Low-field NMR Relaxometry Research Articles

NMR T1 dispersion of crude oils from 10 kHz to 20 MHz

In this article T1 dispersion measurements on a set of crude oils that span a viscosity range of 0.7 cP up to 2·104 cP are reported. Larmor frequencies were varied from 10 kHz up to 20 MHz. The relaxation dispersion measurements are interpreted in terms of the threshold viscosity model, which allows model applicability tests presented in literature to be extended to Larmor frequencies below 1 MHz. It is shown that the measurements can be equally well described by assuming a proton-proton interaction process as by assuming proton-electronic spin interactions. A power-law frequency dependence of the threshold viscosity parameter is observed for both types of spin interactions. Modifications to the description of rotational diffusion in the threshold viscosity model are suggested that may account for the observed frequency dependence in the threshold viscosity parameter. Without modifications, the threshold viscosity model is shown to have a limited application range of η ≥ 40 cP and ω0/2π ≥ 700 kHz, in which model parameters have a physically justifiable order of magnitude for the set of crude oils studied. Outside this range, the threshold viscosity model can still be applied as a parametrization of T1 dispersion effects for the complete set of experiments presented in this study. This explicit viscosity and Larmor frequency dependent parametrization may be used as first-order approximation to T1 dispersion in crude oils for which only oil viscosity is known and may be applied to polarization level and pulse sequence simulations in low field NMR relaxometry studies up to 20 MHz for a wide range of crude oil viscosities, and in particular for better interpretation of NMR flow measurements on crude oils.

Intermolecular interaction in the hybrid gel of scallop (Patinopecten yessoensis) male gonad hydrolysates and κ-carrageenan.

Various bond disrupting agents including NaCl, GuHCl, urea, and SDS were introduced to investigate the intermolecular interactions between scallop (Patinopecten yessoensis) male gonad hydrolysates (SMGHs) and κ-carrageenan (κ-C), which were monitored by changes in rheological property, water distribution, conformation characterization and microstructure by using rheometer, low field-NMR relaxometry, Fourier transform infrared (FTIR) spectroscopy, cryo-scanning electron microscopy (cryo-SEM), and confocal laser scanning microscopy. The results showed that the bond disrupting agents deteriorated the rheological property of SMGHs/κ-C in a dose-dependent manner. Indeed, at the same concentration of 2 M, NaCl deteriorated the SMGHs/κ-C more obviously than GuHCl and urea. In addition, SMGHs/κ-C with bond disrupting agents possessed higher relaxation times including T21 and T23 , indicating the migration to free water direction of bound and free water. Moreover, the FITR results showed the red-shift in water regions (amide A and B bands), amide I and II bands, and indicated the breakdown of hydrogen bonds and electrostatic interactions, indicating a disordered structure in SMGHs/κ-C by various bond disrupting agents. Furthermore, cryo-SEM results showed the change of SMGHs/κ-C from a homogeneous network to a looser and ruptured one with larger void spaces, and indicated the disrupted and tattered microstructure of SMGHs/κ-C by various bond disrupting agents. Additionally, SMGHs/κ-C as well showed less aggregates stained by RITC by bond disrupting agents. These results suggest that electrostatic interactions would be mainly involved in the maintenance of SMGHs/κ-C gel network. This study could provide theoretical and methodological basis for hydrogel products with modified gel strength and microstructure by understanding the intermolecular interactions in gel system. PRACTICAL APPLICATION: Scallop (Patinopecten yessoensis) male gonads as a high-protein part of scallop, is usually discarded during processing despite its edibility. In recent years, scallop male gonads are regarded as good sources to develop protein matrices due to their high protein content and numerous nutrients. In this study, scallop male gonad hydrolysates (SMGHs) were obtained by trypsin-treated process. The considerable gelation behavior of SMGHs indicated that the SMGHs could be potentially utilized as a novel thickener and additive in production of kamaboko gels, can, sausage and spread with marine flavor.

