Nuclear Magnetic Resonance Relaxometry Research Articles

Swelling of food powders: Kinetics measurement and quantification using NMR relaxometry

Quantitative data on powder swelling kinetics is essential to understand phenomena occurring during rehydration, e.g. lump formation. In this study, swelling kinetics of food powders (gelatin powder, soy protein isolate, pea protein concentrate) were quantified by Nuclear Magnetic Resonance (NMR) relaxometry. Using gelatin plates as a model system, it was successfully demonstrated that NMR relaxometry is an efficient, non-destructive method to study swelling kinetics of non-dissolving systems with moderate swelling speeds. For plant-based proteins, high swelling speeds were observed. The obtained maximum water uptake due to swelling was 5.10 ± 0.80 g/g for soy protein isolate and 3.93 ± 0.16 g/g for pea protein isolate, which is in the expected range. Measurement speed was too low to resolve early swelling kinetics (below 84 s), evaluation was more elaborate and results less unambiguous.

Dynamical properties of solid and hydrated collagen: Insight from nuclear magnetic resonance relaxometry.

1H spin-lattice Nuclear Magnetic Resonance relaxometry experiments have been performed for collagen and collagen-based artificial tissues in the frequency range of 10 kHz-20MHz. The studies were performed for non-hydrated and hydrated materials. The relaxation data have been interpreted as including relaxation contributions originating from 1H-1H and 1H-14N dipole-dipole interactions, the latter leading to Quadrupole Relaxation Enhancement effects. The 1H-1H relaxation contributions have been decomposed into terms associated with dynamical processes on different time scales. A comparison of the parameters for the non-hydrated and hydrated systems has shown that hydration leads to a decrease in the dipolar relaxation constants without significantly affecting the dynamical processes. In the next step, the relaxation data for the hydrated systems were interpreted in terms of a model assuming two-dimensional translational diffusion of water molecules in the vicinity of the macromolecular surfaces and a sub-diffusive motion leading to a power law of the frequency dependencies of the relaxation rates. It was found that the water diffusion process is slowed down by at least two orders of magnitude compared to bulk water diffusion. The frequency dependencies of the relaxation rates in hydrated tissues and hydrated collagen are characterized by different power laws (ωH-β, where ωH denotes the 1H resonance frequency): the first of about 0.4 and the second close to unity.

Exploring Crystal-Phase Molecular Dynamics of the Low-Viscous Mesogen 6CHBT: A Combined FFC and High-Field NMR Relaxometry Investigation.

The molecular dynamics study of thermotropic mesogens exhibiting the crystal phases is valuable in unraveling the complex global (collective) and local (noncollective) motions executed by liquid crystal molecules, which would further advance the existing knowledge on orientationally disordered crystalline (ODIC) phases. Toward the fulfillment of such a task, a combined nuclear magnetic resonance (NMR) relaxometry approach employing the fast field cycling (FFC) NMR (10 kHz-30 MHz) and high-field pulsed NMR (400 MHz) techniques is utilized to sample the broad frequency range offered by molecular motions in the crystal phase of 4-(trans-4'-n-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT). The validity of the observed relaxation data is tested and interpreted by the Bloembergen-Purcell-Pound (BPP) model involving the superposition of four mutually independent Lorentzian spectral densities, reflecting molecular dynamical processes on different time scales. The salient feature of the detailed analysis reveals that the lengthening of temporal dynamics in the crystal phase due to molecular rotations by jumps, which are of intermolecular origin, is evident and further supports the presence of collective-like local dynamics. The analysis does permit decoupling of the molecular reorientations about their short axes (∼100 ns) as well as long axes (∼50 ns) and methyl group rotations (∼0.5 ns) on distinct time scales. The activation energies for reorientations about the short axes and methyl group rotations are found to be 27.3 ± 2.7 and 15.8 ± 1.1 kJ/mol, respectively. The fast methyl rotations in the crystal phase of 6CHBT obtained from FFC NMR are further well complemented by high-field NMR, where 1H NMR line shapes are relatively narrow when compared to those of the nematic phase.

