Capillary Flow-MRI: Quantifying Micron-Scale Cooperativity in Complex Dispersions.

Strongly confined flow of particulate fluids is encountered in applications ranging from three-dimensional (3D) printing to the spreading of foods and cosmetics into thin layers. When flowing in constrictions with gap sizes, w, within 102 times the mean size of particles or aggregates, d, structured fluids experience enhanced bulk velocities and inhomogeneous viscosities, as a result of so-called cooperative, or nonlocal, particle interactions. Correctly predicting cooperative flow for a wide range of complex fluids requires high-resolution flow imaging modalities applicable in situ to even optically opaque fluids. To this goal, we here developed a pressure-driven high-field magnetic resonance imaging (MRI) velocimetry platform, comprising a pressure controller connected to a capillary. Wall properties and diameter could be modified respectively as hydrophobic/hydrophilic, or within w ∼ 100-540 µm. By achieving a high spatial resolution of 9 µm, flow cooperativity length scales, ξ, down to 15 µm in Carbopol with d ∼ 2 µm could be quantified by means of established physical models with an accuracy of 13%. The same approach was adopted for a heterogeneous fat crystal dispersion (FCD) with d and ξ values up to an order of magnitude higher than those for Carbopol. We found that for strongly confined flow of Carbopol in the 100 µm capillary, ξ is independent of flow conditions. For the FCD, ξ increases with gap size and applied pressures over 0.25-1 bar. In both samples, nonlocal interactions span domains up to about 5-8 particles but, at the highest confinement degree explored, ∼8% for FCD, domains of only ∼2 particles contribute to cooperative flow. The developed flow-MRI platform is easily scalable to ultrahigh field MRI conditions for chemically resolved velocimetric measurements of, e.g., complex fluids with anisotropic particles undergoing alignment. Future potential applications of the platform encompass imaging extrusion under confinement during the 3D printing of complex dispersions or in in vitro vascular and perfusion studies.

Quantifying cooperative flow of fat crystal dispersions.

We quantify the cooperative flow behaviour of fat crystal dispersions (FCDs) upon varying crystallization conditions. The latter enabled altering the multiscale microstructure of the FCDs, from the nanometer-sized platelets, and the dispersed fractal aggregates, up to the strength of the mesoscopic weak-link network. To the goal of characterizing strongly-confined flow in these optically-opaque materials, we acquire high-resolution rheo-magnetic-resonance-imaging (rheo-MRI) velocimetry measurements using an in-house developed 500 µm gap Couette cell (CC). We introduce a numerical fitting method based on the fluidity model, which yields the cooperativity length, ξ, in the narrow-gap CC. FCDs with aggregates sizes smaller than the confinement size by an order of magnitude were found to exhibit cooperativity effects. The respective ξ values diverged at the yield stress, in agreement with the Kinetic Elasto-Plastic (KEP) theory. In contrast, the FCD with aggregates sizes in the order of the gap size did not exhibit any cooperativity effect: we attribute this result to the correspondingly decreased mobility of the aggregates. We foresee that our optimized rheo-MRI measurement and fitting analysis approach will propel further similar studies of flow of other multi-scale and optically-opaque materials.

Validation of temperature-controlled rheo-MRI measurements in a submillimeter-gap Couette geometry.

A temperature-controlled submillimeter-gap (500 µm) rheo-magnetic resonance imaging (MRI) Couette cell has been developed to measure confined flow of soft structured materials under controlled temperature. The proposed setup enables performing rheo-MRI measurements using (i) a spatially uniform temperature control over the range 15°C to 40°C and (ii) a high spatial resolution up to 10 µm, as a consequence of the improved mechanical stability of the in-house developed rotating elements. Here, we demonstrate the performance of the cell for the rheo-MRI velocimetry study of a thixotropic fat crystal dispersion, a complex fluid commonly used in food manufacturing. The submillimeter-gap geometry and variable temperature capability of the cell enable observing the effects of shear- and temperature-induced fat recrystallization on both wall slip and shear banding under strongly confined flow. Our improved rheo-MRI setup opens new perspectives for the fundamental study of strongly confined flow, cooperative effects, and the underlying interparticle interactions and for ultimately aiding optimization of products involved in spreading/extrusion, such as cosmetics and foods.