Effect of Molybdenum Trioxide in the Behavior of Poly(vinyl alcohol) Nanocomposites Systems Focusing New Systems for Protection against COVID-19

The purpose of this work was to study the molecular dynamics, morphology, mechanical and thermal performance of nanomaterials formed by poly(vinyl alcohol) and molybdenum trioxide (PVA/MoO3) obtained through solution casting method, focusing new materials with therapeutic applications since the molybdenum trioxide exhibit an excellent antibacterial activity and could be a pathway to prevent viruses. The obtaining materials were characterized by conventional techniques as X-ray diffraction, thermogravimetric and dynamical-mechanical analysis. The unconventional low-field NMR relaxometry was used to evaluate the molecular dynamic and morphology of these systems. The results obtained showed that the MoO3 addition into PVA matrix promote an increase on the thermal stability at higher temperatures and a progressive increase on the rigidity of the PVA systems. Also changes in the molecular mobility of nanomaterials determined through the proton spin-lattice relaxation time showed that low proportion of molybdenum trioxide increased the intercalation of the poly(vinyl alcohol) chains between oxide lamellae while higher quantity of molybdenum trioxide caused an inverse effect on the oxide lamellae delamination. From those results the nanomaterials presented a mixed structural organization as intercalated and exfoliated morphologies. According to these first results, the nanocomposites obtained promise to be antimicrobial and antiviral agent to prevent COVID-19 and similar viruses.

Low-field NMR-relaxometry as fast and simple technique for in-situ determination of SARA-composition of crude oils

In this study a new, fast and simple method based on low field NMR-relaxometry for in-situ determination of SARA (saturates, aromatics, resins and asphaltenes) composition of crude oils was proposed. This method was tested on 22 samples of crude oils with a wide range of SARA-composition and API gravity values (4.6–42.0°), including extra-heavy, heavy, medium and light crude oils. Results obtained by low-field nuclear magnetic resonance (LF-NMR) were compared with conventional SARA analysis method (ASTM D 4124). Comparison shows good coincidence between SARA values determined by LF-NMR and conventional method data for heavy fractions of asphaltenes and resins (R2 is equal to 0.98 and 0.91, respectively) and for the sum of light fractions including saturates and aromatics (R2 = 0.96). However, comparison for saturated and aromatic compounds separately gave low correlation coefficients (R2 ≤ 0.61 and 0.27, respectively) and relatively soaring standard deviation for individual correlations for saturates and aromatics (8.18 and 9.20). Consequently, LF- NMR relaxation as an alternative method for studying the composition of crude oil allows the determination of asphaltenes, resins and the sum of light fractions (saturates and aromatics) without their extraction (in-situ), which greatly simplifies and accelerates conventional chromatographic analysis. This method can be successfully applied for different types of crude oils with a wide range of API gravity and viscosity values.

Structural evolution of salt-free aqueous Laponite dispersions: A study based on low-field NMR relaxometry and rheological investigations

The combination of Low-Field NMR relaxometry (LF-NMR) and rheological analyses was used to investigate the kinetics of aging and structural evolution of salt-free aqueous Laponite dispersions with concentrations ranging from 0.33 to 2.00 wt%. The examination of LF-NMR results reveals that the rate of nanoclay delamination increases with increasing Laponite concentration while its degree decreases. Furthermore, the LF-NMR results were interpreted together with rheological results to assess the kinetics of processes occurring on different length scales reflecting on the time evolution of the three-dimensional structure. The structural evolution is described by the definition and comparison of three different characteristic times. The LF-NMR decay time (tr) designates the time required for Laponite delamination. The induction time (ti) indicates when interparticle edge-face interactions become effective enough for incipient networking. The gelation time (tg) corresponds to sufficiently high degree of interparticle connectivity for the development of a macroscopic gel behavior. The comparison of ti and tg, on one hand, and tr, on the other hand, allows to conclude that for low concentration Laponite dispersions nanoclay delamination is a prerequisite for the formation of the new dispersion structure with a macroscopic gel behavior. Interestingly, the development of the new structure, based on orientation of clay disks into edge-to-face pattern and mutual interparticle attractive interactions, starts when the delamination process is still running.

