Enzymatic biodiesel synthesis – Key factors affecting efficiency of the process

Chemical processes of biodiesel production are energy-consuming and generate undesirable by-products such as soaps and polymeric pigments that retard separation of pure methyl or ethyl esters of fatty acids from glycerol and di- and monoacylglycerols. Enzymatic, lipase-catalyzed biodiesel synthesis has no such drawbacks. Comprehension of the latter process and an appreciable progress in production of robust preparations of lipases may soon result in the replacement of chemical catalysts with enzymes in biodiesel synthesis. Engineering of enzymatic biodiesel synthesis processes requires optimization of such factors as: molar ratio of substrates (triacylglycerols: alcohol), temperature, type of organic solvent (if any) and water activity. All of them are correlated with properties of lipase preparation. This paper reports on the interplay between the crucial parameters of the lipase-catalyzed reactions carried out in non-aqueous systems and the yield of biodiesel synthesis.     

Functional relationships between phytochemicals and drying conditions during the processing of blackcurrant pomace into powders

The effect of convective drying, microwave-vacuum drying and their combination applied to blackcurrant by-product on the quality being measured in terms of the content of phytochemicals in the powders was examined. Convective drying, along with the increase in the temperature, linearly reduced the content of anthocyanins, flavonols and chlorogenic acids. Microwave vacuum drying significantly shortened the drying time, and resulted in higher retention of bioactive compounds at higher temperatures in comparison to convection. No functional relationship was observed between bioactive compounds and the power of magnetrons thus between the processing temperature and the content of individual groups of polyphenols, apart from delphinidin-3-O-rutinoside and delphinidin-3-O-glucoside. During the dehydration of blackcurrant pomace the exponential formation of hydroxymethylfurfural was noticed. The antioxidant capacity decreased along with the increase in drying temperature and in parallel with the decrease in anthocyanins content, thus suggesting that those polyphenols considerably influence the antioxidant potential of final products.     

Evaluation of antioxidant and antimicrobial activity of oregano (Origanum vulgare L.) preparations during storage of low-pressure mechanically separated meat (BAADER meat) from chickens

Food Science and Biotechnology - The goal of this study was to determine the effect of Origanum vulgare L. (oregano) preparations on the storage stability of vacuum-packed low-pressure mechanically...     

FGFR1–4 RNA-Based Gene Alteration and Expression Analysis in Squamous Non-Small Cell Lung Cancer

While fibroblast growth factor receptors (FGFRs) are involved in several biological pathways and FGFR inhibitors may be useful in the treatment of squamous non-small cell lung cancer (Sq-NSCLC), FGFR aberrations are not well characterized in Sq-NSCLC. We comprehensively evaluated FGFR expression, fusions, and variants in 40 fresh-frozen primary Sq-NSCLC (stage IA3–IV) samples and tumor-adjacent normal tissues using real-time PCR and next-generation sequencing (NGS). Protein expression of FGFR1–3 and amplification of FGFR1 were also analyzed. FGFR1 and FGFR4 median gene expression was significantly (p < 0.001) decreased in tumors compared with normal tissue. Increased FGFR3 expression enhanced the recurrence risk (hazard ratio 4.72, p = 0.029), while high FGFR4 expression was associated with lymph node metastasis (p = 0.036). Enhanced FGFR1 gene expression was correlated with FGFR1 protein overexpression (r = 0.75, p = 0.0003), but not with FGFR1 amplification. NGS revealed known pathogenic FGFR2,3 variants, an FGFR3::TACC3 fusion, and a novel TACC1::FGFR1 fusion together with FGFR1,2 variants of uncertain significance not previously reported in Sq-NSCLC. These findings expand our knowledge of the Sq-NSCLC molecular background and show that combining different methods increases the rate of FGFR aberrations detection, which may improve patient selection for FGFRi treatment.     

