Magnetic Resonance Relaxation Research Articles

Slowly Relaxing Local Structure Analysis of 15N Relaxation from the Proteins p50 and Human Neutrophil Gelatinase-Associated Lipocalin: New Insights into the Dynamic Structure of β-Barrel Proteins

Nuclear magnetic resonance relaxation analysis is a powerful method for studying the internal mobility of proteins. We have developed for analysis the slowly relaxing local structure (SRLS) approach. SRLS is general in its nature in several respects, including the tensorial representation of the physical quantities comprising the dynamic model. By controlling tensor symmetry, a broad range of systems can be treated with physical relevance, typically with data-fitting techniques. In simple limits, SRLS yields the traditional model-free (MF) method. In the present context, MF simplicity means featuring the highest possible tensor symmetry. This renders MF-based data-fitting susceptible to the usage of fit parameters, yielding physically ill-defined results. A typical candidate is the Rex term, devised to represent ms-μs motions but often invoked by the fitting scheme just to improve the statistics. Here, we consider two such cases using the N-H bond as probe and the proteins p50 and human neutrophil gelatinase-associated lipocalin as paradigm systems. We illustrate the harm caused by the physically unjustified involvement of Rex in MF-based 15N relaxation analysis. Then, we show that forgoing the usage of Rex, SRLS analysis of the very same experimental data provides interesting new information.

Normative quantitative relaxation atlases for characterization of cortical regions using magnetic resonance fingerprinting.

Quantitative magnetic resonance (MR) has been used to study cyto- and myelo-architecture of the human brain non-invasively. However, analyzing brain cortex using high-resolution quantitative MR acquisition can be challenging to perform using 3T clinical scanners. MR fingerprinting (MRF) is a highly efficient and clinically feasible quantitative MR technique that simultaneously provides T1 and T2 relaxation maps. Using 3D MRF from 40 healthy subjects (mean age = 25.6 ± 4.3years) scanned on 3T magnetic resonance imaging, we generated whole-brain gyral-based normative MR relaxation atlases and investigated cortical-region-based T1 and T2 variations. Gender and age dependency of T1 and T2 variations were additionally analyzed. The coefficient of variation of T1 and T2 for each cortical-region was 3.5% and 7.3%, respectively, supporting low variability of MRF measurements across subjects. Significant differences in T1 and T2 were identified among 34 brain regions (P < 0.001), lower in the precentral, postcentral, paracentral lobule, transverse temporal, lateral occipital, and cingulate areas, which contain sensorimotor, auditory, visual, and limbic functions. Significant correlations were identified between age and T1 and T2 values. This study established whole-brain MRF T1 and T2 atlases of healthy subjects using a clinical 3T scanner, which can provide a quantitative and region-specific baseline for future brain studies and pathology detection.

Highly concentrated solvothermal synthesis of sub-10-nm BaTiO3 nanoparticles for optical applications

Single-crystalline barium titanate: BaTiO3 (BT) nanoparticles (NPs) with sub-10-nm size have been successfully obtained by a highly concentrated solvothermal synthesis using a high concentration of Ba(OH)2 and a titanium complex. To obtain sub-10-nm NPs, we focused on the gradual increase in the OH– ion concentration and the decrease in the dielectric constant of solvents, and BT NPs were produced in 1 h even at a low temperature of 200 °C. High-resolution transmission electron microscopy (HR-TEM) observation revealed that the resulting BT NPs were single-nanometer size, consisting of a single-crystalline structure. 1H-nuclear magnetic resonance (NMR) relaxation time (T2) and zeta potential measurements demonstrated that our BT NPs had high dispersibility and dispersion stability under acidic conditions. The yellowness index measurements revealed that the BT NPs dispersions exhibited colorless property. The resulting single nanometer-sized BT NPs are promising as high refractive index materials for optical applications due to being dispersed in optical resins.