Enhanced photocatalytic reduction of Cr(vi) to Cr(iii) over g-C3N4 catalysts with Ag nanoclusters in conjunction with Cr(iii) quantification based on operando low-field NMR relaxometry

Ag nanoclusters are anchored on g-C3N4 for the photocatalytic reduction of Cr(vi), and experience real-time monitoring by operando low-field NMR relaxometry via quantifying the concentration of paramagnetic Cr(iii) in solution.

Imbibition and dewetting of silica colloidal crystals: An NMR relaxometry study

HypothesisThe wettability of the inner surfaces in a porous network is challenging to be accessed but essential to understand the complex performance of e.g. particulate systems. ExperimentsHere we investigate the water behavior in the macroporous (50–100 nm) voids of dense particle packings by performing low-field 1H NMR relaxometry in solid silica colloid crystals. The systems chosen guarantee a regular, known void size distribution with controllable water affinity (through thermal annealing), where the NMR experiment clearly discriminates the void water from micropore or bound water contributions, allowing separate monitoring. FindingsAnalysis of the saturated state indicates that the interparticle voids are completely filled after imbibition, even for less hydrophilic spheres. Due to the interaction with the silica surface, proton relaxation in void water is up to 100 times faster than that in bulk water, serving for assessment of the hydrophilicity within the sample. The relaxation time evolution upon dewetting provides an empirical measurement of the wettability inside the ensemble, revealing a progressively inhomogeneous wetting of increasingly hydrophobic surfaces. Our results provide insight into the imbibition state and dewetting performance in meso- and macroporous systems, with emphasis in the marked influence of the surface nature on the pore wetting distribution.

On the Optimum Aging Time: Magnetic Resonance Study of Asphaltene Adsorption Dynamics in Sandstone Rock

Wettability is a key factor defining ultimate hydrocarbon recovery. Extensive experimentation is required to replicate the wetting state of reservoir rocks. This involves a rock sample wettability restoration procedure, including an aging step and a concept of an optimum aging time, in which asphaltene chemistry plays a major role. There are numerous reports on significance of various crude oil components and elements of asphaltene structure to their tendency to interact with the solid phase, though subject evidence is contradictory. We investigate a possible relationship between the composition of oil, kinetics of an aging process, and a change of sandstone rock wettability. Wettability state of the cores was monitored using low-field NMR relaxometry. The composition and key components of accumulated deposits were established by matching 1H solution-state NMR and X-band EPR spectra of deposits to the spectra of SARA (saturates-aromatics-resins-asphaltenes) fractions of aging fluids. We determined adsorpt...

Motional Dynamics of Halogen-Bonded Complexes Probed by Low-Field NMR Relaxometry and Overhauser Dynamic Nuclear Polarization.

Halogen bonding is a subject of considerable interest owing to wide-ranging chemical, materials and biological applications. The motional dynamics of halogen-bonded complexes play a pivotal role in comprehending the nature of the halogen-bonding interaction. However, not many attempts appear to have been made to shed light on the dynamical characteristics of halogen-bonded species. For the first time, we demonstrate here that the combination of low-field NMR relaxometry and Overhauser dynamic nuclear polarization (ODNP) makes it possible to obtain a cogent picture of the motional dynamics of halogen-bonded species. We discuss here the advantages of this combined approach. Low-field relaxometry allows us to infer the hydrodynamic radius and rotational correlation time, whereas ODNP probes the molecular translational correlation times (involving the substrate as well as the organic radical) with high sensitivity at low field.

