Transverse Relaxation Measurements Research Articles

Small molecules dominate organic phosphorus in NaOH-EDTA extracts of soils as determined by 31P NMR

Understanding the composition of organic phosphorus (P) in soils is relevant to various disciplines, from agricultural sciences to ecology. Despite past efforts, the precise nature of soil organic P remains an enigma, especially that of the orthophosphate monoesters, which dominate 31P NMR spectra of NaOH-EDTA extracts of soils worldwide. The monoester region often exhibits an unidentified, broad background believed to represent high molecular weight (MW) P. We investigated this monoester background using 1D 31P NMR and 2D 1H31P NMR, as well as 31P transverse relaxation (T2) measurements to calculate its intrinsic linewidth and relate it to MW. Analyzing seven soils from different ecosystems, we observed linewidths of 0.5 to 3 Hz for resolved monoester signals and the background, indicating that it consists of many, possibly >100, sharp signals associated with small (<1.5 kDa) organic P molecules. This result was further supported by 2D 1H31P NMR spectra revealing signals not resolved in the 1D spectra. Our findings align with 31P NMR studies detecting background signals in soil-free samples and modern evidence that alkali-soluble soil organic matter consists of self-assemblies of small organic compounds mimicking large molecules.

Transverse relaxation measurements for moving samples in the presence of strong magnetic field gradients

Nuclear Magnetic Resonance (NMR) is one of the primary techniques used in the oil industry for logging operations and in the laboratory environment to study rock formations due to its reliability in offering a reliable estimation of oil well productivity. Two types of well-logging operations exist, Wireline Logging and Logging While Drilling (LWD). Wireline Logging involves NMR measurements taken under static conditions. In contrast, LWD involves measurements taken during the drilling process while the tool is in motion, translating, rotating, and vibrating relative to the formation. To understand the behavior of NMR signals measured under LWD conditions on a laboratory scale, we developed a setup that includes a single-sided magnet, rf probes, and a mechanical system that emulates a relative sinusoidal motion between the sample and the applied magnetic field. Four representative rock samples were selected according to their relaxation times, which were short, intermediate, and long compared to the oscillation period of the LWD simulator: three sandstone, Fontainebleau, Berea Sandstone, and Portland Red, and one carbonate, Indiana Limestone. The results show that even with the modifications observed in the relaxation times distribution, which could lead to misinterpreting the geological formation parameters, the total porosity remains unaffected and independent of the sample motion during the NMR measurements, even under severe conditions and using the standard procedures of the data processing.

Sodium Dynamics in the Cellular Environment.

Sodium ions are essential for the functions of biological cells, and they are maintained at the balance between intra- and extracellular environments. The quantitative assessment of intra- and extracellular sodium as well as its dynamics can provide crucial physiological information on a living system. 23Na nuclear magnetic resonance (NMR) is a powerful and noninvasive technique to probe the local environment and dynamics of sodium ions. However, due to the complex relaxation behavior of the quadrupolar nucleus in the intermediate-motion regime and because of the heterogeneous compartments and diverse molecular interactions in the cellular environment, the understanding of the 23Na NMR signal in biological systems is still at the early stage. In this work, we characterize the relaxation and diffusion of sodium ions in the solutions of proteins and polysaccharides, as well as in the in vitro samples of living cells. The multi-exponential behavior of 23Na transverse relaxation has been analyzed according to the relaxation theory to derive the crucial information related to the ionic dynamics and molecular binding in the solutions. The bi-compartment model of transverse relaxation and diffusion measurements can corroborate each other to quantify the fractions of intra- and extracellular sodium. We show that 23Na relaxation and diffusion can be used to monitor the viability of human cells, which offers versatile NMR metrics for in vivo studies.