A Bayesian Optimization Approach to the Simultaneous Extraction of Intrinsic Physical Parameters fromT1 andT2 Relaxation Responses

SummaryNuclear magnetic resonance (NMR) relaxation responses in porous media provide a sensitive probe of the microstructure and yet are influenced by a number of factors which are not easily detangled. Low-field T2 transverse relaxation measurements can be carried out quickly and are frequently used as pore size distributions, while adding T1 longitudinal relaxation measurements provides additional insights into surface properties and fluid content. Here we present an inverse solution workflow extracting related intrinsic physical parameters of the system by fitting experiment and numerical simulation(s). An efficient NMR forward solver for the simultaneous calculation of T1 and T2 responses is introduced, which honors existing inequality relationships between T1 and T2 parameters. We propose a Bayesian optimization approach that jointly identifies T1- and T2-related properties satisfying physical constraints by simultaneously fitting T1 and T2 experiments to simulations. This dual-task inverse solution workflow (DT-ISW) identifies the solution by minimizing the sum of the L2 norm of the fitting residuals of both T1 and T2 distributions into a single objective and jointly models the two highly correlated objectives with high efficiency using the vector-valued Gaussian process (GP) kernel for transfer learning. A multimodal search strategy is used to identify nonunique solution sets of the problem. The workflow is demonstrated on Bentheimer sandstone, identifying five intrinsic physical parameters. The performance of the joint DT-ISW (DT-ISW-J) is compared to a sequential DT-ISW (DT-ISW-S) approach as well as an independent single-task ISW (ST-ISW) of the T1 and T2 responses. Both dual-task versions converge more than two times faster than the single-task version. DT-ISW-J equally minimizes the L2 norm of T1 and T2 fitting residuals whereas DT-ISW-S only preferentially minimizes the objective assigned higher importance. A Pareto optimal solution (POS) is provided to allow operators to subjectively balance the preference of T1 and T2 data fits for the slightly conflicting objectives. The ability to extract five intrinsic physical parameters simultaneously provides new techniques for tracking wettability alteration and assessing the influence of clay amount and distribution on petrophysical property estimates.

A litmus test for classifying recognition mechanisms of transiently binding proteins

Partner recognition in protein binding is critical for all biological functions, and yet, delineating its mechanism is challenging, especially when recognition happens within microseconds. We present a theoretical and experimental framework based on straight-forward nuclear magnetic resonance relaxation dispersion measurements to investigate protein binding mechanisms on sub-millisecond timescales, which are beyond the reach of standard rapid-mixing experiments. This framework predicts that conformational selection prevails on ubiquitin’s paradigmatic interaction with an SH3 (Src-homology 3) domain. By contrast, the SH3 domain recognizes ubiquitin in a two-state binding process. Subsequent molecular dynamics simulations and Markov state modeling reveal that the ubiquitin conformation selected for binding exhibits a characteristically extended C-terminus. Our framework is robust and expandable for implementation in other binding scenarios with the potential to show that conformational selection might be the design principle of the hubs in protein interaction networks.

Physicochemical and Morphological Study of the Saccharomyces cerevisiae Cell-Based Microcapsules with Novel Cold-Pressed Oil Blends

