Enzymes in organic synthesis. 2. Synthesis of enantiomerically pure prostaglandin intermediates by Enzymatic Hydrolysis of (1SR, 5RS, 6RS, 7RS)-7-acetoxy-6-acetoxymethyl-2-oxabicyclo[3.3.0]octan-3-one

Subtilisin DY as well as alkaline protease from Bacillus licheniformis 41 p catalyze the hydrolysis of (1SR, 5RS, 6RS, 7RS)-7-acetoxy-6-acetoxymethyl-2-oxabicyclo[3.3.0]octan-3-one ( rac-1 ) with practically useful enantio- and regioselectivity. Under the hitherto found optimal conditions (1S, 5R, 6R, 7R)-7-hydroxy-6-hydroxymethyl-2-oxabicyclo[3.3.0]octan-3-one ( 4 ), an important intermediate in prostaglandin syntheses, could be prepared in a yield of 16% with an enantiomeric excess of 99%. The enantiomer ( ent-4 ) was obtained with the same enantiomeric excess in 20% yield. The chemical yields are related to the racemic starting material rac-1 .     

Effect of ALDH1A1 Gene Knockout on Drug Resistance in Paclitaxel and Topotecan Resistant Human Ovarian Cancer Cell Lines in 2D and 3D Model

Ovarian cancer is the most common cause of gynecological cancer death. Cancer Stem Cells (CSCs) characterized by drug transporters and extracellular matrix (ECM) molecules expression are responsible for drug resistance development. The goal of our study was to examine the role of aldehyde dehydrogenase 1A1 (ALDH1A1) expression in paclitaxel (PAC) and topotecan (TOP) resistant ovarian cancer cell lines. In both cell lines, we knocked out the ALDH1A1 gene using the CRISPR/Cas9 technique. Additionally, we derived an ALDH1A1 positive TOP-resistant cell line with ALDH1A1 expression in all cells via clonal selection. The effect of ALDH1A1 gene knockout or clonal selection on the expression of ALDH1A1, drug transporters (P-gp and BCRP), and ECM (COL3A1) was determined by Q-PCR, Western blot and immunofluorescence. Using MTT assay, we compared drug resistance in two-dimensional (2D) and three-dimensional (3D) cell culture conditions. We did not observe any effect of ALDH1A1 gene knockout on MDR1/P-gp expression and drug resistance in the PAC-resistant cell line. The knockout of ALDH1A1 in the TOP-resistant cell line resulted in a moderate decrease of BCRP and COL3A1 expression and weakened TOP resistance. The clonal selection of ALDH1A1 cells resulted in very strong downregulation of BCPR and COL3A1 expression and overexpression of MDR1/P-gp. This finally resulted in decreased resistance to TOP but increased resistance to PAC. All spheroids were more resistant than cells growing as monolayers, but the resistance mechanism differs. The spheroids’ resistance may result from the presence of cell zones with different proliferation paces, the density of the spheroid, ECM expression, and drug capacity to diffuse into the spheroid.     

Three-dimensional simulation with a CFD tool of the airflow phenomena in single floor double-skin facade equipped with a venetian blind

Nowadays different kinds of double-skin facades are developed and used in new architectural projects. The aim of these facades is, on the one hand, to increase internal comfort and, on the other hand, to decrease energy consumption. In order to optimise the overall performance of the double-skin façades, their detailed behaviour needs to be better understood. The prediction of the airflow within the channel (between the two glazings) is very important for understanding of the double-skin facades behaviour, especially in summer conditions. A comprehensive modelling of a compact double-skin facade equipped with a venetian blind and forced ventilation is proposed here. The modelling is done using the CFD (computational fluid dynamics) approach to assess the air movement within the ventilated facade channel. Three-dimensional airflow is modelled using a homogeneous porous media representation, in order to reduce the size of the mathematical model. A parametric study is proposed here, analysing the impact of three parameters on the airflow development: slat tilt angle, blind position and air outlet position. The distance between the blind and the external glazing was found to have a major impact on the velocity profiles inside the double-skin facade channel.     

