Characterization of artisanally and semiautomatically extracted argan oils from Morocco

The present study was conducted to know the possible influence of the seed treatment, method of extraction and geographical origin on the quality and chemical composition of argan oil. Artisanally and semiautomatically extracted argan oils, from roasted and unroasted seeds, from interior and coast areas, were studied. The quality parameters analyzed were acid value, peroxide value, K₂₃₂ and K₂₇₀, triacylglycerols and fatty acid composition, polar compounds, total phenols, tocopherol content and oil stability index (OSI). Seed treatment and extraction method showed a higher influence on quality parameters than geographical area; the quality parameters of the different oils were discussed. The total phenolic content in all analyzed samples was lower than 10 ppm. γ‐Tocopherol was the major tocopherol (84.4–86.4%) with a high contribution to the total tocopherol content (383–485 ppm). The OSI of the argan oil samples were well correlated (R = 0.97) with the tocopherol contents. The argan oil samples obtained from roasted seeds presented higher stability (26–38 h) than the oils from unroasted seeds (16–32 h).     

Effect of the Leaving Group and Solvent Combination on the LFER Reaction Constants

Fine effects that influence the variations of the reaction constants s(f) in LFER log k = s(f)(N(f) + E(f)) have been summarized here. Increasing solvent polarity in the series of binary mixtures increases the solvolysis rates for the same factor for all benzhydryl derivatives in which the solvation of the leaving group moiety in the transition state is substantial, i.e., log k vs. E(f) correlation lines are parallel (same s(f)). For the substrates in which the demand for solvation of the leaving groups moiety is reduced, (e.g., carbonates) s(f) parameters decrease as the fraction of the water in a given solvent/water mixture increases (log k vs. E(f) plots converge), due to decreasing solvation of the electrofuge moiety toward bigger electrofugality. The abscissa of the intersection of the converging plots might indicate the critical electrofugality above which the solvolysis rates should not depend of the water fraction. Larger reaction constant s(f) indicate later transition state for structurally related substrates only, while s(f) parameters for structurally different substrates cannot be compared likely due to different intrinsic barriers. Inversion in relative abilities of leaving groups is possible if they have similar reactivities and are characterized with different reaction constants.     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Thermal stability of catechin and epicatechin upon disaccharides addition

Influence of sucrose and trehalose addition on epimerisation and thermal degradation of catechin and epicatechin have been studied. Sucrose addition accelerated epimerisation of catechin and epicatechin at 80 and 100 °C. Addition of trehalose had protective effect on epimerisation of catechin and epicatechin. Considering thermal degradation, it was confirmed that thermal degradation of catechin and epicatechin follows the first‐order kinetics. Increasing the temperature causes shorter half‐lives of catechin and epicatechin. Addition of sucrose had negative effect on catechin stability. However, in samples with epicatechin, sucrose impact was temperature dependent. Trehalose addition had positive impact on preventing catechin and epicatechin degradation almost doubling the half‐life of studied compounds. Data presented in this study could help to predict chemical conversions of investigated phenolics in various food systems and to prolong their shelf life in thermally processed foods.     

Insights Into Molecular Interaction of Antitumor Drug Mitoxantrone With Anionic Surfactant Sodium Dodecyl Sulfate at Different Temperatures

A study of the interaction of antitumor drug mitoxantrone with anionic surfactant sodium dodecyl sulfate (SDS) has been carried out by UV–Vis absorption spectroscopy at submicellar and micellar surfactant concentrations, pH 7.4 and 10, and over a temperature range of 293.15–323.15 K. The variation of the monomer drug absorbance as a function of SDS concentration indicates, at pH 7.4 and all investigated temperatures, two definite processes: process I in the submicellar range, attributed to the electrostatic interaction between mitoxantrone and SDS monomers; and process II in the micellar range, when the drug is incorporated into SDS micelles in monomer form. At pH 10, the results have indicated only the process II at micellar SDS concentrations. The monomer absorbance changes occurring as a result of the interactions between mitoxantrone and SDS were rationalized in terms of binding constant, micelle/water partition coefficient, and the corresponding thermodynamic parameters for binding and partitioning processes. Thermodynamic parameters indicate that at pH 7.4 both binding process of mitoxantrone to SDS and partition process of mitoxantrone between micellar and bulk aqueous phases are spontaneous and enthalpy controlled, while at pH 10 both processes are spontaneous and entropy controlled.     

In Vitro Photodynamic Activity of N‐Methylated and N‐Oxidised Tripyridyl Porphyrins with Long Alkyl Chains and Their Inhibitory Activity in Sphingolipid Metabolism

A series of N‐methylated and N‐oxidised tripyridyl porphyrins were synthesised, characterised, and their PDT activity was studied with six cell lines. All the tested porphyrins with a long alkyl chain, except one, were more efficient for PDT than an N‐methylated hydrophilic porphyrin and N‐oxidised porphyrin without the long alkyl chain. Generally, N‐methylated tripyridyl porphyrins were more active than those N‐oxidised, but IC₅₀ values for phototoxicity of two N‐oxides, named TOPyP3‐C₁₇H₃₃O and TOPyP3‐C₁₇H₃₅ , were still in the nanomolar concentration range for most of the tested cell lines. However, TOPyP3‐C₁₇H₃₅ did not show phototoxicity on human foreskin fibroblast cells. Two methylated amphiphilic porphyrins, named TMPyP3‐C₁₇H₃₃ and TMPyP4‐C₁₇H_{35 ,} showed significant dark toxicity, whereas none of the oxidopyridyl porphyrins were toxic without light activation. The selected photosensitisers were shown to be apoptosis inducers, and had inhibitory effects on the clonogenic growth of HCT116 and HeLa cells. All three N‐methylated amphiphilic porphyrins significantly reduced the migratory potential of HCT116 cells. Porphyrins TMPyP3‐C₁₇H₃₅ and TOPyP3‐C₁₇H₃₅ reduced the activity of acid ceramidase, whereas TOPyP3‐C₁₇H₃₃O had a significant inhibitory effect on sphingosine kinase 1 activity in HeLa cells. Compounds with this dual activity were shown to be the most promising photosensitisers, with potential to treat invasive cancers.     

GWCNN: A Metric Alignment Layer for Deep Shape Analysis

Deep neural networks provide a promising tool for incorporating semantic information in geometry processing applications. Unlike image and video processing, however, geometry processing requires handling unstructured geometric data, and thus data representation becomes an important challenge in this framework. Existing approaches tackle this challenge by converting point clouds, meshes, or polygon soups into regular representations using, e.g., multi‐view images, volumetric grids or planar parameterizations. In each of these cases, geometric data representation is treated as a fixed pre‐process that is largely disconnected from the machine learning tool. In contrast, we propose to optimize for the geometric representation during the network learning process using a novel metric alignment layer. Our approach maps unstructured geometric data to a regular domain by minimizing the metric distortion of the map using the regularized Gromov–Wasserstein objective. This objective is parameterized by the metric of the target domain and is differentiable; thus, it can be easily incorporated into a deep network framework. Furthermore, the objective aims to align the metrics of the input and output domains, promoting consistent output for similar shapes. We show the effectiveness of our layer within a deep network trained for shape classification, demonstrating state‐of‐the‐art performance for nonrigid shapes.