Anomalous NMR relaxation in cartilage matrix components and native cartilage: fractional-order models

We present a fractional-order extension of the Bloch equations to describe anomalous NMR relaxation phenomena (T(1) and T(2)). The model has solutions in the form of Mittag-Leffler and stretched exponential functions that generalize conventional exponential relaxation. Such functions have been shown by others to be useful for describing dielectric and viscoelastic relaxation in complex, heterogeneous materials. Here, we apply these fractional-order T(1) and T(2) relaxation models to experiments performed at 9.4 and 11.7 Tesla on type I collagen gels, chondroitin sulfate mixtures, and to bovine nasal cartilage (BNC), a largely isotropic and homogeneous form of cartilage. The results show that the fractional-order analysis captures important features of NMR relaxation that are typically described by multi-exponential decay models. We find that the T(2) relaxation of BNC can be described in a unique way by a single fractional-order parameter (α), in contrast to the lack of uniqueness of multi-exponential fits in the realistic setting of a finite signal-to-noise ratio. No anomalous behavior of T(1) was observed in BNC. In the single-component gels, for T(2) measurements, increasing the concentration of the largest components of cartilage matrix, collagen and chondroitin sulfate, results in a decrease in α, reflecting a more restricted aqueous environment. The quality of the curve fits obtained using Mittag-Leffler and stretched exponential functions are in some cases superior to those obtained using mono- and bi-exponential models. In both gels and BNC, α appears to account for micro-structural complexity in the setting of an altered distribution of relaxation times. This work suggests the utility of fractional-order models to describe T(2) NMR relaxation processes in biological tissues.     

A computational modeling approach of the jet-like acoustic streaming and heat generation induced by low frequency high power ultrasonic horn reactors

High power ultrasound reactors have gained a lot of interest in the food industry given the effects that can arise from ultrasonic-induced cavitation in liquid foods. However, most of the new food processing developments have been based on empirical approaches. Thus, there is a need for mathematical models which help to understand, optimize, and scale up ultrasonic reactors. In this work, a computational fluid dynamics (CFD) model was developed to predict the acoustic streaming and induced heat generated by an ultrasonic horn reactor. In the model it is assumed that the horn tip is a fluid inlet, where a turbulent jet flow is injected into the vessel. The hydrodynamic momentum rate of the incoming jet is assumed to be equal to the total acoustic momentum rate emitted by the acoustic power source. CFD velocity predictions show excellent agreement with the experimental data for power densities higher than W(0)/V ≥ 25kWm(-3). This model successfully describes hydrodynamic fields (streaming) generated by low-frequency-high-power ultrasound.     

Interpretation of vicinal proton–proton coupling constants of heteroaromatic molecules in terms of topological electron density descriptors

The indirect vicinal proton–proton coupling constants for pyrrole, furan, thiophene and 15 related heteroaromatic compounds were calculated using the Khon–Sham approximation. An analysis of the four Ramsey contributions to the coupling constants was carried out showing that the Fermi contact term is always positive and dominant, although the remaining contributions have a nonnegligible net negative contribution. The trends observed for the proton–proton coupling constants were rationalized in terms of the properties of the electron density. It was found that electron delocalization between the corresponding hydrogen atoms plays a major role on the observed behavior with the charges of the carbon atoms bonded to them and the accompanying geometric variations being also of importance in the coupling mechanism. Copyright © 2010 John Wiley & Sons, Ltd.     

Computational Study of Proton Transfer in Tautomers of 3‐ and 5‐Hydroxypyrazole Assisted by Water

The tautomerism of 3‐ and 5‐hydroxypyrazole is studied at the B3LYP, CCSD and G3B3 computational levels, including the gas phase, PCM–water effects, and proton transfer assisted by water molecules. To understand the propensity of tautomerization, hydrogen‐bond acidity and basicity of neutral species is approached by means of correlations between donor/acceptor ability and H‐bond interaction energies. Tautomerism processes are highly dependent on the solvent environment, and a significant reduction of the transition barriers upon solvation is seen. In addition, the inclusion of a single water molecule to assist proton transfer decreases the barriers between tautomers. Although the second water molecule further reduces those barriers, its effect is less appreciable than the first one. Neutral species present more stable minima than anionic and cationic species, but relatively similar transition barriers to anionic tautomers.     