Physical and Chemical Methods to Assess Performance of TPO-Modified Asphalt Binder

The demand for effective asphalt additives is growing as road infrastructure ages and more sustainable pavement solutions are needed. Tire pyrolysis oil (TPO) is an example material that has been gaining attention as a potential asphalt additive. While physical performance grade (PG) temperatures are the predominant performance requirements for asphalt binders, chemical properties are also significant in the evaluation of asphalt performance. There is a need to chemically characterize the aging of asphalt binders modified with TPO and link chemical changes in binder components to binder performance. This study compares 2%, 4%, and 8% TPO and asphalt binder blends via dynamic shear rheometry (DSR), Fourier-transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) relaxometry. The variability in the modified blends was seen by both physical and chemical testing during four different blending times (1, 60, 120, and 240 min). After blending, high and intermediate PGs were determined by physical testing. The 8% TPO blend reduced the high PG of the binder from 64 °C to 58 °C. This effect was confirmed by chemical testing through changes in carbonyl indices and NMR relaxation times. With more oil present in the binder matrix, the binder’s resistance to rutting was reduced. While the high PG was hindered, the intermediate PG remained unchanged for all TPO blends. This physical similarity was mirrored in chemical testing. The chemical and physical variability along with the hindrance of the high PG temperature indicate that more treatment may be needed before TPO can be effectively applied to asphalt binders. This study suggests a correlation between physical performance and key chemical indicators.

Textural, rheological, melting properties, particle size distribution, and NMR relaxometry of cocoa hazelnut spread with inulin-stevia addition as sugar replacer.

This study investigated the influence of substituting 60, 80, and 100% of the sugar in traditional cocoa hazelnut paste (control) formulation with inulin-stevia (90:10, w/w) mixture on textural and rheological characteristics, melting behavior, water activity (aw), particle size distribution (PSD), and color. Textural, rheological, melting properties, and color of samples were analyzed after 1, 2, and 3 months of storage at 11°C. Nuclear magnetic resonance (NMR) relaxometry experiments were also performed to understand the interaction of new ingredients with oil. Replacement of sugar with inulin-stevia gave darker color, reduced Casson yield stress, and changed the textural parameters and melting profile of the samples depending on the level but did not create a remarkable effect on PSD and Casson plastic viscosity. Increasing inulin-stevia content yielded lower aw and higher T2a values indicating decreased mobility of water. Complete removal of sugar caused low spreadability. The results showed that an 80% replacement level yielded a product with similar textural parameters and fat-melting mouth feeling compared to control sample. Cocoa hazelnut spreads prepared with inulin and stevia showed good textural stability during storage.

Hydration and wetting mechanism of borosilicate – Polyvinyl alcohol (PVA) hybrid aerogels of potential bioactivity

Mesoporous borosilicate – polyvinyl alcohol (PVA) hybrid aerogels show positive bioactivity when interacting with dental pulp stem cells. The surface characteristics and the nanostructures of the hydrated aerogel particles are important in determining the biological response. This study reports the comparative structural characterization of pristine and stepwise hydrated hybrid aerogels, and proposes a qualitative mechanism for the wetting and pore-filling processes of these mesoporous materials. Nuclear magnetic resonance (NMR) relaxometry and cryoporometry revealed the extensive hydration of PVA macromolecules in the hybrid skeleton when contrasted to the wetting of pure silica aerogels. In spite of this extensive hydration, the open and permeable pore-structure of the hybrid borosilicate-PVA aerogels are preserved even when completely filled with liquid water. The conservation of the nanoscale architecture of the hybrid aerogels upon wetting was further confirmed by SANS. Finally, it was shown that the incorporation of microcrystalline hydroxyapatite into the hybrid skeleton does not alter the advantageous morphological features and wetting mechanism of the hybrid aerogels. The rough nanostructured skeleton is advantageous for cell binding and ensures facile mass transport through the particles in aqueous suspensions.

The Influence of Lyophilization Pretreatment and Whey Content on Whey and Gelatin-Based Hydrogels.

