Rheo-NMR in food science-Recent opportunities.

For over 25 years, nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) techniques have been used to study materials under mechanical deformation. Collectively, these methods are referred to as Rheo-NMR. In many cases, it provides spatially and temporally resolved maps of NMR spectra, intrinsic NMR parameters (such as relaxation times), or motion (such as diffusion or flow). Therefore, Rheo-NMR is complementary to conventional rheological measurements. This review will briefly summarize current capabilities and limitations of Rheo-NMR in the context of material science and food science in particular. It will report on recent advances such as the incorporation of torque sensors or the implementation of large amplitude oscillatory shear and point out future opportunities for Rheo-NMR in food science.

Multilamellar Vesicle Formation Probed by Rheo-NMR and Rheo-SALS under Large Amplitude Oscillatory Shear.

The formation of multilamellar vesicles (MLVs) in the lyotropic lamellar phase of the system triethylene glycol mono n-decyl ether (C10E3)/water is investigated under large amplitude oscillatory shear (LAOS) using spatially resolved rheo-NMR spectroscopy and a combination of rheo-small angle light scattering (rheo-SALS) and conventional rheology. Recent advances in rheo-NMR hardware development facilitated the application of LAOS deformations in high-field NMR magnets. For the range of investigated strain amplitudes (10-50) and frequencies (1 and 2 rad s-1), MLV formation is observed in all NMR and most SALS experiments. It is found that the MLV size depends on the applied frequency in contrast to previous steady shear experiments where the shear rate is the controlling parameter. The onset of MLV formation, however, is found to vary with the shear amplitude. The LAOS measurements bear no indication of the intermediate structures resembling aligned multilamellar cylinders observed in steady shear experiments. Lissajous curves of stress vs strain reveal a transition from a viscoelastic solid material to a pseudoplastic material.

Effect of magnetic pore surface coating on the NMR relaxation and diffusion signal in quartz sand.

Magnetic impurities are ubiquitous in natural porous media such as sand and soil. They generate internal magnetic field gradients because of increased magnetic susceptibility differences between solid and liquid phase in the pore space and because of the presence of magnetic centers. These internal gradients accelerate NMR relaxation rates and thus might limit the possibility of pore space characterization using NMR. In this study, we investigate the effects of coating the surface of natural sands by the antiferromagnetic iron oxyhydroxide goethite on NMR relaxation and diffusion properties. We found a non-quadratic dependence of the relaxation time distributions on the echo time indicating that the relaxation experiments were not performed in the fast diffusion limit, while the weak dependence on the external magnetic field strength is explained by the preponderance of the surface relaxation over the effect of diffusion in internal gradients. The surface to volume ratio of the pore space, determined by NMR diffusimetry ((S/V)NMR ) remains approximately constant, whereas the same quantity, determined from gas adsorption ((S/V)BET ) increases proportional to the coating density. This is because gas adsorption measures surface roughness on sub-nanometer scale, whereas NMR diffusimetry averages over structures smaller than few microns. This has consequences for the calculation of the surface relaxivities. The usage of the (S/V)NMR leads to constant values, whereas the usage of (S/V)BET leads to apparently decreasing relaxivities with increasing coating, which is unrealistic. Copyright © 2016 John Wiley & Sons, Ltd.

On the influence of rotational motion on MRI velocimetry of granular flows - Theoretical predictions and comparison to experimental data.

Continuum dynamics of granular materials are known to be influenced by rotational, as well as translational, motion. Few experimental techniques exist that are sensitive to rotational motion. Here we demonstrate that MRI is sensitive to the rotation of granules and that we can quantify its effect on the MRI signal. In order to demonstrate the importance of rotational motion, we perform discrete element method (DEM) simulations of spherical particles inside a Couette shear cell. The variance of the velocity distribution was determined from DEM data using two approaches. (1) Direct averaging of the individual particle velocities. (2) Numerical simulation of the pulsed field gradient (PFG) MRI signal acquisition based on the DEM data. Rotational motion is found to be a significant effect, typically contributing up to 50% of the signal attenuation, thus amplifying the calculated velocity variance. A theoretical model was derived to relate an MRI signal to the angular velocity distribution. This model for the signal was compared to previously published experimental data as well as simulated MRI results and found to be consistent.

Recrystallization inhibition in ice due to ice binding protein activity detected by nuclear magnetic resonance.

Liquid water present in polycrystalline ice at the interstices between ice crystals results in a network of liquid-filled veins and nodes within a solid ice matrix, making ice a low porosity porous media. Here we used nuclear magnetic resonance (NMR) relaxation and time dependent self-diffusion measurements developed for porous media applications to monitor three dimensional changes to the vein network in ices with and without a bacterial ice binding protein (IBP). Shorter effective diffusion distances were detected as a function of increased irreversible ice binding activity, indicating inhibition of ice recrystallization and persistent small crystal structure. The modification of ice structure by the IBP demonstrates a potential mechanism for the microorganism to enhance survivability in ice. These results highlight the potential of NMR techniques in evaluation of the impact of IBPs on vein network structure and recrystallization processes; information useful for continued development of ice-interacting proteins for biotechnology applications.

Magnetic resonance diffusion and relaxation characterization of water in the unfrozen vein network in polycrystalline ice and its response to microbial metabolic products.

Polycrystalline ice, as found in glaciers and the ice sheets of Antarctica, is a low porosity porous media consisting of a complicated and dynamic pore structure of liquid-filled intercrystalline veins within a solid ice matrix. In this work, Nuclear Magnetic Resonance measurements of relaxation rates and molecular diffusion, useful for probing pore structure and transport dynamics in porous systems, were used to physically characterize the unfrozen vein network structure in ice and its response to the presence of metabolic products produced by V3519-10, a cold tolerant microorganism isolated from the Vostok ice core. Recent research has found microorganisms that can remain viable and even metabolically active within icy environments at sub-zero temperatures. One potential mechanism of survival for V3519-10 is secretion of an extracellular ice binding protein that binds to the prism face of ice crystals and inhibits ice recrystallization, a coarsening process resulting in crystal growth with ice aging. Understanding the impact of ice binding activity on the bulk vein network structure in ice is important to modeling of frozen geophysical systems and in development of ice interacting proteins for biotechnology applications, such as cryopreservation of cell lines, and manufacturing processes in food sciences. Here, we present the first observations of recrystallization inhibition in low porosity ice containing V3519-10 extracellular protein extract as measured with Nuclear Magnetic Resonance and Magnetic Resonance Imaging.