Breakdown potential modelling of austenitic stainless steel

The breakdown potential is a crucial factor in the study of pitting corrosion resistance of stainless steel. This work aims to demonstrate the advantage of different chemometric techniques to estimate the breakdown potential of austenitic stainless steel. In order to predict pitting corrosion behaviour of stainless steel, a total of 60 samples of this alloy were subjected to electrochemical tests varying chloride ion concentration, pH and temperature. The experimental values of the breakdown potential, in addition to the tested environmental factors, were used to construct the predictive models based on support vector machines and artificial neural networks. A multiple‐comparison study based on statistic tests was applied to determine the optimal configuration for each technique. According to the results, support vector machines became a suitable and reliable technique to be applied in the modelling of the breakdown potential of austenitic stainless steels. This technique outperformed the models based on artificial neural networks and provided a useful tool to compare the pitting corrosion resistance of stainless steel in different environmental conditions without recourse to polarization tests. Therefore, this model presented a relevant meaning in science and engineering applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Super-nucleation in nanocomposites and confinement effects on the crystallizable components within block copolymers, miktoarm star copolymers and nanocomposites

In this paper we reexamine recent results obtained by our group on the crystallization of nanocomposites and linear and miktoarm star copolymers in order to obtain some general features of their crystallization properties. Different nanocomposites have been prepared where a close interaction between the polymer matrix and the nano-filler has been achieved: in situ polymerized high density polyethylene (HDPE) on carbon nanotubes (CNT); and polycaprolactone (PCL) and poly(ethylene oxide) (PEO) covalently bonded to carbon nanotubes. In all these nanocomposites a “super-nucleation” effect was detected where the CNTs perform a more efficient nucleating action than the self-nuclei of the polymer matrix. It is believed that such a super-nucleation effect stems from the fact that the polymer chains are tethered to the surface of the CNT and can easily form nuclei. For polystyrene (PS) and PCL block copolymers, miktoarm star copolymers (with two arms of PS and two arms of PCL) were found to display more compact morphologies for equivalent compositions than linear PS-b-PCL diblock copolymers. As a consequence, the crystallization of the PCL component always experienced much higher confinement in the miktoarm stars case than in the linear diblock copolymer case. The consequences of the topological confinement of the chains in block copolymers and nanocomposites on the crystallization were the same even though the origin of the effect is different in each case. For nanocomposites a competition between super-nucleation and confinement was detected and the behavior was dominated by one or the other depending on the nano-filler content. At low contents the super-nucleation effect dominates. In both cases, the confinement increases as the nano-filler content increases or the second block content increases (in this case a non-crystallizable block such as PS). The consequences of confinement are: a reduction of both crystallization and melting temperatures, a strong reduction of the crystallinity degree, an increase in the supercooling needed for isothermal crystallization, a depression of the overall crystallization rate and a decrease in the Avrami index until values of one or lower are achieved indicating a nucleation control on the overall crystallization kinetics.     

Effects of High-Pressure Treatment on the Sensory Quality of White Grape Juice

The effects of high-pressure treatment on the colour (objective measurement) and sensory characteristics of white grape juice were studied during storage at 4 °C for 60 days. Grape juice was subjected to three different treatments: 400 or 500 MPa at 2 u °C, and 400 MPa at 40 °C during 10 min. Untreated juice was used as control. Colour parameters (CIE L * a * b *), hue angle (tan m 1 b */ a *), chroma {( a * 2 + b * 2 ) 1/2 }, luminosity Q *{(10 2 log( L *) + 100} and saturation S *( C */ L *) were measured. Juices were evaluated for sweetness, acidity, off-flavour and aroma. High-pressure treatments did not affect the colour parameters of juice, and similar sensory characteristics were observed in both control and treated samples on the first day. The colour and sensory characteristics of pressure-treated samples remained more stable than those of the control juice during 60 days of storage. The control juice was slightly fermented developing some changes in flavour and colour.     

Applications of High-Hydrostatic Pressure on Milk and Dairy Products

Interest in high-pressure (HP) applications on milk and dairy products has recently increased. Pressures between 300 and 600 MPa has been shown to be an effective method to inactivate microorganisms including most infectious food-borne pathogens. In addition to microbial destruction, it has been reported that HP improves rennet or acid coagulation of milk without detrimental effects on important quality characteristics, such as taste, flavour, vitamins, and nutrients. These characteristics offer to dairy industry numerous practical applications to produce microbial safety, minimally processed dairy products with improved performances, and to develop novel dairy products of high nutritional and sensory quality, novel texture and increased shelf life.     

Chemiluminescence as a condition monitoring method for thermal aging and lifetime prediction of an HTPB elastomer

Chemiluminescence (CL) has been applied as a condition monitoring technique to assess aging related changes in a hydroxyl-terminated-polybutadiene based polyurethane elastomer. Initial thermal aging of this polymer was conducted between 110 and 50 °C. Two CL methods were applied to examine the degradative changes that had occurred in these aged samples: isothermal “wear-out” experiments under oxygen yielding initial CL intensity and “wear-out” time data, and temperature ramp experiments under inert conditions as a measure of previously accumulated hydroperoxides or other reactive species. The sensitivities of these CL features to prior aging exposure of the polymer were evaluated on the basis of qualifying this method as a quick screening technique for quantification of degradation levels. Both the techniques yielded data representing the aging trends in this material via correlation with mechanical property changes. Initial CL rates from the isothermal experiments are the most sensitive and suitable approach for documenting material changes during the early part of thermal aging.