Nucleation behavior of blended high‐melting fractions of milk fat as affected by emulsifiers

The effect of highly hydrophobic emulsifiers, the palmitic sucrose ester P‐170 (hydrophilic/lipophilic balance (HLB) = 1.0), the stearic sucrose ester S‐170 (HLB = 1.0), the polyglycerol ester decaglycerol decastearate DAS 7S (HLB = 3.7) and the polyglycerol ester decaglycerol dodecabehenate DDB 750 (HLB = 2.6), on the nucleation of a high melting point milk fat fraction (HMF) and its blends with sunflower oil (SFO) was investigated by polarized laser light turbidimetry, X‐ray diffractometry and polarized light microscopy (PLM). Addition of polyglycerol esters accelerated nucleation, giving shorter induction times for the same supercooling. On the contrary, sucrose esters inhibited nucleation since induction times were elongated in all conditions selected. Addition of emulsifiers modified the polymorphic behavior in the blends with SFO. The β' form was promoted especially with the addition of S‐170. DAS 7S and DDB 750 promoted crystallization. PLM images showed many small crystals that did not appear in HMF images. Addition of P‐170 and S‐170 delayed nucleation and inhibited crystal growth. Crystals were notoriously smaller than the ones that appeared in HMF images. The Fisher–Turnbull model was used to calculate activation free energies of nucleation. In all cases, sucrose esters elevated the energy barrier for nucleation. Polyglycerol esters, however, if they had an effect on the energy barrier, lowered the values.     

<Emphasis Type="Italic">In situ</Emphasis> monitoring of solid fat content by means of pulsed nuclear magnetic resonance spectrometry and ultrasonics

An ultrasonic technique was developed to study the crystallization process of edible fats on-line. A chirp wave was used instead of the conventional pulser signal, thus achieving a higher signal-to-noise ratio. This enabled measurements to be made in concentrated systems [≈20% solid fat content (SFC)] through a 8.11-cm thick sample without significant signal loss. Fat samples were crystallized at 20, 25, and 30°C at a constant agitation rate of 400 rpm for 90 min. The crystallization process was followed by ultrasonic spectroscopy and a low-resolution pulsed nuclear magnetic resonance spectrometer. Specific relationships were found between ultrasonic parameters [integrated response, time of flight (TF), and full width half maximum] and SFC. TF, which is an indirect measurement of the ultrasonic velocity (v), was highly correlated to SFC (r ²>0.9) in a linear fashion (v=2.601 SFC+1433.0).     

Biodegradable composites with improved barrier properties and transparency from the impregnation of PLA to bacterial cellulose membranes

Poly(lactic acid) (PLA) was impregnated in bacterial cellulose (BC) membranes. BC/PLA films were prepared by solvent casting and mechanical, optical and barrier properties, and biodegradation process were investigated. The transparency of processed films was higher than that of neat BC and increased with PLA content. Moreover, the incorporation of PLA to BC enhanced significantly the water vapor barrier properties of the BC membranes. The bionanocomposites contained a high percentage of cellulose due to the impregnation method that leads to the film with a BC content of 94%, which practically maintains the excellent mechanical properties of BC. However, when increasing the PLA content in the bionanocomposites the mechanical properties decreased slightly with respect to BC. Biodegradation under real soil conditions was determined indirectly through the study of the visual degradation and disintegration, demonstrating that the bionanocomposites were degraded faster than the neat PLA. The successful production of BC/PLA bionanocomposites suggested the possible application of them for active food packaging. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43669.     

Molecular Networking for Drug Toxicities Studies: The Case of Hydroxychloroquine in COVID-19 Patients

Using drugs to treat COVID-19 symptoms may induce adverse effects and modify patient outcomes. These adverse events may be further aggravated in obese patients, who often present different illnesses such as metabolic-associated fatty liver disease. In Rennes University Hospital, several drug such as hydroxychloroquine (HCQ) have been used in the clinical trial HARMONICOV to treat COVID-19 patients, including obese patients. The aim of this study is to determine whether HCQ metabolism and hepatotoxicity are worsened in obese patients using an in vivo/in vitro approach. Liquid chromatography high resolution mass spectrometry in combination with untargeted screening and molecular networking were employed to study drug metabolism in vivo (patient’s plasma) and in vitro (HepaRG cells and RPTEC cells). In addition, HepaRG cells model were used to reproduce pathophysiological features of obese patient metabolism, i.e., in the condition of hepatic steatosis. The metabolic signature of HCQ was modified in HepaRG cells cultured under a steatosis condition and a new metabolite was detected (carboxychloroquine). The RPTEC model was found to produce only one metabolite. A higher cytotoxicity of HCQ was observed in HepaRG cells exposed to exogenous fatty acids, while neutral lipid accumulation (steatosis) was further enhanced in these cells. These in vitro data were compared with the biological parameters of 17 COVID-19 patients treated with HCQ included in the HARMONICOV cohort. Overall, our data suggest that steatosis may be a risk factor for altered drug metabolism and possibly toxicity of HCQ.     

Double-stimuli responsive O/W emulsion gel based on a novel amidoamine surfactant

A heat-induced O/W emulsion gel that undergoes a phase transition from sol to gel on heating was formed from the addition of aqueous HCl to a toluene solution of a long-chain amidoamine derivative (C18AA). The heat induced O/W emulsions are highly sensitive to temperature, and the sol-gel transition temperature could be simply controlled by adjusting the C18AA concentration. Interestingly, the sol-gel transition of the O/W emulsions was also very sensitive to pH. Thus, we have successfully prepared a novel double-stimuli responsive gel based on O/W emulsions consisting of C18AA and HCl.     