Vegetable oils rich in polyunsaturated fatty acids are a valuable component of the human diet. Properly composed oil blends are characterized by a 5:1 ratio of ω6/ω3 fatty acids, which is favorable from a nutritional point of view. Unfortunately, their composition makes them difficult to use in food production, as they are susceptible to oxidation and are often characterized by a strong smell. Encapsulation in yeast cells is a possible solution to these problems. This paper is a report on the use of native and autolyzed yeast in the encapsulation of oils. The fatty acid profile, encapsulation efficiency, morphology of the capsules obtained, and thermal behavior were assessed. Fourier transform infrared analysis and low-field nuclear magnetic resonance relaxation time measurements were also performed. The process of yeast autolysis changed the structure of the yeast cell membranes and improved the loading capacity. Lower encapsulation yield was recorded for capsules made from native yeast; the autolysis process significantly increased the value of this parameter. It was observed that NY-based YBMCs are characterized by a high degree of aggregation, which may adversely affect their stability. The average size of the AY capsules for each of the three oil blends was two times smaller than the NY-based capsules. The encapsulation of oils in yeast cells, especially those subjected to the autolysis process, ensured better oxidative stability, as determined by DSC, compared to fresh blends of vegetable oils. From LF NMR analysis of the relaxation times, it was shown that the encapsulation process affects both spin-lattice T1 and spin-spin T2* relaxation times. The T1 time values of the YBMCs decreased relative to the yeast empty cells, and the T2* time was significantly extended. On the basis of the obtained results, it has been proven that highly unsaturated oils can be used as an ingredient in the preparation of functional food via protection through yeast cell encapsulation.

TAPBPR employs a ligand-independent docking mechanism to chaperone MR1 molecules.

Chaperones tapasin and transporter associated with antigen processing (TAP)-binding protein related (TAPBPR) associate with the major histocompatibility complex (MHC)-related protein 1 (MR1) to promote trafficking and cell surface expression. However, the binding mechanism and ligand dependency of MR1/chaperone interactions remain incompletely characterized. Here in vitro, biochemical and computational studies reveal that, unlike MHC-I, TAPBPR recognizes MR1 in a ligand-independent manner owing to the absence of major structural changes in the MR1 α2-1 helix between empty and ligand-loaded molecules. Structural characterization using paramagnetic nuclear magnetic resonance experiments combined with restrained molecular dynamics simulations reveals that TAPBPR engages conserved surfaces on MR1 to induce similar adaptations to those seen in MHC-I/TAPBPR co-crystal structures. Finally, nuclear magnetic resonance relaxation dispersion experiments using 19F-labeled diclofenac show that TAPBPR can affect the exchange kinetics of noncovalent metabolites with the MR1 groove, serving as a catalyst. Our results support a role of chaperones in stabilizing nascent MR1 molecules to enable loading of endogenous or exogenous cargo.

Evaluation of crotamine based probes as intracellular targeted contrast agents for magnetic resonance imaging

Crotamine is a lysine and cysteine rich 42 amino acids long bio-active polypeptide, isolated from the venom of a South American rattlesnake, that can also be used as cell penetrating peptide. A facile synthetic scheme for coupling cargo molecules like fluorophores (carboxyfluorescein) or MRI probes (Gd-DO3A-based macrocycle) is presented. The toxicity, cellular internalization and steady-state accumulation after long-term incubation for 18 h, as well as magnetic resonance relaxivities and cellular relaxation rates of crotamine based probes were evaluated and compared to its shorter synthetic fragment CyLoP-1. The longitudinal relaxivity (r1) of the conjugates of CyLoP-1 and crotamine is significantly lower in medium than in water indicating to the lower contrast enhancement efficacy of DO3A-based probes in biological samples. Carboxyfluorescein labeled crotamine did not exhibit toxicity up to a concentration of 2.5 µM. CyLoP-1 accumulated about four times better within the cells compared to crotamine. Fluorescence microscopy suggests different predominant uptake mechanisms for crotamine and CyLoP-1 in 3T3 cells. While crotamine is predominantly localized in vesicular structures (most likely endosomes and lysosomes) within the cell, CyLoP-1 is mainly homogeneously distributed in the cytosol. The cellular relaxation rate (R1, cell) of the crotamine based probe was not significantly increased whereas the corresponding CyLoP-1-derivative showed a slightly elevated R1, cell. This study indicates the potential of crotamine and in particular the shorter fragment CyLoP-1 to be useful for an efficient transmembrane delivery of agents directed to intracellular (cytosolic) targets. However, the applicability of the conjugates synthesized here as contrast agents in MR imaging is limited. Further improvement is needed to prepare more efficient probes for MRI applications, i.e., by replacing the DO3A- with a DOTA-based chelate.