Whey and gelatin, natural polymers within the protein category, find widespread use in hydrogel formulations applied across the food, medical, and pharmaceutical industries. This study presents new characteristics of hydrogels based on whey, gelatin, and copper sulfate as a consequence of the additional steps in the preparation method, specifically refrigeration and freezing storage followed by lyophilization. The water state in hydrogels prior to lyophilization impacts the morphological appearance, with refrigerated hydrogels exhibiting a more regular and dense pore distribution, as shown by the Scanning Electron Microscopy (SEM) images. This observation aligns with the higher mobility of polymer chains indicated by T2 distributions in 1H nuclear magnetic resonance (RMN) relaxometry measurements. Changes in the intensity and amide-specific wavenumbers of the FTIR spectra of whey and gelatin proteins are evident in the Fourier Transformed Infrared (FTIR) spectra of crosslinked and frozen hydrogels before lyophilization. Moreover, the reinforcing effect in the hydrogel matrix, noted in mechanical tests, is attributed to increased polymer chain content and copper sulfate crosslinking.

Unraveling motion in proteins by combining NMR relaxometry and molecular dynamics simulations: A case study on ubiquitin.

Nuclear magnetic resonance (NMR) relaxation experiments shine light onto the dynamics of molecular systems in the picosecond to millisecond timescales. As these methods cannot provide an atomically resolved view of the motion of atoms, functional groups, or domains giving rise to such signals, relaxation techniques have been combined with molecular dynamics (MD) simulations to obtain mechanistic descriptions and gain insights into the functional role of side chain or domain motion. In this work, we present a comparison of five computational methods that permit the joint analysis of MD simulations and NMR relaxation experiments. We discuss their relative strengths and areas of applicability and demonstrate how they may be utilized to interpret the dynamics in MD simulations with the small protein ubiquitin as a test system. We focus on the aliphatic side chains given the rigidity of the backbone of this protein. We find encouraging agreement between experiment, Markov state models built in the χ1/χ2 rotamer space of isoleucine residues, explicit rotamer jump models, and a decomposition of the motion using ROMANCE. These methods allow us to ascribe the dynamics to specific rotamer jumps. Simulations with eight different combinations of force field and water model highlight how the different metrics may be employed to pinpoint force field deficiencies. Furthermore, the presented comparison offers a perspective on the utility of NMR relaxation to serve as validation data for the prediction of kinetics by state-of-the-art biomolecular force fields.

Effects of high hydrostatic pressure on the functional properties of soy protein isolate

AbstractIn this study, functional properties of high hydrostatic pressure (HHP)‐treated soy protein isolate (SPI) samples including protein solubility, emulsification activity (EA), and water holding capacity (WHC) were studied. Fourier transform infrared spectroscopy (FTIR), viscosity, and nuclear magnetic resonance (NMR) relaxometry experiments were performed. Three pressure (300, 400, and 500 MPa), two pH (5.0 and 7.0), and two temperature levels (25 and 40°C) were used to prepare SPI samples. Solubility of SPI was more pH‐dependent than HHP‐dependent, whereas WHC was more sensitive to pressure. Samples processed at 300 MPa, pH 5.0, and 40°C demonstrated higher EA (p < .05) than the untreated samples. Pressure application significantly reduced the viscosity of SPI dispersions (p < .05). Samples processed at 300 MPa, pH 5.0, and 40°C and at 400 MPa, pH 5.0, and 40°C attained the longest transverse relaxation time (T2) values reflecting their low solubility profiles. Thus, results indicated that HHP was able to modify the functional properties of SPI at different temperature and pH conditions.Practical ApplicationsHigh hydrostatic pressure (HHP) is an emerging technology with its diverse range of applications in food industry. Modification of functional properties of food ingredients is one of the latest applications of HHP treatment. This study demonstrated that HHP treatment was able to modify some functional properties of soy protein isolate (SPI) samples including water holding capacity, solubility, and emulsification activity. Pressure level, pH, and temperature affected the functional properties of SPI samples. The parameter type/range and results of this study could be used in model HHP studies to improve some functional properties of SPI for different purposes.

Microscopic and Macroscopic Characterization of Hydrogels Based on Poly(vinyl-alcohol)-Glutaraldehyde Mixtures for Fricke Gel Dosimetry.