Application of low-field, 1H/13C high-field solution and solid state NMR for characterisation of oil fractions responsible for wettability change in sandstones

Asphaltene adsorption on solid surfaces is a standing problem in petroleum industry. It has an adverse effect on reservoir production and development by changing rock wettability, plugging pore throats, and affects oil transport through pipelines. Asphaltene chemistry constitutes important part of the ageing process as part of petrophysical studies and core analysis. The mechanisms and contribution of various oil components to adsorption processes is not fully understood. To investigate the kinetics of the ageing process and address the relative contribution of different oil components, we prepared three sets of sandstone core plugs aged in different oil mixtures over various time intervals. Cores were then re-saturated with decane to evaluate their wetting state using low-field NMR relaxometry by monitoring a change of surface relaxivity. Adsorbed deposits were then extracted from cores for solution-state NMR analysis. Their 1H and 1H-13C correlation spectra obtained using heteronuclear single quantum coherence (HSQC) technique were matched to spectra of four SARA (saturates, aromatics, resins and asphaltenes) components of oil mixtures to deduce components of deposits and inter-component interactions. We notice that wettability reversal of rock is inversely proportional to initial asphaltene concentration. Analysis of deposits reveals an increase in their aliphatic content over ageing time, which is accompanied by a change of the morphology of the pore space due to cluster aggregates forming a network. Results suggest that the ageing process in respect to the wetting state of rock samples consists of three distinctive stages: (i) an early-time period, when the fraction of most polar asphaltenes creates a discontinuous layer corresponding to mixed-wet state; (ii) an intermediate-time interval, at which the full grain coverage may be achieved (at favourable chemical environment) corresponding to strong oil-wetting; (iii) a late-time stage, where intense macro-aggregates accumulation occurs, changing the pore space integrity. It is likely asphaltene-aliphatic interactions leading to growth of sub-micron size macro-aggregates.

Microscopic and Macroscopic Properties of Carbohydrate Solutions in the Ionic Liquid 1-Ethyl-3-methyl-imidazolium Acetate.

Solutions of glucose, cellobiose, and microcrystalline cellulose in the ionic liquid 1-ethyl-3-methyl-imidazolium acetate ([C2mim][OAc]) have been examined using low-field (20 MHz) NMR relaxometry and rheology. The spin-lattice ( T1) and spin-spin ( T2) relaxation times have been determined from 30 to 70 °C inclusive, for a range of concentrations (0-15 wt %) of each carbohydrate in [C2mim][OAc]. The zero shear rate viscosities for the same samples across the same temperature range were studied. The viscosity, NMR relaxometry, and previously published diffusion data were all analyzed together through the Debye-Stokes-Einstein equations. Microscopically, these systems behave as an "ideal mixture" of free ions and ions associated with the carbohydrate molecules. The molar ratio of carbohydrate OH groups to ionic liquid molecules, α, is the key parameter in determining the NMR relaxometry and hence the local microscopic environment of the ions. NMR relaxometry data are found to follow an Arrhenius type behavior, and the difference in rotational activation energy between free and associated ions is determined at 6.2 ± 0.5 kJ/mol.

Water and cell wall contributions to apple mechanical properties

Relations between the apple cortex viscoelastic properties, water dynamics, histological, and chemical characteristics were investigated. Water mobility in four apple genotypes was studied by low-field NMR relaxometry prior and after plasmolysis of the cortex tissue. A discrete and a continuous method for decomposing the multi-exponential T2 curves were implemented and compared. The results show that both methods of relaxation curve decomposition had close ability to discriminate genotypes before and after plasmolysis. Although the sensitivity of T2 relaxometry allowed distinguishing microstructures among genotypes even after cellular fluids were mixed and diffused in plasmolyzed tissues, no relaxation component correlated with apple viscoelasticiy. Galactose and arabinose cell wall content were correlated with the storage modulus (E′) prior and after plasmolysis though the correlation signs were opposite and pointed to a potential key role of pectin RGI side chains in regulating apple texture in turgid tissue.

Insight into Liquid Interactions with Fibrous Absorbent Filter Media Using Low-Field NMR Relaxometry. Prospective Application to Water/Jet Fuel Filter–Coalescence

We describe a low-field NMR relaxometry study of water and aviation turbine fuel (jet fuel) in contact with samples of fibrous media removed from an unused aviation fuel filter cartridge. This media was studied both in its as-received state and after modifying its wettability. The interaction of liquid droplets with fibers is the basis for fibrous coalescence widely used industrially to separate different types of liquid–liquid dispersion. Here, we are specifically concerned with interactions that potentially occur during the removal of entrained water from jet fuels, an application that is of particular importance on safety grounds, primarily to prevent ice formation in aircraft fuel tanks which could otherwise lead to fuel-line filter blockage and fuel starvation to the engines. Jet fuel is treated using various filtration systems, including cartridge-type microfilters and filter–coalescers, at different points between refinery and aircraft fuel tank in order to remove dirt (particulates) and water and ...