Evaluation of alumina slurry dispersion by nuclear magnetic resonance relaxation as a comparison to conventional dispersion evaluation methods.

In this paper, we evaluated the particle dispersion degree of alumina slurry containing a dispersant by solvent nuclear magnetic resonance (NMR) relaxation and compared it with conventional dispersion evaluation methods such as viscosity, particle size, and sedimentation height measurements. The dispersion of slurry was evaluated via numerical analysis of the transverse relaxation time (T2 ). The effect of the changes in different parameters of the experiment in terms of milling time, solid loading, and dispersant amount was investigated by NMR relaxation as well as conventional methods. The results of NMR relaxation measurements revealed that T2 correlates well with other dispersion evaluation methods; thus, it is an efficient technique to evaluate the dispersion of alumina slurry, specifically, when studying the effect of the change in milling time and dispersion amount.

NMR transverse relaxation of the clay-rich shale in inhomogeneous magnetic field: A numerical study

We conducted comprehensive numerical simulations to probe the low field nuclear magnetic resonance (NMR) relaxation of the clay-rich shale in inhomogeneous magnetic field. Under the guidance of the Bloch equation, the relaxation property of a unimodal distributed clay-rich shale is simulated using the Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence. Both the magnetization and the transverse relaxation time (T2) spectrum are obtained to investigate influential factors such as the excitation pulse angle, the refocusing pulse angle, the pulse duration, the echo spacing, as well as the off-resonance frequency. The simulation result showed that the field inhomogeneity contributes great influence on the NMR relaxation, particular in high magnetic field strength and high off-resonance frequency. We observed that in standard CMPG pulse sequence, the amplitude of the T2 distribution is negatively correlated with the off-resonance frequency and can be compensated by the empirical regression. Moreover, the excitation pulse angle poses great impact on the amplitude of the T2 distribution, but has less influence on the T2 distribution and its peak value. On the contrary, both the amplitude and the peak value of the T2 spectrums are also impacted by the refocusing pulse angle, especially in higher magnetic field inhomogeneity. The refocusing pulse angle is preferable higher than 150° for the clay-rich shale since it helps the spins to rephrase quickly. In additional, the echo spacing is ideally reduced to as low as its minimal value for the measurement of samples with short relaxation component. The result provides comprehensive knowledge on influential factors of the NMR relaxation of the clay-rich shale, which is useful for the optimization of the pulse sequence, the acquisition conditions, as well as the manipulation of the magnetization data.

The Metal Ion Release of Manganese Ferrite Nanoparticles: Kinetics, Effects on Magnetic Resonance Relaxivities, and Toxicity.

Mn2+ release is particularly important for biological application of manganese-based nanomaterials. However, the Mn2+ release profiles of the manganese ferrite nanoparticles are under clarification. Here, we synthesized 3, 10, and 18 nm manganese ferrite nanoparticles (MFNPs) as model systems to study the Mn2+ release behavior, size, and pH-dependent kinetics. The Mn2+ release kinetic study showed that the first-order kinetic model was suitable for 3 and 10 nm MFNPs, while the Higuchi model was suitable for 18 nm MFNPs in a neutral PBS buffer (pH 7.4). In an acidic PBS buffer (pH 4.8), the Mn2+ release from all sizes of MFNPs follows first-order kinetics, which is possible due to the reaction between MFNPs and H+. The influence of Mn2+ release was evaluated by comparing the variations of magnetic resonance (MR) relaxation and magnetic properties before and after Mn2+ release of MFNPs. The results showed that the saturation magnetization (Ms), longitudinal relaxivity (r1), and transverse relaxivity (r2) values declined due to Mn2+ release, while the ratio of r2/r1 increased slightly, showing that all sizes of MFNPs exhibited the same MR mode as the synthesized MFNPs. More importantly, the release kinetics were employed to estimate the toxicity of the released Mn2+in vivo. The potential toxicity is acceptable for MFNP administration since the calculated amount of Mn2+ is in the range of safe doses.

