Portable single-sided NMR measurements at variable temperatures: Implementation of a thermo-controlled device and application to the heating of bread dough

A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample.     

Localization and quantification of radical production in cavitating flows with luminol chemiluminescent reactions

Hydrodynamic cavitation experiments in microfluidic systems have been performed with an aqueous solution of luminol as the working fluid. In order to identify where and how much reactive radical species are formed by the violent bubble collapse, the resulting chemiluminescent oxidation reaction of luminol was scrutinized downstream of a constriction in the microchannel. An original method was developed in order to map the intensity of chemiluminescence emitted from the micro-flow, allowing us to localize the region where radicals are produced. Time averaged void fraction measurements performed by laser induced fluorescence experiments were also used to determine the cavitation cloud position. The combination void fraction and chemiluminescence two-dimensional mapping demonstrated that the maximum chemiluminescent intensity area was found just downstream of the cavitation clouds. Furthermore, the radical yield can be obtained with our single photon counting technique. The maximum radical production rates of 1.2*10⁷ OH/s and radical production per processed liquid volume of 2.15*10¹⁰ HO/l were observed. The proposed technique allows for two-dimensional characterisation of radical production in the microfluidic flow and could be a quick, non-intrusive way to optimise hydrodynamic cavitation reactor design and operating parameters, leading to enhancements in wastewater treatments and other process intensifications.     

An analysis of over-relaxation in a kinetic approximation of systems of conservation laws

The over-relaxation approach is an alternative to the Jin–Xin relaxation method in order to apply the equilibrium source term in a more precise way. This is also a key ingredient of the lattice Boltzmann method for achieving second-order accuracy. In this work, we provide an analysis of the over-relaxation kinetic scheme. We compute its equivalent equation, which is particularly useful for devising stable boundary conditions for the hidden kinetic variables.     

Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

Small activation entropy bestows high-stability of nanoconfined D-mannitol

It has been a long-standing puzzling problem that some glasses exhibit higher glass transition temperatures(denoting high stability) but lower activation energy for relaxations(denoting low stability). In this paper, the relaxation kinetics of the nanoconfined D-mannitol(DM) glass was studied systematically using a high-precision and high-rate nanocalorimeter.The nanoconfined DM exhibits enhanced thermal stability compared to the free DM. For example, the critical cooling rate for glass formation decreases from 200 K/s to below 1 K/s; the Tg increases by about 20 K–50 K. The relaxation kinetics is analyzed based on the absolute reaction rate theory. It is found that, even though the activation energy E~*decreases,the activation entropy S~*decreases much more for the nanoconfined glass that yields a large activation free energy G~*and higher thermal stability. These results suggest that the activation entropy may provide new insights in understanding the abnormal kinetics of nanoconfined glassy systems.     

Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations

The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399     

Comparison of fast field-cycling magnetic resonance imaging methods and future perspectives

ABSTRACT

Fast field-cycling (FFC) nuclear magnetic resonance relaxometry is a well-established method to determine the relaxation rates as a function of magnetic field strength. This so-called nuclear magnetic relaxation dispersion gives insight into the underlying molecular dynamics of a wide range of complex systems and has gained interest especially in the characterisation of biological tissues and diseases. The combination of FFC techniques with magnetic resonance imaging (MRI) offers a high potential for new types of image contrast more specific to pathological molecular dynamics. This article reviews the progress in FFC-MRI over the last decade and gives an overview of the hardware systems currently in operation. We discuss limitations and error correction strategies specific to FFC-MRI such as field stability and homogeneity, signal-to-noise ratio, eddy currents and acquisition time. We also report potential applications with impact in biology and medicine. Finally, we discuss the challenges and future applications in transferring the underlying molecular dynamics into novel types of image contrast by exploiting the dispersive properties of biological tissue or MRI contrast agents.     

T1Effects in Sequential Dynamic Susceptibility Contrast Experiments

Residual effects of an initial bolus of gadolinium contrast agent have been previously demonstrated in sequential dynamic susceptibility contrast MR experiments. While these residual effects quickly reach a saturation steady state, their etiology is uncertain, and they can lead to spurious estimates of hemodynamic parameters in activation experiments. The possible influence ofT₁effects is now investigated with experiments in whichT₁weighting is varied as well as with serial regionalT₁measurements. Little evidence for significant residualT₁effects is found, suggesting instead that susceptibility effects underlie these observations. An initial saturation dose of contrast agent minimizes this effect.     

WEAK CONVERGENCE FOR NON-UNIFORM φ-MIXING RANDOM FIELDS

Let $\{\xi_{\bold t}, {\bold t} \in {\bold Z}^d\}$ be a nonuniform $\varphi$-mixing strictly stationary real random field with $E\xi_{\bold 0}=0, E|\xi_{\bold 0}|^{2+\delta}<\infty$ for some $0<\delta<1$. A sufficient condition is given for the sequence of partial sum set-indexed process $\{Z_n(A),\ A\in \Cal A\}$ to converge to Brownian motion. By a direct calculation, the author shows that the result holds for a more general class of set index ${\Cal A}$, where ${\Cal A}$ is assumed only to have the metric entropy exponent $r, 0相似文献