Designing healthier comminuted meat products: Effect of dietary fibers on water distribution and texture of a fat-reduced meat model system

Development of healthier meat products is needed to meet consumers' request. The effects of dietary fiber addition on the water distribution, water binding capacity (WBC), and textural properties of a fat-reduced model meat system enriched with inulin, cellulose, carboxymethyl cellulose (CMC), chitosan, pectin, respectively, were investigated in this study. The fibers were incorporated in powder form to constitute 2% (w/w) of the meat batter. In general, fiber enrichment resulted in significant lower cooking loss and improved WBC, while the impact on texture was dependent on the specific dietary fiber. Low-field NMR relaxometry revealed that chitosan impacted the heating-induced changes in water distribution differently from other fibers and that CMC had a higher capability to counteract the impact of heat-induced protein denaturation on water expulsion than the other fiber types. It is anticipated that this knowledge is useful in the development of novel strategies where dietary fiber enrichment is optimized to promote specific and desired technological attributes of healthy meat products.

Studies of relationship between polymer structure and hydration environment in amphiphilic polytartaramides

ABSTRACTThe relationships between the chemical structures and hydration environment of the polymers can provide significant insight into the water‐amphiphilic polymer interactions. Here, the hydrophobicity of amphiphilic block copolymers poly(ethylene tartaramide‐b‐alkyl isocyanate) is gradually tuned by using of a series of pendant alkyl (isopropyl, n‐butyl, cyclopentyl, and cyclohexyl) groups. Dynamics of hydration probed by low‐field NMR relaxometry exhibits a heterogeneous environment of water molecules, corresponding to tightly bound water with slow re‐orientational mobility and loosely bound water with fast re‐orientational mobility. Progressively larger amounts of bound water are present in the copolymers, ongoing from pendant isopropyl, n‐butyl, cyclopentyl, and finally to cyclohexyl group. Water in the copolymer bearing the cyclohexyl group has a significantly high partial specific heat capacity. Therefore, hydrophobic interaction between the polymer and water is enhanced when the hydrophobicity of the polymer is increased, resulting in considerable hydrophobic hydration with decreased mobility of the bound water. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 138–145

Rapid method for monitoring chitosan coagulation using low-field NMR relaxometry

Time-domain NMR relaxometry was proposed as a simple, rapid method to monitor chitosan (CS) coagulation as a function of pH. The longitudinal (T1) and transverse (T2) relaxation times of three CS concentrations (0.022, 0.22, and 2.2gL−1) were simultaneously measured by CP-CWFPx-x pulse sequences in a 0.47T spectrometer. T1 and T2 were shown to be independent of pH as well as to assume values similar to the relaxation time of water (2.7s) at the lowest tested CS concentration. At the highest concentration, T1 increased whereas T2 decreased as pH varied from 6.0 to 7.0. This indicates a remarkable effect of CS on water relaxation at pH values higher than the pKa of CS amino groups (6.5). Therefore, CS reduced the water mobility at the highest CS concentration and greatest pH values, suggesting a CS supramolecular structure (gel) that entraps the solvent in confined regions. The method proposed here can be further used to study the coagulation of other polysaccharides.