Orientation dependent proton transverse relaxation in human brain white matter: The magic angle effect on a cylindrical helix

PurposeTo overcome some limitations of previous proton orientation-dependent transverse relaxation formalisms in the human brain white matter (WM) by a generalized magic angle effect function. MethodsA cylindrical helix model was developed embracing anisotropic rotational and translational diffusion of restricted molecules in WM, with the former characterized by an axially symmetric system. Transverse relaxation rates R2 and R2∗ were divided into isotropic R2i and anisotropic parts, R2a ∗ f(α,Φ − ε0), with α denoting an open angle and ε0 an orientation (Φ) offset from DTI-derived primary diffusivity direction. The proposed framework (Fit A) was compared to prior models without ε0 on previously published water and methylene proton transverse relaxation rates from developing, healthy, and pathological WM at 3 T. Goodness of fit was represented by root-mean-square error (RMSE). F-test and linear correlation were used with statistical significance set to P ≤ 0.05. ResultsFit A significantly (P < 0.01) outperformed prior models as demonstrated by reduced RMSEs, e.g., 0.349 vs. 0.724 in myelin water. Fitted ε0 was in good agreement with calculated ε0 from directional diffusivities. Compared with those from healthy adult, the fitted R2i, R2a, and α from neonates were substantially reduced but ε0 increased, consistent with developing myelination. Significant positive (R2i) and negative (α and R2a) correlations were found with aging (demyelination) in elderly. ConclusionThe developed framework can better characterize orientation dependences from a wide range of proton transverse relaxation measurements in the human brain WM, thus shedding new light on myelin microstructural alterations at the molecular level.

Monitoring the Effect of Calcium Nitrate on the Induction Period of Cement Hydration via Low-Field NMR Relaxometry.

The hydration process of Portland cement is still not completely understood. For instance, it is not clear what produces the induction period, which follows the initial period of fast reaction, and is characterized by a reduced reactivity. To contribute to such understanding, we compare here the hydration process of two cement samples, the simple cement paste and the cement paste containing calcium nitrate as an accelerator. The hydration of these samples is monitored during the induction period using two different low-field nuclear magnetic resonance (NMR) relaxometry techniques. The transverse relaxation measurements of the 1H nuclei at 20 MHz resonance frequency show that the capillary pore water is not consumed during the induction period and that this stage is shortened in the presence of calcium nitrate. The longitudinal relaxation measurements, performed at variable Larmor frequency of the 1H nuclei, reveal a continuous increase in the surface-to-volume ratio of the capillary pores, even during the induction period, and this increase is faster in the presence of calcium nitrate. The desorption time of water molecules from the surface was also evaluated, and it increases in the presence of calcium nitrate.

A Bayesian optimization approach to the extraction of intrinsic physical parameters from T2 relaxation responses

NMR transverse relaxation responses in porous media provide a sensitive probe of the micro-structure yet are influenced by a set of factors which are not easily detangled. Low-field T2 transverse relaxation measurements can be carried out quickly and are frequently used to derive pore size distributions and determine derivate parameters like movable fluid volumes or permeability. Here we present an inverse solution workflow extracting related intrinsic physical parameters of the system by tightly fitting experiment and numerical simulation(s). We propose a Bayesian optimization approach that determines five T2 related properties associated with two values of temperature simultaneously. This concurrent optimization (CO-OPT) utilizes Gaussian process regression to determine the intrinsic physical parameters leading to a match to experiment with a minimal number of function evaluations. A multi-modal search strategy is employed to identify non-unique solution sets of the problem. The workflow is demonstrated on Bentheimer sandstone, identifying five intrinsic physical parameters simultaneously, namely the surface relaxivity of quartz and the effective diffusion and relaxation times of the clay regions at 20∘ C and 60∘ C, providing the temperature-dependent quartz surface relaxivity and effective clay parameters. Given the generality of the method, it can easily be adapted to transverse relaxation experiments, or dynamic conditions where e.g., a change in wettability is monitored by intrinsic NMR parameters.