In recent decades, hydrogels have emerged as innovative soft materials with widespread applications in the medical and biomedical fields, including drug delivery, tissue engineering, and gel dosimetry. In this work, a comprehensive study of the macroscopic and microscopic properties of hydrogel matrices based on Poly(vinyl-alcohol) (PVA) chemically crosslinked with Glutaraldehyde (GTA) was reported. Five different kinds of PVAs differing in molecular weight and degree of hydrolysis were considered. The local microscopic organization of the hydrogels was studied through the use of the 1H nuclear magnetic resonance relaxometry technique. Various macroscopic properties (gel fraction, water loss, contact angle, swelling degree, viscosity, and Young's Modulus) were investigated with the aim of finding a correlation between them and the features of the hydrogel matrix. Additionally, an optical characterization was performed on all the hydrogels loaded with Fricke solution to assess their dosimetric behavior. The results obtained indicate that the degree of PVA hydrolysis is a crucial parameter influencing the structure of the hydrogel matrix. This factor should be considered for ensuring stability over time, a vital property in the context of potential biomedical applications where hydrogels act as radiological tissue-equivalent materials.

Vegan and sugar-substituted chocolates: assessing physicochemical characteristics by NMR relaxometry, rheology, and DSC

The main physicochemical characteristics of novel artisanal chocolates (both dark and milky) intended for vegan consumers or for those requiring assumption of fewer simple sugars, were analysed. Replacement of milk (with coconut copra, almonds, and soy protein isolates), and sucrose (with coconut sugars, stevia and erythritol, respectively) in dark chocolate, were accounted for by means of texture analysis, rheology, water activity, fatty acid composition, differential scanning calorimetry (DSC) and fast field cycling (FFC) nuclear magnetic resonance (NMR) relaxometry. The vegan sample (i.e., the milk-less one) showed lower values of hardness and adhesiveness as well as a larger peak in the melting behavior at the calorimetric evaluation (DSC). Moreover, the absence of milk resulted in the halving of the yield stress and a decrease in both the apparent and Casson’s viscosity. In the sample of chocolate with less sucrose, the peak temperatures measured at the DSC indicate crystallization of cocoa butter in its best form (Vβ2), unlike in dark chocolate, due to the different sugar composition. Similarly, the Casson yield stress (τ0), increased significantly (almost 70%), with the substitution of sugar. Finally, the results of NMR FFC relaxometry made it possible to identify aggregates of different sizes, laying the basis for its use as a rapid, non-destructive method for chocolate analysis.

Alginate aerogels by spray gelation for enhanced pulmonary delivery and solubilization of beclomethasone dipropionate

Aerogel technology is an emerging platform that offers alternative and cost-effective dry carriers with advanced performances for the pharmaceutical industry. The innovative combination of compressed air-assisted spray gelation and “green” supercritical fluid (SCF) technology was used in this study to produce alginate aerogel microparticles with adequate properties for pulmonary drug delivery. Beclomethasone dipropionate (BDP), a poorly water-soluble anti-inflammatory drug for asthma treatment, was loaded into alginate aerogel particles by SCF-assisted impregnation ensuring high loading, as well as the amorphization of the drug. The production of aerogels was optimized through the fine-tuning of parameters in compressed air-assisted spray gelation, specifically adjusting the air flow rate and the pump speed. Alginate aerogels were aimed to be produced with an appropriate aerodynamic diameter from 1 to 5 µm, measured by in vitro deposition tests with Next Generation impactor and potential for deep lung penetration. Nuclear magnetic resonance (NMR) relaxometry was used to assess aerogel hydration and unveiled structure–property relationships leading to the sudden release of the drug. Finally, in vitro cytotoxicity tests in fibroblasts and ex vivo permeability tests were conducted. These biological tests confirmed the excellent biocompatibility of the aerogel formulations and demonstrated the efficient deposition of BDP in porcine bronchial tissues assisted by the porous alginate aerogel carrier.

Multivariate Machine Learning Models of Nanoscale Porosity from Ultrafast NMR Relaxometry.