Non-Invasive Rheo-MRI Study of Egg Yolk-Stabilized Emulsions: Yield Stress Decay and Protein Release.

A comprehensive understanding of the time-dependent flow behavior of concentrated oil-in-water emulsions is of considerable industrial importance. Along with conventional rheology measurements, localized flow and structural information are key to gaining insight into the underlying mechanisms causing time variations upon constant shear. In this work, we study the time-dependent flow behavior of concentrated egg-yolk emulsions with (MEY) or without (EY) enzymatic modification and unravel the effects caused by viscous friction during shear. We observe that prolonged shear leads to irreversible and significant loss of apparent viscosity in both emulsion formulations at a mild shear rate. The latter effect is in fact related to a yield stress decay during constant shearing experiments, as indicated by the local flow curve measurements obtained by rheo-MRI. Concurrently, two-dimensional D-T2 NMR measurements revealed a decrease in the T2 NMR relaxation time of the aqueous phase, indicating the release of surface-active proteins from the droplet interface towards the continuous water phase. The combination of an increase in droplet diameter and the concomitant loss of proteins aggregates from the droplet interface leads to a slow decrease in yield stress.

Hydration-Dependent Dynamical Modes in Xyloglucan from Molecular Dynamics Simulation of 13C NMR Relaxation Times and Their Distributions.

Macromolecular dynamics in biological systems, which play a crucial role for biomolecular function and activity at ambient temperature, depend strongly on moisture content. Yet, a generally accepted quantitative model of hydration-dependent phenomena based on local relaxation and diffusive dynamics of both polymer and its adsorbed water is still missing. In this work, atomistic-scale spatial distributions of motional modes are calculated using molecular dynamics simulations of hydrated xyloglucan (XG). These are shown to reproduce experimental hydration-dependent 13C NMR longitudinal relaxation times ( T1) at room temperature, and relevant features of their broad distributions, which are indicative of locally heterogeneous polymer reorientational dynamics. At low hydration, the self-diffusion behavior of water shows that water molecules are confined to particular locations in the randomly aggregated XG network while the average polymer segmental mobility remains low. Upon increasing water content, the hydration network becomes mobile and fully accessible for individual water molecules, and the motion of hydrated XG segments becomes faster. Yet, the polymer network retains a heterogeneous gel-like structure even at the highest level of hydration. We show that the observed distribution of relaxations times arises from the spatial heterogeneity of chain mobility that in turn is a result of heterogeneous distribution of water-chain and chain-chain interactions. Our findings contribute to the picture of hydration-dependent dynamics in other macromolecules such as proteins, DNA, and synthetic polymers, and hold important implications for the mechanical properties of polysaccharide matrixes in plants and plant-based materials.

Direct 1H NMR evidence of spin-rotation coupling as a source of para → ortho-H2 conversion in diamagnetic solvents.

At ambient temperature, conversion from 100% enriched para-hydrogen (p-H2; singlet state) to ortho-hydrogen (o-H2; triplet state) leads necessarily to the thermodynamic equilibrium proportions: 75% of o-H2 and 25% of p-H2. When p-H2 is dissolved in a diamagnetic organic solvent, conversion is very slow and can be considered as arising from nuclear spin relaxation phenomena. A first relaxation mechanism, specific to the singlet state and involving a combination of auto-correlation and cross correlation spectral densities, can be retained: randomly fluctuating magnetic fields due to inter-molecular dipolar interactions. We demonstrate here that (i) this dipolar mechanism is not sufficient for accounting for the para→ortho conversion rate, (ii) spin-rotation interaction, an intra-molecular mechanism, behaves similarly to random-field interaction and, thus, may be involved in the singlet relaxation rate. Also, as the para→ortho conversion is monitored by proton nuclear magnetic resonance (NMR) of dissolved o-H2 (p-H2 is NMR-silent), one has to account for H2 exchange between the liquid phase and the gas phase within the NMR tube, as well as for dissolution effects. Experimental evidence of the above statements is brought here in the case of two organic solvents: acetone-d6 and carbon disulfide. The observed temperature dependence of the para→ortho conversion rate shows that spin-rotation can be the dominant contribution to the p-H2 relaxation rate in the absence of tangible dipolar interactions. Our findings shed new light on the "mysterious" mechanism of the para→ortho conversion which has been searched for several decades.