Tailoring the Selective Permeation Properties of Asymmetric Cellulose Acetate/Silica Hybrid Membranes and Characterisation of Water Dynamics in Hydrated Membranes by Deuterium Nuclear Magnetic Resonance.

In this work, the water order and dynamics in hydrated films of flat asymmetric cellulose acetate (CA)/silica, CA/SiO2, and hybrid membranes, covering a wide range of nanofiltration (NF) and ultrafiltration (UF) permeation properties, were characterised by deuterium nuclear magnetic resonance (DNMR) relaxation. The range of NF/UF characteristics was attained by subjecting three CA/SiO2 membranes, prepared from casting solutions with different acetone/formamide ratios to drying post-treatments of solvent exchange and conditioning with surfactant mixtures. Post-treated and pristine CA/SiO2 membranes were characterised in terms of hydraulic permeability, selective permeation properties and molecular weight cut-off. These results were correlated with the DNMR relaxation findings. It was found that the post-treatment by solvent exchange caused membrane shrinkage that led to very different permeation characteristics and a significant enhancement of the DNMR relaxation observables. In contrast, conditioning with surfactant solutions exhibited a weaker effect over those properties. Scanning electron microscopy (SEM) images were obtained for the membranes post-treated with solvent exchange to confirm their asymmetric nature. This work provides an essential indication that DNMR relaxometry is a reliable tool to characterise the asymmetric porous structures of the NF/UF CA/SiO2 hybrid membranes.

The role of overbalance pressure on mud induced alteration of sandstone rock pore system

Overbalance pressure is a very critical parameter in drilling operations. It has a great impact on formation damage, depending on other downhole parameters such as temperature, time, type and composition of mud, and rock mineralogical content. The objective of this study is to determine the degree of the impact of overbalance pressure on mud–rock interaction and the resultant effects on the rock pore system. This research presents an experimental study for the interaction of a Berea Buff sandstone and barite water-based under different overbalance pressure (300, 700, and 1000 psi) under the same temperature and interaction time. The experiments involved the use of the scanning electron microscope and nuclear magnetic resonance relaxation measurements to monitor changes in the pore system of the rock samples. A modified filtration cell was used to accommodate the rock samples and mud at different overbalance pressures. The obtained results showed that the filtration properties, rock flow characteristics (rock permeability, pore throat radius, and pore system scale type) are all affected by increasing the overbalance pressure. The filtration properties increased in terms of mud cake thickness and filtrate volume by 111% and 36% respectively when the overbalance pressure was increased from 300 to 1000 psi. The total rock porosity showed a decrease from 21.6% (pre-mud interaction) to 17.6, 15.2, and 14.2% under 300, 700, and 1000 psi, respectively. The rock permeability decreased by 75% under 1000 psi overbalance pressure while pore throat radius decreased by 45%. However, the rock pore type remains on the same scale (Macro) after interaction with the mud. Statistical analysis showed that the rock porosity and permeability decreased with the overbalance pressure increase through a polynomial relationship with a high determination coefficient of 0.99. Analysis of the internal pore system by the scanning electron microscope showed that the formation damage is mainly attributed to the precipitations of mud solids as overbalance pressure is increased.

One-Step Determination of Alkaline Phosphatase in Human Serum Based on Manganese (IV) Dioxide/Manganese (II)-Mediated Nuclear Magnetic Resonance (NMR) Relaxation