Nanoporous materials are of great interest in many applications, such as catalysis, separation, and energy storage. The performance of these materials is closely related to their pore sizes, which are inefficient to determine through the conventional measurement of gas adsorption isotherms. Nuclear magnetic resonance (NMR) relaxometry has emerged as a technique highly sensitive to porosity in such materials. Nonetheless, streamlined methods to estimate pore size from NMR relaxometry remain elusive. Previous attempts have been hindered by inverting a time domain signal to relaxation rate distribution, and dealing with resulting parameters that vary in number, location, and magnitude. Here we invoke well-established machine learning techniques to directly correlate time domain signals to BET surface areas for a set of metal-organic frameworks (MOFs) imbibed with solvent at varied concentrations. We employ this series of MOFs to establish a correlation between NMR signal and surface area via partial least squares (PLS), following screening with principal component analysis, and apply the PLS model to predict surface area of various nanoporous materials. This approach offers a high-throughput, non-destructive way to assess porosity in c.a. one minute. We anticipate this work will contribute to the development of new materials with optimized pore sizes for various applications.

Multivariate Machine Learning Models of Nanoscale Porosity from Ultrafast NMR Relaxometry

AbstractNanoporous materials are of great interest in many applications, such as catalysis, separation, and energy storage. The performance of these materials is closely related to their pore sizes, which are inefficient to determine through the conventional measurement of gas adsorption isotherms. Nuclear magnetic resonance (NMR) relaxometry has emerged as a technique highly sensitive to porosity in such materials. Nonetheless, streamlined methods to estimate pore size from NMR relaxometry remain elusive. Previous attempts have been hindered by inverting a time domain signal to relaxation rate distribution, and dealing with resulting parameters that vary in number, location, and magnitude. Here we invoke well‐established machine learning techniques to directly correlate time domain signals to BET surface areas for a set of metal‐organic frameworks (MOFs) imbibed with solvent at varied concentrations. We employ this series of MOFs to establish a correlation between NMR signal and surface area via partial least squares (PLS), following screening with principal component analysis, and apply the PLS model to predict surface area of various nanoporous materials. This approach offers a high‐throughput, non‐destructive way to assess porosity in c.a. one minute. We anticipate this work will contribute to the development of new materials with optimized pore sizes for various applications.

Glass spectrum, excess wing phenomenon, and master curves in molecular glass formers: A multi-method approach.

The relaxation spectra of glass formers solely displaying an α-peak and excess wing contribution collected by various methods are reanalyzed to pin down their different spectral evolution. We show that master curve construction encompassing both α-peak and emerging excess wing works for depolarized light scattering (DLS) and nuclear magnetic resonance (NMR) relaxometry. It reveals the self-part of the slow dynamics' spectrum. Master curves are to be understood as a result of a more extensive scaling covering all temperatures instead of strict frequency-temperature superposition. DLS and NMR display identical relaxation spectra; yet, comparing different systems, we do not find a generic structural relaxation at variance with recent claims. Dielectric spectroscopy (DS) spectra show particularities, which render master curve construction obsolete. The DS α-peak is enhanced or suppressed with respect to that of DLS or NMR, yet, not correlated to the polarity of the liquid. Attempting to single out the excess wing from the overall spectrum discloses a stronger exponential temperature dependence of its amplitude compared to that below Tg and a link between its exponent and that of the fast dynamics' spectrum. Yet, such a decomposition of α-peak and excess wing appears to be unphysical. Among many different glasses, the amplitude of the excess wing power-law spectrum is found to be identical at Tg, interpreted as a relaxation analog to the Lindemann criterion.

Diffusion of Water Molecules on the Surface of Silica Nanoparticles─Insights from Nuclear Magnetic Resonance Relaxometry.

1H spin-lattice nuclear magnetic resonance (NMR) relaxation experiments have been performed for water dispersions of functionalized silica nanoparticles of diameters of 25 and 45 nm. The experiments have been performed in a broad frequency range spanning 3 orders of magnitude, from 10 kHz to 10 MHz, versus temperature, from 313 to 263 K. On the basis of the data, two-dimensional translation diffusion (diffusion close to the nanoparticle surface within a layer of the order of a few diameters of water molecules) has been revealed. The translational correlation times as well as the residence life times on the nanoparticle surface have been determined. It has turned out that the residence lifetime is temperature-independent and is on the order of 5 × 10-6 s for the smaller nanoparticles and by about a factor of 3 longer for the larger ones. The translational correlation time for the case of 25 nm nanoparticles is also temperature-independent and yields about 6 × 10-7 s, while for the dispersion of the larger nanoparticles, the correlation times changed from about 8 × 10-7 s at 313 K to about 1.2 × 10-6 s at 263 K. In addition to the quantitative characterization of the two-dimensional translation diffusion, correlation times associated with bound water molecules have been determined. The studies have also given insights into the population of the bound and diffusing water on the surface water fractions.