Simultaneous Assessment of Wettability and Water Saturation Through Integration of 2D NMR and Electrical Resistivity Measurements

Summary Nuclear magnetic resonance (NMR) transverse relaxation (T2) measurements are sensitive to fluid saturations and wettability of the rocks. However, quantifying wettability index solely from NMR T2 models relies on accurate estimates of water saturation. It has been shown that integrating resistivity measurements and NMR T2 distributions enables simultaneous assessment of wettability and water saturation. Nevertheless, there still exist significant uncertainties in this approach in the presence of multiple types of fluids with overlapping transverse relaxation times or multimodal pore-size distribution. Thus, the objectives of this paper are (a) to introduce a new multiphysics workflow integrating 2D NMR with resistivity measurements to simultaneously quantify wettability index and water/hydrocarbon saturation and (b) to verify the reliability of the introduced workflow with core measurements in different rock types. The workflow starts by using 2D diffusivity-transverse relaxation (D-T2) or longitudinal-transverse relaxation (T1-T2) measurements to estimate fluid saturations. We use a nonlinear inversion algorithm to fit a multimodal Gaussian distribution to the 2D NMR measurements. We then calculate water and hydrocarbon saturations using the fluid volumes estimated from the multimodal Gaussian distribution. This estimate of water/hydrocarbon saturation is an input to our new physics-based resistivity model that explicitly incorporates the influence of wettability. The inputs to the resistivity model include water saturation, resistivity index, and pore-geometry-related parameters. In the core-scale verification step, we compare the results of wettability and fluid saturations obtained from the new workflow with gravimetrically assessed water saturation and Amott index measurements on core sample. We successfully verified the reliability of the new workflow with experimental measurements. Estimated water saturation using the introduced workflow resulted in an average relative error of less than 7% compared to the gravimetrically assessed water saturations. Wettability indices obtained from the workflow were in agreement with those estimated using Amott indices. The average absolute error between the estimated wettability indices and the Amott indices was 0.27. In conclusion, results demonstrated that integration of 2D NMR and electrical resistivity measurements enables reliable and simultaneous assessment of wettability and water saturation in different rock types. The method introduced in this paper is promising for reliable and real-time wettability assessment, both in the laboratory and in-situ condition. It provides a physics-based and robust method to accurately and simultaneously estimate water/hydrocarbon saturation and wettability in hydrocarbon-bearing rocks.

Non-Invasive Method to Predict the Composition of Requeijão Cremoso Directly in Commercial Packages Using Time Domain NMR Relaxometry and Chemometrics

Low Field Time-Domain Nuclear Magnetic Resonance (TD-NMR) relaxometry was used to determine moisture, fat, and defatted dry matter contents in “requeijão cremoso” (RC) processed cheese directly in commercial packaged (plastic cups or tubes with approximately 200 g). Forty-five samples of commercial RC types (traditional, light, lactose-free, vegan, and fiber) were analyzed using longitudinal (T1) and transverse (T2) relaxation measurements in a wide bore Halbach magnet (0.23 T) with a 100 mm probe. The T1 and T2 analyses were performed using CWFP-T1 (Continuous Wave Free Precession) and CPMG (Carr-Purcell-Meiboom-Gill) single shot pulses. The scores of the principal component analysis (PCA) of CWFP-T1 and CPMG signals did not show clustering related to the RC types. Optimization by variable selection was carried out with ordered predictors selection (OPS), providing simpler and predictive partial least squares (PLS) calibration models. The best results were obtained with CWFP-T1 data, with root-mean-square errors of prediction (RMSEP) of 1.38, 4.71, 3.28, and 3.00% for defatted dry mass, fat in the dry and wet matter, and moisture, respectively. Therefore, CWFP-T1 data modeled with chemometrics can be a fast method to monitor the quality of RC directly in commercial packages.

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.