Alkaline phosphatase (ALP) is a significant biomarker of diseases, such as osteoblastic bone cancer, hepatitis, and myeloma, and hence its determination is essential and important. MnO2/Mn2+ conversion-based magnetic relaxation sensing was developed to directly determine ALP in blood. In the presence of ALP, 2-phospho-L-ascorbic acid trisodium salt was catalyzed to produce ascorbic acid (AA), which reduced MnO2 to Mn2+, causing transverse relaxation time (T2) decay. A linear relationship of ALP from 5 mU·L−1 to 500 mU·L−1 with T2 signal and a low limit of detection (LOD) of 3.32 mU·L−1 were obtained using the optimized conditions of 200 µM of ascorbic acid-phosphate (AAP), 10 µg·mL−1 of MnO2, 37 °C, pH 7.4, and a 30 min reaction time. When directly measuring ALP in serum with the proposed method, the recoveries were from 99.2% to 101.3%, in accordance with values obtained by a commercial assay. In conclusion, a sensitive one-step method for ALP in complex samples was established which has potential for clinical applications.

NMR Characterization of unfrozen brine vein distribution and structure in model packed beds

When a brine mixed with particles is frozen, some liquid water persists due to the freezing point depression caused by the solute impurity, surface energy, and disjoining pressure (wetting forces). This unfrozen water forms a complex “liquid vein network” (LVN). However, details of the freezing process are still not fully understood, including the permeability/tortuosity of the LVN, and the unfrozen water content at a given temperature. Here, we have applied nuclear magnetic resonance (NMR) relaxation, self-diffusion measurements and magnetic resonance imaging (MRI) to investigate the distribution and structure of LVNs. Magnesium chloride (MgCl2) salt concentrations of 15, 30, and 60 mM were investigated with and without poly-methyl methacrylate (PMMA) particles of diameter 0.4, 9.9, and 102.2 μm, allowing us to quantify unfrozen water content and the structure of the LVN as a function of temperature, MgCl2 concentration, and PMMA particle size. The results of magnetic resonance imaging (MRI) and self-diffusion confirm that the inhibition of ice recrystallization is a function of particle size. To gain information on LVN structure, we compared NMR results to Monte Carlo simulations of freezing in brine-particle systems. Comparisons between laboratory and simulation data suggest that, for our experimental range of temperature (−17.4 °C to −0.9 °C ± 0.5 °C), solutes make the dominant contribution to the unfrozen liquid fraction for particle sizes larger than a few microns, whereas in the finest grained porous media we tested, the unfrozen liquid fraction is controlled primarily by the films that wet particle-ice interfaces.

Water and lipid migration in salted duck eggs during storage with different packaging conditions as studied using LF-NMR and MRI techniques.

Herein, the water and lipid migration of salted duck eggs during storage were systematically explored in three different packaging conditions of long-term salting, no packaging, and vacuum packaging. Bound water, multilayer bound water, lipid, and bulk water were observed in the whole duck egg by low-field nuclear magnetic resonance (LF-NMR) relaxation. Five weeks of salting process led to the redistribution of water and lipid due to the watery state of egg white and the gelation of egg yolk due to the permeation of salt, and boiling mainly caused an obvious decrease in the mobility of bulk water due to the gelation of egg white. Among these three conditions, long-term salting with 6 months storage caused the most serious redistribution of water and lipid as well as the rupture of the vitelline membrane, but could prevent the oxidation of egg yolk. Vacuum packaging had the least influence on the water and lipid distribution, mass change, and water content but led to lipid oxidation with high degree in egg yolk. However, the most obvious mass loss was observed in the salted duck eggs during the storage without packaging. In addition, principal component analysis of Carr-Purcell-Meiboom-Gill data suggested that LF-NMR could distinguish the salted duck eggs with different storage times during the early stage of the storage. Practical Application Water and lipid migration of salted duck eggs during storage with three packaging conditions were explored by using low-field nuclear magnetic resonance and magnetic resonance imaging. Understanding the impacts of packaging conditions on water and lipid migration of salted duck eggs during storage could provide a new method for the quality identification.