How the replacement of cholesterol by 25-hydroxycholesterol affects the interactions with sphingolipids: The Langmuir Monolayer Study complemented with theoretical calculations

In this paper, a representative of chain-oxidized sterols, 25-hydroxycholesterol (25-OH), has been studied in Langmuir monolayers mixed with the sphingolipids sphingomyelin (SM) and ganglioside (GM₁) to build lipid rafts. A classical Langmuir monolayer approach based on thermodynamic analysis of interactions was complemented with microscopic visualization of films (Brewster angle microscopy), surface-sensitive spectroscopy (polarization modulation–infrared reflection–absorption spectroscopy) and theoretical calculations (density functional theory modelling and molecular dynamics simulations). Strong interactions between 25-OH and both investigated sphingolipids enabled the formation of surface complexes. As known from previous studies, 25-OH in pure monolayers can be anchored to the water surface with a hydroxyl group at either C(3) or C(25). In this study, we investigated how the presence of additional strong interactions with sphingolipids modifies the surface arrangement of 25-OH. Results have shown that, in the 25-OH/GM₁ system, there are no preferences regarding the orientation of the 25-OH molecule in surface complexes and two types of complexes are formed. On the other hand, SM enforces one specific orientation of 25-OH: being anchored with the C(3)–OH group to the water. The strength of interactions between the studied sphingolipids and 25-OH versus cholesterol is similar, which indicates that cholesterol may well be replaced by oxysterol in the lipid raft system. In this way, the composition of lipid rafts can be modified, changing their rheological properties and, as a consequence, influencing their proper functioning.     

β‐Aminopeptidase‐Catalyzed Biotransformations of β2‐Dipeptides: Kinetic Resolution and Enzymatic Coupling

We have previously shown that the β‐aminopeptidases BapA from Sphingosinicella xenopeptidilytica and DmpA from Ochrobactrum anthropi can catalyze reactions with non‐natural β³‐peptides and β³‐amino acid amides. Here we report that these exceptional enzymes are also able to utilize synthetic dipeptides with N‐terminal β²‐amino acid residues as substrates under aqueous conditions. The suitability of a β²‐peptide as a substrate for BapA or DmpA was strongly dependent on the size of the C_α substituent of the N‐terminal β²‐amino acid. BapA was shown to convert a diastereomeric mixture of the β²‐peptide H‐β²hPhe‐β²hAla‐OH, but did not act on diastereomerically pure β²,β³‐dipeptides containing an N‐terminal β²‐homoalanine. In contrast, DmpA was only active with the latter dipeptides as substrates. BapA‐catalyzed transformation of the diastereomeric mixture of H‐β²hPhe‐β²hAla‐OH proceeded along two highly S‐enantioselective reaction routes, one leading to substrate hydrolysis and the other to the synthesis of coupling products. The synthetic route predominated even at neutral pH. A rise in pH of three log units shifted the synthesis‐to‐hydrolysis ratio (v_S/v_H) further towards peptide formation. Because the equilibrium of the reaction lies on the side of hydrolysis, prolonged incubation resulted in the cleavage of all peptides that carried an N‐terminal β‐amino acid of S configuration. After completion of the enzymatic reaction, only the S enantiomer of β²‐homophenylalanine was detected (ee>99 % for H‐(S)‐β²‐hPhe‐OH, E>500); this confirmed the high enantioselectivity of the reaction. Our findings suggest interesting new applications of the enzymes BapA and DmpA for the production of enantiopure β²‐amino acids and the enantioselective coupling of N‐terminal β²‐amino acids to peptides.     

The effect of the surface nanostructure and composition on the antiwear properties of zirconia–titania coatings

This study describes the preparation, surface imaging and tribological properties of titania coatings modified by zirconia nanoparticles agglomerated in the form of island-like structures on the titania surface. Titania coatings and titania coatings with embedded zirconia nanoparticles were prepared by the sol–gel spin coating process on silicon wafers. After deposition the coatings were heat-treated at 500 °C or 1000 °C. The natural tendency of nanoparticles to form agglomerates was used to build separated island-like structures unevenly distributed over the titania surface having the size of 1.0–1.2 μm. Surface characterization of coatings before and after frictional tests was performed by atomic force microscopy (AFM) and optical microscopy. Zirconia nanoparticles were imaged with the use of transmission electron microscopy (TEM). The tribological properties were evaluated with the use of microtribometer operating in ambient air at technical dry friction conditions under normal load of 80 mN. It was found that nanocomposite coatings exhibit lower coefficient of friction (CoF) and considerably lower wear compared to titania coating without nanoparticles. The lowering of CoF is about 40% for coatings heated at 500 °C and 33% for the coatings heated at 1000 °C. For nanocomposites the wear stability was enhanced by a factor of 100 as compared to pure titania coatings. We claim that enhanced tribological properties are closely related to the reduction of the real contact area, lowering of the adhesive forces in frictional contacts and increasing of the composite hardness. The changes in materials composition in frictional contact has secondary effect.