In vivo irreversible and reversible transverse relaxation rates in human cerebral cortex via line scans at 7 T with 250 micron resolution perpendicular to the cortical surface

Understanding how and why MR signals and their associated relaxation rates vary with cortical depth could ultimately enable the noninvasive investigation of the laminar architecture of cerebral cortex in the living human brain. However, cortical gray matter is typically only a few millimeters thick, making it challenging to sample many cortical depths with the voxel sizes commonly used in MRI studies. Line-scan techniques provide a way to overcome this challenge and here we implemented a novel line-scan GESSE pulse sequence that allowed us to measure irreversible and reversible transverse relaxation rates—R2 and R2´, respectively—with extremely high resolution (250 μm) in the radial direction, perpendicular to the cortical surface. Eight healthy human subjects were scanned at 7 T using this sequence, with primary visual cortex (V1) targeted in three subjects and primary motor (M1) and somatosensory cortex (S1) targeted in the other five. In all three cortical areas, a peak in R2 values near the central depths was seen consistently across subjects—an observation that has not been made before, to our knowledge. On the other hand, no consistent pattern was apparent for R2´ values as a function of cortical depth. The intracortical R2 peak reported here is unlikely to be explained by myelin content or by deoxyhemoglobin in the microvasculature; however, this peak is in accord with the laminar distribution of non-heme iron in these cortical areas, known from prior histology studies. Obtaining information about tissue microstructure via measurements of transverse relaxation (and other quantitative MR contrast mechanisms) at the extremely high radial resolutions achievable through the use of line-scan techniques could therefore bring us closer to being able to perform “in vivo histology” of the cerebral cortex.

Spectroscopic signatures of bilayer ordering in native biological membranes

Membrane proteins and polycyclic lipids like cholesterol and hopanoids coordinate phospholipid bilayer ordering. This phenomenon manifests as partitioning of the liquid crystalline phase into liquid-ordered (Lo) and liquid-disordered (Ld) regions. In Eukaryotes, microdomains are rich in cholesterol and sphingolipids and serve as signal transduction scaffolds. In Prokaryotes, Lo microdomains increase pathogenicity and antimicrobial resistance. Previously, we identified spectroscopically distinct chemical shift signatures for all-trans (AT) and trans-gauche (TG) acyl chain conformations, cyclopropyl ring lipids (CPR), and hopanoids in prokaryotic lipid extracts and used Polarization Transfer (PT) SSNMR to investigate bilayer ordering. To investigate how these findings relate to native bilayer organization, we interrogate whole cell and whole membrane extract samples of Burkholderia thailendensis to investigate bilayer ordering in situ. In 13C-13C 2D SSNMR spectra, we assigned chemical shifts for lipid species in both samples, showing conservation of lipids of interest in our native membrane sample. A one-dimensional temperature series of PT SSNMR and transverse relaxation measurements of AT versus TG acyl conformations in the membrane sample confirm bilayer ordering and a broadened phase transition centered at a lower-than-expected temperature. Bulk protein backbone Cα dynamics and correlations consistent with lipid-protein contacts within are further indicative of microdomain formation and lipid ordering. In aggregate, these findings provide evidence for microdomain formation in vivo and provide insight into phase separation and transition mechanics in biological membranes.

White Matter Metabolite Relaxation and Diffusion Abnormalities in First-Episode Psychosis: A Longitudinal Study.

Microstructural abnormalities in the white matter (WM) are implicated in the pathophysiology of psychosis. In vivo magnetic resonance spectroscopy (MRS) can probe the brain's intracellular microenvironment through the measurement of transverse relaxation and diffusion of neurometabolites and possibly provide cell-specific information. In our previous studies, we observed differential metabolite signal abnormalities in first episode and chronic stages of psychosis. In the present work, longitudinal data were presented for the first time on white matter cell-type specific abnormalities using a combination of diffusion tensor spectroscopy (DTS), T2 MRS, and diffusion tensor imaging (DTI) from a group of 25 first episode psychosis patients and nine matched controls scanned at baseline and one and two years of follow-up. We observed significantly reduced choline ADC in the year 1 of follow-up (0.194 µm2/ms) compared to baseline (0.229 µm2/ms), followed by a significant increase in NAA ADC in the year 2 follow-up (0.258 µm2/ms) from baseline (0.222 µm2/ms) and year 1 follow-up (0.217 µm2/ms). In contrast, NAA T2 relaxation, reflecting a related but different aspect of microenvironment from diffusion, was reduced at year 1 follow-up (257 ms) compared to baseline (278 ms). These abnormalities were observed in the absence of any abnormalities in water relaxation and diffusion at any timepoint. These findings indicate that abnormalities are seen in in glial-enriched (choline) signals in early stages of psychosis, followed by the subsequent emergence of neuronal-enriched (NAA) diffusion abnormalities, all in the absence of nonspecific water signal abnormalities.