Novel low-field NMR method for characterization content and SARA composition of bitumen in rocks

In the oil industry, there is a need for fast and non-invasive methods for determining the bitumen content and group composition in rock samples. Determination of bitumen saturation of reservoir or source rocks has some difficulties due to existing methods limitations. For this purpose, the novel method is based on a combination of free induction decay (FID) and modified Carr-Purcell-Meilboom-Gill (CPMG) measurements using a low-frequency nuclear magnetic resonance (NMR) relaxation technique was developed. It allows obtaining the content and group composition (SARA fractions) of bitumen directly in the porous media without extraction. FID data fitting based on a combination of Voigt and exponential functions for liquid phase, as well as Abragam and exponential functions for solid phase components respectively was proposed. The developed method was tested on 20 rock samples collected from the productive formation (horizon M) located at the depth of 601–708 m of the wellbore 3001 of the Boca de Jaruco oilfield (Republic of Cuba). The bitumen content in the samples was obtained and compared with data determined by thermogravimetric analysis (TGA) and Rock-Eval pyrolysis. A good agreement of NMR results with TGA and pyrolysis was shown (R2 = 0.99 and 0.97 respectively). The values of liquid HC components (saturates, aromatics and resins) and solid HC components (asphaltenes) were compared with TGA data (R2 = 0.97 and 0.98 respectively). Finally, the proposed NMR method was applied to determine the SARA composition of the bitumen in the samples. To assess the accuracy of determining the SARA composition by the NMR method, SARA analysis (ASTM D4124-09) of extracts from the samples 632, 638, 658, 676, 689, 708 was carried out. NMR and conventional SARA analysis showed close results. To assess the completeness of the bitumen extraction from the mineral matrix, microCT and FIB-SEM were performed before and after extraction. It was found that after extraction the part of the bitumen remains in the pores, which distorts the results of SARA analysis. The proposed NMR method can be used to calculate the bitumen saturation and SARA composition for characterization of bitumen, selecting and modeling the effectiveness of applying the optimal EOR without destroying the samples. Also, the method is promising for the operational control of technological processes of oil production.

The Effect of Gadolinium-Based Contrast Agents on Longitudinal Changes of Magnetic Resonance Imaging Signal Intensities and Relaxation Times in the Aging Rat Brain.

ObjectivesThe aim of the study was to investigate the possible influence of changes in the brain caused by age on relaxometric and relaxation time–weighted magnetic resonance imaging (MRI) parameters in the deep cerebellar nuclei (DCN) and the globus pallidus (GP) of Gd-exposed and control rats over the course of 1 year.Materials and MethodsTwenty-five Wistar-Han rats were equally subdivided into 5 groups and initially received 8 injections on 4 consecutive days per week of either 3.6 mL/kg body weight saline (group I–III) or 1.8 mmol Gd/kg body weight gadobutrol (group IV) or gadodiamide (group V). T1- and T2-weighted scans, as well as relaxation maps, were acquired at 1 week (all groups); 5, 12, 20, and 26 weeks (saline II, gadobutrol, gadodiamide); and at 35, 44, and 52 weeks (saline III, gadobutrol, gadodiamide) after the last administration. Saline I was euthanized after 1 week, saline II after 26 weeks, and the remaining groups after 52 weeks. Signal intensities (SIs) were evaluated for the DCN/pons (P) and the GP/piriform cortex (PC) ratios, and relaxation times for the DCN and the GP. Brain tissue was extracted, and the gadolinium, iron, and manganese contents were quantified with inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation–ICP-MS imaging.ResultsT1-weighted SI ratios did not show any significant trend with age in any region. The between-group analysis at 52 weeks resulted in a significant difference for the DCN/P and GP/PC region ratio between gadodiamide and its comparators. T1 relaxation times dropped with increasing age in the GP with a 10% to 20% difference between first and last measurement for all groups, and in the DCN <10% with a significant decrease for the gadodiamide group only (DCN: P = 0.0158). Group-related differences were observed at the last measurement time point for T1 values between gadodiamide and saline III in the DCN (P = 0.0153) and gadodiamide and gadobutrol in the GP (P = 0.0287). Analysis of the SI ratios of the T2-weighted images revealed a significant increase for the DCN/P and a decrease for the GP/PC with increasing age for all groups and no differences at 52 weeks after the last injection between groups. T2 values of the GP showed a significant linear decrease over time for all groups (saline I–III: P = 0.0101; gadobutrol: P = 0.0001; gadodiamide: P = 0.0142) in the aging rat brain. Quantitative imaging of manganese and iron by laser ablation–ICP-MS showed a linear increase for the saline groups in the GP for both metals (Fe: P < 0.0001; Mn: P = 0.0306) and in the DCN for manganese only (P = 0.0187), but no differences between groups at 52 weeks.ConclusionsExtensive MRI evaluation did not reveal an indication of SI or relaxation time changes associated with multiple exposure to the macrocyclic-chelated GBCA gadobutrol in the DCN and the GP. With increasing age, a T1 and T2 shortening in the GP and an increase in T2-weighted SI ratio in the DCN/P, as well as a decrease in the GP/PC, were observed for all groups. Such age-related changes can potentially bias MRI results as an indicator for gadolinium presence in the brain.