High pressure/thermal combinations on texture and water holding capacity of chicken batters

Abstract The effects of pressure/thermal combination treatments, i.e. heating before pressure treatment (H-P), pressure treatment before heating (P-H), and heating under pressure (P + H), on chicken batters were investigated using heating (H) as control. The appearance, texture, water holding capacity (WHC), water mobility and distribution, and microstructure were determined. P + H and P-H treatments promoted the batter gelation process, forming a gel with fine strands which resulted in improved appearance, texture and water holding capacity, while H-P treatment, with a similar coarse gel network to H treatment, showed little improvement in texture and appearance, but had increased released water and centrifugation loss. By treating with 200 MPa at 75 °C for 30 min in a single-step process, the chicken sausage had the smoothest appearance, lowest released water and an improved texture. The water mobility and distribution were studied by low-field NMR relaxometry, which showed that H-P and P + H treatment increased the proportion of immobilized water as indicated by T21 relaxation times and population (P21). Microstructure further explained the quality improvement of P-H and P + H treatment which could be ascribed to the pressure effects before/during protein denaturation promoting formation of a fine gel network, while H-P treatment limited the resulting effects of pressure on the cooked sample. Hence, P-H and P + H treatment can be used to improve the texture and WHC of gel-type meat products. Industrial relevance Temperature and pressure are two important thermodynamic parameters which can be combined in several ways in meat product processing. The sequence of pressure and thermal treatment has a significant effect on the quality of meat products. This information will help meat industry to adopt suitable pressure/thermal treatment to produce meat products.

Water mobility and microstructure evolution in the germinating Medicago truncatula seed studied by NMR relaxometry. A revisited interpretation of multicomponent relaxation.

The water status of Medicago truncatula Gaertn. seed was followed by low-field NMR relaxometry during germination with and without oryzalin or fusicoccin used as growth modulators. T1 and T2 relaxation times and proportions P1 and P2 were determined on fresh, frozen, and freeze-thawed samples to characterize changes in water dynamics and compartmentation and in the nonfreezing water fraction. The results demonstrate that low-field NMR relaxometry allowed differentiating germination phases and events occurring during them as well as perturbations related to the presence of growth modulators. The results provide clear evidence that the classical multicomponent relaxation interpretation cannot directly relate T2 components and morphological compartments in biological tissue.

High-pressure low-field 1H NMR relaxometry in nanoporous materials

A low-field NMR sensor with NdFeB permanent magnets (B0=118mT) and a pressure cell made of PEEK (4cm outer diameter) were designed for 1H relaxation time studies of adsorbed molecules at pressures of up to 300bar. The system was used to investigate methane uptake of microporous metal–organic frameworks and nanoporous activated carbon. T2 relaxation time distribution of pure methane and of methane under co-adsorption of carbon dioxide show that the host–guest interaction lead to a relaxation time contrasts, which may be used to distinguish between the gas phase and the different adsorbed phases of methane. Adsorption isotherms, exchange of methane between adsorbent particles and the surrounding gas phase, successive displacement of methane from adsorption sites by co-adsorption of carbon dioxide and CO2/CH4 adsorption separation factors were determined from the observed NMR relaxation time distributions.

Preparation of high-impact polystyrene nanocomposites with organoclay by melt intercalation and characterization by low-field nuclear magnetic resonance

Recycled high-impact polystyrene nanocomposites with organoclay were prepared. Clay of the smectite group (montmorillonite) with two types of intercalated compounds was used (Viscogel S4 and Viscogel S7). The polymer nanocomposites were prepared by melt intercalation, applying two shear intensities in a twin screw extruder. The nanostructured materials obtained were characterized by NMR relaxometry, X-ray diffraction, thermogravimetric analysis, melt flow index and mechanical analyses. The results showed that the nanostructured materials presented a mixed intercalated/exfoliated morphology. The organophilic clay, Viscogel S7, generated polymer nanocomposites with better dispersion and distribution (at low concentrations) than those produced with the Viscogel S4. The shear rate was effective for dispersion of the nanoparticles. The materials processed at 600rpm showed better dispersion than those processed at 450rpm. The characterization techniques chosen were effective. They were complementary and permitted comparison among the polymer nanocomposites. The use of low-field NMR relaxometry allowed measurement of the spin–lattice relaxation time of hydrogen (T1H), which provided more precise information on the mobility of the materials, thus complementing and explaining the results obtained by X-ray diffraction.