Sense current dependent coercivity and magnetization relaxation in Gd-Fe-Co Hall bar

The understanding of the characteristics of a magnetic layer in a different environment is crucial for any spintronics application. Before practical applications, thorough scrutiny of such devices is compulsory. Here we study such a potential Hall device of MgO-capped Hf/GdFeCo bilayer (FeCo-rich) for magnetization relaxation around nucleation fields at different voltage probe line widths and dc sensing currents. The device is characterized by anomalous Hall measurements in transverse and longitudinal Hall geometries for two different probe widths A (5 µm) and B (1 µm). The coercivities of the Hall loops (ρxy-H and Rxx-H) drop with increasing the sense current for both the probes. For probe B, the sharp and large drop in coercivity (ρxy-H loops) at comparatively lower sensing currents is observed, which is attributed to the negligible current shunting and presence of pinning site at B caused by the patterning process. The average domain wall velocities at various sensing currents for probe B are found to be smaller than probe A, from the transverse and longitudinal Hall geometry magnetization relaxation measurements, which agrees with pinning sites and Joule heating effect at probe B. The notch position in the pattern and the longitudinal Hall resistance curve peak shape suggest the domain wall propagation direction from probe B to probe A in the current channel. This study highlights the domain wall propagation at different nucleation fields, sensing currents, and the Hall probe aspect ratios.

Physicochemical and Antioxidant Properties Based on Fish Sarcoplasmic Protein/Chitosan Composite Films Containing Ginger Essential Oil Nanoemulsion

The appeal for environment friendly films with bioactive components to replace synthetic plastic packaging has been increasing in recent years. In this study, ginger essential oil (GEO) nanoemulsion at different levels (0.5%, 1.0%, 1.5%, 2.0%, and 3.0%) were incorporated into fish sarcoplasmic protein (FSP) and chitosan (CH) blend films to evaluate the physical, mechanical, antioxidant, and thermal properties. The water distribution state of films was also determined by NMR transverse relaxation (T2) measurements. The tensile strength (TS) of samples was significantly reduced with increasing GEO nanoemulsion contents (p < 0.05), while the value of elongation at break (EAB) was the highest when the film with 1.0% GEO nanoemulsion. The addition of GEO nanoemulsion enhanced the water barrier properties and affected the water distributions of films, but had negative effects on thermal degradation of films. Scanning electric microscope (SEM) demonstrated the different microstructure at varied levels of GEO nanoemulsion and Fourier transform infrared (FTIR) spectroscopy gave the detailed information about the interactions at molecular level. These results revealed that FSP blended with CH was excellent film-forming material and mixing defined amount of GEO nanoemulsion into film-forming solution enhanced the physical and antioxidant properties of films.

An organogel library for solution NMR analysis of nanoparticle suspensions in non-aqueous samples

Surface contrast solution NMR methods (scNMR) are emerging as powerful tools to investigate the adsorption of small molecule ligands to the surface of nanoparticles (NP), returning fundamental insight into the kinetics and thermodynamics of sorption, as well as structural information on the adsorbed species. A prerequisite for the acquisition of high quality solution NMR data is the preparation of homogeneous and stable samples that return consistent NMR spectra and allow extensive signal averaging. Unfortunately, this condition does not apply to NMR samples containing NPs that often show a tendency to sediment and accumulate at the bottom of the NMR tube over the course of the experiment. We have recently shown that preparing NMR samples in an agarose gel matrix inhibits sedimentation and allows the characterization of small molecule-NP interactions by scNMR. Unfortunately, as the agarose gel only forms in aqueous solution, this sample preparation method cannot be used to stabilize NP suspensions in a non-aqueous environment. Here, we introduce a library of 48 organogels, based on low molecular-mass organic gelators (LMOGs), to prepare NMR samples of small molecule/NP systems in a wide range of organic solvents. In addition, we present a simple method that takes advantage of 1H transverse relaxation (1H-R2) measurements to screen the library and identify the best gelator to characterize the small molecule-NP interaction of interest in the solvent of choice. We expect the results of this study will enable the preparation of homogeneous and stable samples of NPs in non-aqueous environments, therefore dramatically increasing the applicability of scNMR to the characterization of heterogeneous interactions and to the investigation of the role played by solvent molecules in regulating the kinetics and thermodynamics of sorption.

