechanisms from 3D printed DDS systems.

Phase structures of a broad compositional range of polyethylenes by TD-NMR

A number of morphological features of polyethylenes across a wide range of densities were studied using time-domain nuclear magnetic resonance (TD-NMR) relaxometry. The populations and T2 relaxation times of both the interphase and amorphous phase exhibit a transition at a density of ca. 935 kg/m3. At a density range of 900–935 kg/m3, the interphase is almost as populous as the crystalline phase. Aging of the samples at ambient temperature was monitored using NMR relaxometry over the course of one month, during which slight decreases in T2 relaxation times of the amorphous phase was found, possibly accompanied by a slight increase of crystallinity, by ca. 0.5 %, and the decrease of the amorphous population by a comparable amount, for the samples with higher crystallinities. The interphase T2 relaxation time was found to exhibit a strong linear correlation with the population of the amorphous phase, similar to what was observed for a series of polypropylenes in a previous study. The heat-treated and aged samples display similar crystallinities as untreated samples at the lower density range, while the former exhibit significantly higher crystallinity than the latter at the higher density range.

Dynamic water profile in various types of cheese analyzed by means of nuclear magnetic resonance relaxometry

Dynamic water profile in various types of cheese analyzed by means of nuclear magnetic resonance relaxometry