Nanostructural effects on polymer and water dynamics in cellulose biocomposites: (2)h and (13)c NMR relaxometry.

Improved moisture stability is desired in cellulose biocomposites. In order to clarify nanostructural effects, a new approach is presented where water and polymer matrix mobilities are characterized separately. Nanocomposites from cellulose nanofibers (CNF) in the xyloglucan (XG) biopolymer matrix are investigated at different hydration states. Films of XG, CNF, and CNF/XG composites are subjected to detailed (2)H and (13)C NMR relaxation studies. Since the (2)H NMR signal arises from heavy water and the (13)C signal from the polysaccharides, molecular water and polymer dynamics is for the first time investigated separately. In the neat components, (2)H transverse relaxation (T2) data are consistent with water clustering at the CNF fibril surfaces, but bulk spread of moisture in XG. The new method results in a description of water interaction with the nanoscale phases. At low hydration, water molecules at the CNF/XG interface exhibit higher water mobility than in neat CNF or XG, due to locally high water concentration. At the same time, CNF-associated interphase segments of XG show slower NMR-dynamics than that in neat XG.

Noninvasive monitoring of moisture uptake in Ca(NO3)2 -polluted calcareous stones by 1H-NMR relaxometry.

NMR transverse relaxation time (T(2)) distribution of (1)H nuclei of water has been used to monitor the moisture condensation kinetics in Ca(NO(3))(2) · (4)H(2)O-polluted Lecce stone, a calcareous stone with highly regular porous structure often utilized as basic material in Baroque buildings. Polluted samples have been exposed to water vapor adsorption at controlled relative humidity to mimic environmental conditions. In presence of pollutants, the T(2) distributions of water in stone exhibit a range of relaxation time values and amplitudes not observed in the unpolluted case. These characteristics could be exploited for in situ noninvasive detection of salt pollution in Lecce stone or as damage precursors in architectural buildings of cultural heritage interest.

Model-free phasor image analysis of quantitative myocardial T1 mapping.

Model-free phasor image analysis, well established in fluorescence lifetime imaging and only recently applied to qMRI [Formula: see text] data processing, is here adapted and validated for myocardial qMRI [Formula: see text] mapping. Contrarily to routine mono-exponential fitting procedures, phasor enables mapping the lifetime information from all image voxels to a single plot, without resorting to any regression fitting analysis, and describing multi-exponential qMRI decays without biases due to violated modelling assumptions. In this feasibility study, we test the performance of our recently developed full-harmonics phasor method for unravelling partial-volume effects, motion or pathological tissue alteration, respectively on a numerically-simulated dataset, a healthy subject scan, and two pilot patient datasets. Our results show that phasor analysis can be used, as alternative method to fitting analysis or other model-free approaches, to identify motion artifacts or partial-volume effects at the myocardium-blood interface as characteristic deviations, or delineations of scar and remote myocardial tissue in patient data.

Non-invasive monitoring of in vitro gastric milk protein digestion kinetics by 1H NMR magnetization transfer.

Processing of milk involves heating, which can modify the structure and digestibility of its proteins. In vitro models are useful for studying protein digestion. However, validating these models with in vivo data is challenging. Here, we non-invasively monitor in vitro gastric milk protein digestion by protein-water chemical exchange detected by 1H nuclear magnetic resonance (NMR) magnetization transfer (MT). We obtained either a fitted composite exchange rate (CER) with a relative standard error of ≤10% or the MT ratio (MTR) of the intensity without or with an off-resonance saturation pulse, from just a single spectral acquisition. Both CER and MTR, affected by the variation in the amount of semi-solid protons, decreased during in vitro gastric digestion in agreement with standard protein content analyses. The decrease was slower in heated milk, indicating slower breakdown of the coagulum. Our results open the way to future quantification of protein digestion in vivo by MRI.

Chemical Feedback in Templated Reaction-Assembly Networks.