Sea sand seawater geopolymer concrete

Geopolymers are cementitious materials known for their environmental benefits and comparable characteristics to conventional Portland cement. This paper investigates the mechanical properties of eight geopolymer mixes with varying mix designs. The objectives of this study are to investigate the effect of how unwashed sea sand and seawater influence the mechanical properties of the geopolymer mixes, as well as the impact of different binders, activators and curing conditions. Fly ash, slag and metakaolin are investigated as binders, while pentahydrate sodium metasilicate (Na2SiO3·5H2O), anhydrous sodium metasilicate (Na2SiO3) and sodium hydroxide solution are employed as alkaline activators. The geopolymer specimens were cured at room temperature for 24h, contrasting curing conditions between an atmospheric environment and submerged in seawater. The materials properties were characterized via compressive strength, density, cone penetration, sorptivity and nuclear magnetic resonance relaxation measurements. Compressive strength was measured after 3-, 28- and 56-days. The ultimate compressive strength of 54.28 MPa was obtained by incorporating fly ash, slag and normal silica sand, and sodium hydroxide solution submerged in seawater. Our results showed that the fly ash based geopolymer mixes activated by sodium hydroxide may be optimized to achieve high compressive strength. The use of unwashed sea sand affected geopolymer workability but had little influence on compressive strength.

1D magnetic resonance imaging and low-field nuclear magnetic resonance relaxometry of water-based silica nanofluids

The purpose of this research is to investigate 1-D Magnetic Resonance Imaging (MRI) and low-field Nuclear Magnetic Resonance (NMR) relaxation characteristics of silica nanofluids. The results show that presence of silica nanoparticles increases the MRI signal intensity and influences the NMR relaxation by shifting the relaxation peaks toward faster times compared to deionized water (DIW). Additionally, inversion recovery sequences show that nanoparticles reduce longitudinal relaxation time. For the tested nanofluid of EOR-12, signal intensity, longitudinal relaxation rate and transverse relaxation rate show a strong linear dependence on nanoparticle concentration with the highest enhancement of 1.75-fold, 2.57-fold and 3.20-fold, respectively compared to DIW. Additionally, investigation of the effect of nanoparticle size shows that below an optimal size, the MRI signal intensity and the NMR relaxation rates show a positive correlation with nanoparticle size but above the optimal size, the behavior reverses. For the nanoparticle with the optimal diameter, signal intensity, longitudinal relaxation rate and transverse relaxation rate enhancement was 2.21-fold, 4.44-fold and 4.45-fold, respectively compared to DIW. Application of the observed improvement in signal intensity to obtain the profile of the aqueous phase volume fraction in a Pickering emulsion shows a maximum error of 8% which indicates that the proposed technique can be applied for emulsion characterization with good accuracy.