Impact of chemical exchange on transverse relaxation at low and moderate magnetic field strengths for sugar solutions representative of fruit tissues analyzed by simulation and MRI experiments

Proton exchange effects on transverse relaxation rate were studied at low and moderate magnetic fields. Analysis was conducted on low-concentrate simple sugar (fructose and glucose) solutions modeling the vacuolar liquid in fruits. Simulated data obtained from Carver and Richards equations were used to analyze the effects of temperature and pH on parameters involved in the chemical exchange mechanisms. The results have highlighted that measurement conditions and tissue characteristics (echo time, magnetic field strength, temperature, pH, etc.) significantly impact the transverse relaxation rate via chemical exchange, even for low and mid magnetic fields and the narrow echo time ranges of TD-NMR and MRI measurements. This explains some of the divergent relaxation data from plant tissue NMR measurements reported in the literature and emphasizes the importance of taking experimental conditions and tissue characteristics into account when interpreting results. It also clearly demonstrates that the appropriate choice of experimental conditions can emphasize the effects of sugar concentration or pH variations on transverse relaxation in vacuolar liquids, making it possible to monitor these parameters accurately via transverse relaxation measurements. The impact of concentration, solute type, pH and temperature on transverse relaxation of sugar solutions were demonstrated experimentally at 1.5 T with an MRI scanner. These data were interpreted using the Carver–Richards model which was effective in estimating parameters involved in chemical exchange mechanism in the imaging experiment.

Microstructure-driven self-assembly and rheological properties of multi-responsive soft microgel suspensions

HypothesesThe deformation and swelling ability of microgels is influenced by the crosslinking distribution. Varying microgels microstructure is expected to obtain suspensions with different flow behavior and thereby, different rheological properties. ExperimentsDifferent multi-responsive microgels were synthesized using two different crosslinkers and varying their amounts: N,N-methylene bis-acrylamide (MBA) and oligo(ethylene glycol) diacrylate (OEGDA). The rheological results were obtained by zero-shear viscosity and long-time creep measurements on concentrated microgel suspensions Microgel microstructure was analyzed by 1H nuclear magnetic resonance transverse relaxation measurements. FindingsAt a constant crosslinking rate, we show that the viscosity of OEGDA-crosslinked microgels diverges at a higher concentration than MBA ones, suggesting a looser shell and less restricted dangling chains at the periphery for the later. By scaling with the effective volume fraction, the viscosity curves of the different microgel suspensions reduce into a single curve and closely follow hard sphere models up to ϕeff < 0.45. The results from creep tests revealed a much higher yield stress for MBA-crosslinked microgels, strengthening the hypothesis of a looser shell for the later. Finally, transverse relaxation (T2) NMR measurements demonstrated that, although all microgels exhibit a core–shell microstructure, MBA samples present a less crosslinked shell corroborating with the rheological results.

Revealing the Influence of Microparticles on Geopolymers' Synthesis and Porosity.