Chemical feedback between building block synthesis and their subsequent supramolecular self-assembly into nanostructures has profound effects on assembly pathways. Nature harnesses feedback in reaction-assembly networks in a variety of scenarios including virion formation and protein folding. Also in nanomaterial synthesis, reaction-assembly networks have emerged as a promising control strategy to regulate assembly processes. Yet, how chemical feedback affects the fundamental pathways of structure formation remains unclear. Here, we unravel the pathways of a templated reaction-assembly network that couples a covalent polymerization to an electrostatic coassembly process. We show how the supramolecular staging of building blocks at a macromolecular template can accelerate the polymerization reaction and prevent the formation of kinetically trapped structures inherent to the process in the absence of feedback. Finally, we establish a predictive kinetic reaction model that quantitatively describes the pathways underlying these reaction-assembly networks. Our results shed light on the fundamental mechanisms by which chemical feedback can steer self-assembly reactions and can be used to rationally design new nanostructures.

Full-Harmonics Phasor Analysis: Unravelling Multiexponential Trends in Magnetic Resonance Imaging Data.

Phasor analysis is a robust, nonfitting, method for the study of multiexponential decays in lifetime imaging data, routinely used in Fluorescence Lifetime Imaging Microscopy (FLIM) and only recently validated for Magnetic Resonance Imaging (MRI). In the established phasor approach, typically only the first Fourier harmonic is used to unravel time-domain exponential trends and their intercorrelations across image voxels. Here, we demonstrate the potential of full-harmonics (FH) phasor analysis by using all frequency-domain data points in simulations and quantitative MRI (qMRI) T2 measurements of phantoms with bulk liquids or liquid-filled porous particles and of a human brain. We show that FH analysis, while of limited advantage in FLIM due to the correlated nature of shot noise, in MRI outperforms single-harmonic phasor in unravelling multiple physical environments and partial-volume effects otherwise undiscernible. We foresee application of FH phasor to, e.g., big-data analysis in qMRI of biological or other multiphase systems, where multiparameter fitting is unfeasible.

Enabling High Spectral Resolution of Liquid Mixtures in Porous Media by Antidiagonal Projections of Two-Dimensional 1H NMR COSY Spectra.

The noninvasive, in situ chemical identification of liquid mixtures confined in porous materials is experimentally challenging. NMR is chemically resolved and applicable to optically opaque systems but suffers from a significant loss in spectral resolution in the presence of the magnetic field inhomogeneities typical of porous media. In this work, we introduce a method of analysis of conventional two-dimensional (2D) 1H NMR correlation spectroscopy (COSY) spectra based on the extraction of 1D antidiagonal projections, which are free from line-broadening effects and can therefore be used for chemical species identification. Here, we show the application of the technique to the measurement of linear n-alkanes where the cross-to-diagonal peak ratios are shown to follow a power-law curve as a function of the chain length. This calibration enables quantifying mixtures of linear hydrocarbons confined in any porous material independently of temperature or inter-molecular dynamics. Thus, this is a promising tool for quantitative chemical reaction monitoring studies in heterogeneous systems under operando experimental conditions.

Spatially-resolved 1H NMR relaxation-exchange measurements in heterogeneous media.

In the last decades, the 1H NMR T2-T2 relaxation-exchange (REXSY) technique has become an essential tool for the molecular investigation of simple and complex fluids in heterogeneous porous solids and soft matter, where the mixing-time-evolution of cross-correlated T2-T2 peaks enables a quantitative study of diffusive exchange kinetics in multi-component systems. Here, we present a spatially-resolved implementation of the T2-T2 correlation technique, named z-T2-T2, based on one-dimensional spatial mapping along z using a rapid frequency-encode imaging scheme. Compared to other phase-encoding methods, the adopted MRI technique has two distinct advantages: (i) is has the same experimental duration of a standard (bulk) T2-T2 measurement, and (ii) it provides a high spatial resolution. The proposed z-T2-T2 method is first validated against bulk T2-T2 measurements on homogeneous phantom consisting of cyclohexane uniformly imbibed in finely-sized α-Al2O3 particles at a spatial resolution of 0.47 mm; thereafter, its performance is demonstrated, on a layered bed of multi-sized α-Al2O3 particles, for revealing spatially-dependent molecular exchange kinetics properties of intra- and inter-particle cyclohexane as a function of particle size. It is found that localised z-T2-T2 spectra provide well resolved cross peaks whilst such resolution is lost in standard bulk T2-T2 data. Future prospective applications of the method lie, in particular, in the local characterisation of mass transport phenomena in multi-component porous media, such as rock cores and heterogeneous catalysts.

Non-exchanging hydroxyl groups on the surface of cellulose fibrils: The role of interaction with water.