Linear correlation between pH value of stimulated beef and electrical current intensity

The aim of the present study was to determine mathematical relationships between pH changes in beef 24 h post-slaughter and changes in the intensity of electrical current flowing through bull and heifer carcasses during high-voltage electrical stimulation. The electrical stimulation was applied 40 min postmortem for 120 s. The pH values of m. longissimus thoracis et lumborum were analyzed in the function of electrical current intensity changes and its change during electrical stimulation. Mathematical linear correlations of the y = ax ± b type were demonstrated between pH values at 2, 6, and 24 h postmortem and the initial (I_i) and ultimate (I_u) electrical current intensity values, the difference between them and the initial pH values determined before electrical stimulation. High multiple correlation coefficients (R² = 0.416, α ≤ 0.001) between I_u and pH values 24 h post-slaughter enabled concluding that there is a possibility to predict a pH value of stimulated carcass with high accuracy, and thus also beef quality, based merely on the ultimate electrical current intensity values.     

Hydroxyl Group Separation Distances in Anti-Freeze Compounds and Their Effects on Ice Nucleation

Since the discovery of biological antifreeze glycoproteins (AFGPs), which can inhibit ice nucleation, there has been considerable interest in understanding their mechanisms and mimicking them in synthetic polymers. In this study, we used molecular dynamics simulations of modified polyvinyl alcohol (PVA) compounds to show that the hydroxyl (OH) group distance is a key factor in whether certain compounds promote or inhibit ice nucleation. A hydroxyl distance smaller than ~2.8 Å but greater than ~7.1 Å in modified PVA (MPVA) compounds was associated with the promotion of ice nucleation, while a hydroxyl group separation distance of approximately ~5.0 Å was correlated with a delay in ice nucleation, owing to changes in the energy of the system. Thus, these results may help explain some of the mechanisms of current known anti-freeze compounds and may have implications for designing new anti-freeze compounds in the future.     

The influence of volume fraction of amorphous phase on corrosion resistance of Mg67Zn 29Ca 4 alloy

The aim of this study was to investigate the structure and corrosion resistance of amorphous, amorphous‐crystalline, and crystalline Mg₆₇Zn₂₉Ca₄ alloy for biodegradable applications. This paper presents a preparation method and results of the structural characterization and corrosion resistance analysis of the material. Samples were prepared in the form of 3 mm diameter rods. The structure of the alloy was examined with the use of X‐ray diffractometry and scanning electron microscopy. The thermal properties of the samples were examined with differential scanning calorimetry (DSC). Results of DSC analysis were used to determine heat treatment temperatures, allowing to obtain different fractures of crystalline phase in the material. Corrosion resistance of heat‐treated samples was investigated by immersion tests and electrochemical measurements performed in the simulated body fluid. The X‐ray diffraction results confirmed that the prepared Mg₆₇Zn₂₉Ca₄ alloy's structure is fully amorphous. After heat treatment, samples with different fractions of amorphous phase in the structure were obtained. Immersion tests of the samples showed that the structure significantly influenced corrosion resistance in examined materials. It should be pointed out, that certain amounts of crystalline phase in amorphous matrix can greatly improve the corrosion resistance of Mg₆₇Zn₂₉Ca₄ alloy.     

Thermal conductivity measurement of erythritol,xylitol, and their blends for phase change material design: A methodological study

This work presents and discusses a detailed thermal conductivity assessment of erythritol, xylitol, and their blends: 25 mol% erythritol and 80 mol% erythritol using the transient plane source (TPS) method with a Hot Disk Thermal Constants Analyzer TPS‐2500S. Thereby, the thermal conductivities of xylitol, 25 mol% erythritol, 80 mol% erythritol, and erythritol were here found for respectively in the solid state to be 0.373, 0.394, 0.535, and 0.589 W m^?1 K^?1 and in the liquid state to be 0.433, 0.402, 0.363, and 0.321 W m^?1 K^?1. These obtained results are comprehensively and critically analyzed as compared to available literature data on the same materials, in the phase change materials (PCMs) design context. This study clearly indicates that these thermal conductivity data in literature have considerable discrepancies between the literature sources and as compared to the data obtained in the present investigation. Primary reasons for these disparities are identified here as the lack of sufficiently transparent and repeatable data and procedure reporting, and relevant standards in this context. To exemplify the significance of such transparent and repeatable data reporting in thermal conductivity evaluations in the PCM design context, here focused on the TPS method, a comprehensive measurement validation is discussed along various residual plots obtained for varying input parameters (ie, the heating power and time). Clearly, the variations in the input parameters give rise to various thermal conductivity results, where choosing the most coherent result requires a sequence of efforts per material, because there are no universally valid conditions. Transparent and repeatable data and procedure reporting are the key to achieve comparable thermal conductivity results, which are essential for the correct design of thermal energy storage systems using PCMs.