Food packaging based on polymer nanomaterials

Since its starting in the 19th century, modern food packaging has made great advances as results of global trends and consumer preferences. These advances are oriented to obtain improved food quality and safety. Moreover, with the move toward globalization, food packaging requires also longer shelf life, along with the monitoring of safety and quality based upon international standards. Nanotechnology can address all these requirements and extend and implement the principal packaging functions - containment, protection and preservation, marketing and communications. Applications of polymer nanotechnology in fact can provide new food packaging materials with improved mechanical, barrier and antimicrobial properties, together with nano-sensors for tracing and monitoring the condition of food during transport and storage.The latest innovations in food packaging, using improved, active and smart nanotechnology will be analyzed. It will be also discuss the limits to the development of the new polymer nanomaterials that have the potential to completely transform the food packaging industry.     

Modeling the kinetics of anionic polymerization in cyclohexane as a non-complexing solvent

In this work it is presented a model of alkyllithium initiated anionic polymerization. The model was developed from the balance of living polymer chains of each chain length, taking into account the participation of molecular aggregates of lithium compounds in initiation and propagation reactions. The model was applied to styrene polymerization in cyclohexane, where the known but not explained acceleration of initiation reaction takes place. The well established reaction order respect to polystyryllithium in propagation reaction allowed some simplification of the model. A more simplified model of three parameters was also developed by using apparent kinetic constants. As part of the work, the apparent propagation constants were determined experimentally and are reported in the Arrhenius equation form. The remainder kinetic parameters used in the model were assumed or fitted to experimental data and are described into the work. The model allows explaining acceleration of the initiation reaction and experimental data of molecular weight averages (M_n, M_w and M_z) during the polymerization. The three-parameter model was only able to explain the acceleration of initiation reaction and monomer conversion data.     

Modeling the Electrical Conductive Paths within All-Solid-State Battery Electrodes

All-solid-state batteries constitute a very promising energy storage device. Two very important properties of these battery cells are the ionic and the electrical conductivity, which describe the ion and the electron transport through the electrodes, respectively. In this work, a numerical method is presented to model the electrical conductivity, considering the outcome of discrete-element method simulations and the intrinsic conductivities of both the active material particles and the conductive additive particles. The results are calibrated and validated with the help of experimental data of real manufactured electrodes. The tortuosity, which strongly influences the ionic conductivity, is also presented for the analyzed electrodes, taking their microstructure into account.     

Dry Fractionation of Cupuassu (Theobroma grandiflorum) Fat: Physical–Chemical Properties and Polymorphic Behavior

Physical chemical properties of cupuassu fat were modified by dry fractionation. Stearin and olein fractions were obtained at 29, 26, and 24 °C. Polymorphic behavior of unfractionated cupuassu fat (UCF) and its fractions were studied in situ by small-angle (SAXS) and wide-angle (WAXS) X-ray scattering using synchrotron light. Polymorphic transitions were followed in real time tempering samples with a thermal cycle. For UCF, the main polymorphic form crystallized under selected conditions was the β’₂. α and β’₁-forms appeared in trace amounts. β₂-form was obtained after storage at 25 °C for 3 months. Stearins obtained at 26 (S-26) and 24 °C (S-24) showed a similar polymorphic behavior. However, S-26 with improved physical properties might be more suitable for chocolate production or as a trans-fat alternative than UCF. Stearin fraction obtained at 29 °C (S-29) had a complex polymorphic behavior. The α-form was the first polymorphic form detected followed by β’₂-form. There was a polymorphic transition from α to β’₁-form but no transition between β’-forms. They were independent to each other showing fractionation in two different solid solutions. Increased contents of the triacylglycerols (TAG) SOA and SOB together with lower contents of SOO compared to UCF led to co-crystallization because there was no complete compatibility among all TAG present in S-29. β₁-form crystallized after storage forming crystals with a double-layer arrangement and a characteristic morphology. This form could be useful for accelerating crystallization process in melted liquid systems.     

Photopolymerizable multifunctional monomers and their evaluation as reactive Bis‐GMA eluents

Bis‐GMA {2,2‐bis[4‐(2′‐hydroxy‐3′‐methacryloyloxy‐propoxy)‐phenyl]‐propane}, TEGDMA <2‐{2‐[2‐(2‐methylprop‐2‐enoyloxy)ethoxy]ethoxy}ethyl‐2‐methylprop‐2‐enoate>, and methyl methacrylate (MMA) are some of the most commonly used monomers in the field of restorative dentistry. These compounds are characterized by having one or two terminal double bonds. Besides the effort to synthesize new monomers, several problems still affect the clinical behavior of contemporary dental materials. In this work, two monomers with three terminal double bonds, 5A13DA and 5A13DMA, were synthesized. Both monomers were used to completely replace TEGDMA as reactive diluent of photopolymerizable dental resin composites containing Bis‐GMA. The effects of 5A13DA and 5A13DMA on flexural properties, double bond conversion, water sorption, solubility, and polymerization shrinkage were evaluated. In addition, both monomers were evaluated as crosslinking agents for methylmethacrylate, resulting in copolymers with enhanced thermal stability. The results obtained suggest that newly synthesized monomers are potential substitutes for TEGDMA in the formulation of dental composites, providing 50% lower volumetric shrinkage than the composite resin used as control and adequate mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46240.