The interaction of water with cellulose stages many unresolved questions. Here 2H MAS NMR and IR spectra recorded under carefully selected conditions in 1H-2H exchanged, and re-exchanged, cellulose samples are presented. It is shown here, by a quantitative and robust approach, that only two of the three available hydroxyl groups on the surface of cellulose fibrils are exchanging their hydrogen with the surrounding water molecules. This finding is additionally verified and explained by MD simulations which demonstrate that the 1HO(2) and 1HO(6) hydroxyl groups of the constituting glucose units act as hydrogen-bond donors to water, while the 1HO(3) groups behave exclusively as hydrogen-bond acceptors from water and donate hydrogen to their intra-chain neighbors O(5). We conclude that such a behavior makes the latter hydroxyl group unreactive to hydrogen exchange with water.

Electron Spin Polarization Transfer to ortho-H2 by Interaction of para-H2 with Paramagnetic Species: A Key to a Novel para → ortho Conversion Mechanism.

We report that at ambient temperature and with 100% enriched para-hydrogen (p-H2) dissolved in organic solvents, paramagnetic spin catalysis of para → ortho hydrogen conversion is accompanied at the onset by a negative ortho-hydrogen (o-H2) proton NMR signal. This novel finding indicates an electron spin polarization transfer, and we show here that this can only occur if the H2 molecule is dissociated upon its transient adsorption by the paramagnetic catalyst. Following desorption, o-H2 is created until the thermodynamic equilibrium is reached. A simple theory confirms that in the presence of a static magnetic field, the hyperfine coupling between unpaired electrons and nuclear spins is responsible for the observed polarization transfer. Owing to the negative electron gyromagnetic ratio, this explains the experimental results and ascertains an as yet unexplored mechanism for para → ortho conversion. Finally, we show that the recovery of o-H2 magnetization toward equilibrium can be simply modeled, leading to the para → ortho conversion rate.

Core-shell cellulose nanofibers for biocomposites - nanostructural effects in hydrated state.

Core-shell wood cellulose nanofibers (CNF) coated by an XG hemicellulose polymer are prepared and used to make biocomposites. CNF/XG biocomposites have interest as packaging materials and as hydrated CNF/XG plant cell wall analogues. Structure and properties are compared between Core-shell CNF/XG and more inhomogeneous CNF/XG. Experiments include XG sorption, dynamic light scattering of CNF nanoparticle suspensions, FE-SEM of nanostructure, moisture sorption, tensile testing in moist conditions and dynamic mechanical analysis. (2)H NMR relaxometry is performed on materials containing sorbed (2)H2O2 in order to assess water molecular dynamics in different materials. The results clarify the roles of CNF, XG and the CNF/XG interface in the biocomposites, both in terms of moisture sorption mechanisms and mechanical properties in moist state. The concept of core-shell nanofiber network biocomposites, prepared by filtering of colloids, provides improved control of polymer matrix distribution and interface structure. Also, present mechanical properties are much superior to comparable plant fiber biocomposites.

Wood microstructure explored by anisotropic 1H NMR line broadening: experiments and numerical simulations.

The cellular structure of wood, which is highly anisotropic along its main growth directions, is responsible for the observed anisotropy in its physical and mechanical properties that depend in a complex manner on the moisture content. Here, we demonstrate that the (1)H NMR spectra of wood from Norway spruce exhibit a strong and characteristic dependence on the direction of the sample relative to the applied magnetic field. By comparing spectra recorded at different magnetic-field strengths, we show that this variation is caused by the magnetic-field distribution created by the anisotropic and inhomogeneous distribution of matter and thereby magnetic susceptibility. On the basis of the observations that (i) the recorded spectral peak predominantly arises from translationally mobile water molecules and (ii) the spectral broadening is large if the long axis of the wood tracheid cells is perpendicular to the magnetic field, we set out to test the hypothesis that it is the susceptibility variation on the tracheid length scale that is responsible for the observed spectral features. To verify this, we numerically calculate in a discrete grid approximation the NMR line shapes obtained in realistic tracheid models, and we find that the calculated NMR line shapes are in good agreement with the corresponding experimental ones. We envisage the application of these findings for revealing the inhomogeneous distribution of water and its molecular properties in wood and wood-based materials at varying degrees of humidity.