Microscopic moisture localisation in unsaturated materials using nuclear magnetic resonance relaxometry

Due to the detrimental effects of moisture in the built environment, there is a continuous interest in non-destructive experimental techniques that quantify and/or localise moisture in materials. Most existing experimental techniques, however, typically focus on macroscopic moisture contents in samples rather than the microscopic distribution of water in the individual pores of building materials. For the latter, a popular method such as X-ray computed tomography is not readily applicable, due to the gap between its spatial resolution limit and the typical pore sizes of building materials. Nuclear magnetic resonance (NMR) relaxometry is capable of measuring water in pores of both the nanometer and micrometer scale and is therefore an interesting possibility. While most NMR research focusses on water-saturated materials or overall moisture contents, this study determines the size distributions of the water islands in unsaturated materials with NMR, and compares results to X-ray computed tomography (XCT) images and pore network model (PNM) simulations. Results on unsaturated materials show that NMR focusses on the biggest water islands (i.e. in capillary filled pores) and disregards the hydrogen nuclei in smaller water islands (i.e. stored in pore corners). NMR relaxometry is therefore only adept at providing very rough estimates of the size of water-filled pores, especially since post-processing of the NMR experiments to obtain these water island size distributions involves a lot of uncertainty.

Insights into mechanism and modelling of dynamic moisture sorption in dual-porous insulation materials with micro- and nano-scale pores

HypothesisUnderstanding moisture sorption in porous insulation materials is challenging due to the influence of multiscale pore structures on phase behavior and transport properties. Dynamic moisture sorption in dual-porous materials is likely co-determined by interior micro- and nano-scale pores, and an accurate physical model for predicting moisture evolution can be developed by clarifying the sorption mechanisms. ExperimentsMoisture behavior during the dynamic sorption of dual-porous insulation material is measured by low-field nuclear magnetic resonance (NMR) experiments. The contributions of micro- and nano-scale pores to the adsorbed moisture are differentiated using NMR relaxometry, and the evolution of moisture morphology is quantitatively analyzed. FindingsAnalysis of T2 evolution reveals that the moisture in nano-scale pores alters from adsorption layers to liquid with increasing relative humidity (RH), while minimal sorption occurs in micro-scale pores. Moisture is mainly transferred as vapor molecules at low RH levels, with the dynamic sorption enhanced by molecular diffusion in micro-scale pores. Capillary flow in nano-scale pores dominates moisture transport when RH rises above a threshold, leading to a significant increase in apparent moisture diffusivity. According to the elucidated mechanism, a physical model is further developed to predict moisture sorption inside dual-porous insulation materials, and it may serve as a basis for evaluating and optimizing the performance of dual-porous systems in different environments.

Characterization of Functionalized Chromatographic Nanoporous Silica Materials by Coupling Water Adsorption and Intrusion with Nuclear Magnetic Resonance Relaxometry

Characterization of Functionalized Chromatographic Nanoporous Silica Materials by Coupling Water Adsorption and Intrusion with Nuclear Magnetic Resonance Relaxometry

The efficiency of bio-char as bitumen modifier

Improving the mechanical properties of bitumen is an important goal for road pavements design. For this reason, new compounds are now being sought for testing as bitumen modifiers.In this work, the authors studied the effect that two different chars have on two 50/70 bitumens with different chemical and physical characteristics. A complete morphological, surface and bulk characterization of the two additives was carried out. In addition, rheology, Nuclear Magnetic Resonance (NMR) relaxometry and atomic force microscopy were used to analyze the effect that the two additives exert on the properties of the bitumens. According to the results, the char sample with high porosity could be used as a modifier of mechanical properties, while no rejuvenation effects were observed for either of the two additives tested. In addition, the two additives do not give rise to segregation phenomena.