Geopolymers are zeolites like structures based on hydrated aluminosilicates units of SiO4 and AlO4. These units, known as poly(sialate), poly(sialate)-siloxo or poly(sialate)-disiloxo are chemically balanced by the group I cations of K+, Li+, or Na+. Simultaneously, the chemical reaction of formation, known as geopolymerization, governs the orientation of the unit, generating mesoporous structures. Multiple methods can be used for pore structure and porosity characterization. Among them, nuclear magnetic resonance (NMR) relaxometry allows the detection of the porous structure in a completely nonperturbative manner. NMR relaxometry may be used to monitor the relaxation of protons belonging to the liquid molecules confined inside the porous structure and, thus, to get access to the pore size distribution. This monitoring can take place even during the polymerization process. The present study implements transverse relaxation measurements to monitor the influence introduced by the curing time on the residual liquid phase of geopolymers prepared with two different types of reinforcing particles. According to our results, the obtained geopolymers contain three types of pores formed by the arrangement of the OH− and Si groups (Si-OH), Si-O-Si groups, Si-O-Al groups, and Si-O rings. After 48 days, the samples cured for 8 h show a high percentage of all three types of pores, however, by increasing the curing time and the percentage of reinforcing particle, the percent of pores decrease, especially, the gel pores.

Are aqueous solutions of choline-based ionic liquid biocompatible cross-linkers for collagen?

Identification of biocompatible cross-linkers is extremely important in the field of biomaterials, as it aids in improving stability to protein but also elicits less immune response. Towards this, aqueous solution of choline-based ILs (CILs) has been keyed out as biocompatible cross-linkers with an aim to understand their impact and effect on stabilization of collagen. The changes in the hydration dynamics of collagen treated with aqueous solution of CILs has been probed using transverse NMR relaxation and impedance measurements. Upon treatment of aqueous solution of CILs with collagen, there is a reorientation in the surrounding water milieu suggesting compactness in the structure of collagen, which is indicative of crosslinking. Further, the conformational and thermal stability of collagen have been substantiated. It is ascertained that the helicity of collagen remains intact as witnessed from the Rpn values measured through circular dichroic measurements and shifts in frequencies of amide bands as measured through FT-IR measurements. A significant increase in the melting and denaturation temperature suggesting stability of collagen has been observed through DSC measurements. Aqueous solution of CILs treated collagen scaffolds have been further appraised for crosslinking efficiency, enzymatic stability, hemolytic and platelet attachment assays. The efficacy of aqueous solution of CILs treated scaffolds has been evaluated for biocompatibility with NIH-3T3 fibroblasts cells and further confirmed by the phase-contrast microscopic images of these cells. Interaction between the collagen and aqueous solution of choline-based ILs is typically anchored by non-covalent interactions like electrostatic, hydrogen, and van der Waals interactions. Therefore, the current study implies that the aqueous solution of CILs can be explored as biocompatible cross-linkers for collagen and thus can be employed for biomedical applications.

Capillary Trapping of CO2 in Sandstone Using Low Field NMR Relaxometry

AbstractInjecting carbon dioxide into geological formations for long‐term storage is considered integral to reducing greenhouse gas emissions. Residual trapping of CO2 is a primary storage mechanism, whereby CO2 ganglia are trapped in the pore space by capillary forces. Experimental knowledge of residual trapping processes in rocks is critical to the development of safe storage strategies. Here we present a quantitative low field 1H nuclear magnetic resonance (NMR) core flooding study of CO2 residual trapping in three different sandstones. It was found that transverse relaxation (T2) measurements were sensitive to the dissolution of paramagnetic ions from rock matrix minerals after exposure to carbonic acid; this response was observed on time scales relevant to core flooding experiments (i.e., minutes to hours). Subsequently, a brine aging protocol was designed and implemented to minimize this chemical effect, and hence, by applying the well‐known T2‐pore size relationship, changes in T2 time distributions during core flooding could be related to displacement of brine from pores of different sizes. Comparison of T2 distributions for partially CO2/brine‐saturated cores to previously published data for N2/H2O systems shows an increased displacement of brine from small pores by CO2. Furthermore, results from cyclical brine/CO2 injections showed an increase in the total volume of residually trapped CO2 and an increase in trapping efficiency; compared to the results observed for N2/H2O, however, the improvement in trapping efficiency with cyclic injection was less pronounced. Potential causes for the observed differences are discussed in the context of effective N2 and CO2 wetting.