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.     

Cyclopolymerization of cinnamate ester derivatives of alkyl α-(hydroxymethyl) acrylates

Summary Three new monomers for cyclopolymerization were synthesized using phase transfer catalysis of ethyl -(chloromethyl) acrylate (ECMA), t-butyl -(bromomethyl) acrylate (TBBMA) and isobornyl -(bromomethyl)acrylate (IBBMA) with cinnamic acid sodium salt. Bulk and solution polymerization at 70–80°C using AIBN gave soluble cyclopolymers with Mn=13650 and Mw=36540 for the ethyl ester, Mn=47700 and Mw=86900 for the t-butyl ester and Mn=3500 and Mw=4650 for the isobornyl ester monomer. The ester polymerizabilities decreased with increasing substituent bulkiness. FTIR spectra showed ca 30 to 93% cyclic units depending on the concentration of the monomer used in polymerizations. DSC thermograms showed that alkyl group size had little effect on Tg's, with values of 151°C, 156°C, and 164°C for the ethyl, t-butyl and isobornyl esters, respectively.     

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.     

Synthesis and photopolymerizations of new hydroxyl-containing dimethacrylate crosslinkers

Two new hydroxyl-containing di(meth)acrylate monomers were synthesized from the reaction of methyl α-chloromethylacrylate (MCMA) and of ethyl α-chloromethylacrylate (ECMA) with glycerol. The monomers were obtained as mixtures of two isomers in different ratios and in combination with the analogous trimethacrylate monomers. Each monomer was isolated by column chromatography. The photopolymerization of these isomer mixtures and the trimethacrylate monomers was investigated individually by photodifferential scanning calorimetry (photoDSC) at room temperature using 2,2′-dimethoxy-2-phenyl-acetophenone (DMPA) as a photoinitiator. The effect of hydrogen bonding on the rates of polymerizations and conversions was examined. The results obtained for the synthesized monomers were compared to the values obtained for commercial monomers. It was observed that the hydroxyl-containing dimethacrylates polymerize much faster and to considerably higher conversion than the trimethacrylate monomers. The maximum rates of polymerization of the hydroxyl-containing monomers were higher than that of the hexanediol dimethacrylate (HDDMA), comparable to glycerol dimethacrylate and lower than hexanediol diacrylate (HDDA) and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM).     

Polymerization of olefins with bulky substituents. 1. Homo- and copolymerization of 3-(1-adamantyl)propene

The use of bulky substituents like adamantane has been shown in the past to influence the glass transition temperatures of polymers significantly. In this paper the synthesis and homopolymerization of the monomer 3-(1-adamantyl) propene is described, as well as the copolymerization of this monomer with ethene, propene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. The resultant copolymers proved to be largely insoluble in organic solvents. It was also demonstrated that the presence of the bulky methyladamantyl side group influenced the glass transition temperatures of the copolymers in comparison with the corresponding homopolymers.