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The electrochemical initiated heterocoupling of 3-methylcatechol and n-hexylamine was investigated. The oxidation of 3-methylcatechol was performed in an electrochemical flow cell with glassy carbon as the working electrode. As a result, the two-electron, two-proton oxidised chinone intermediate undergoes a C-N coupling reaction in the presence of an amine (Michael addition). This mono coupling product can undergo a second two-electron, two-proton oxidation depending on acidic or basic conditions and substrate ratios. This flow cell was coupled on-line with electrospray ionisation mass spectrometry to identify the possible coupling products. Higher substrate concentrations were performed off-line as first scale-up experiments in a two-step procedure. [ABSTRACT FROM AUTHOR]

Flavonols, a class of flavonoids, are jointly responsible for antioxidant activities as free radical acceptors in flowers, fruits and vegetables. Due to their electroactive behaviour, the oxidation of chrysin, flavonol, kaempferol, morin, quercetin and myricetin in methanol was performed in an electrochemical flow cell with glassy carbon as the working electrode. This flow cell was coupled online with electrospray ionisation mass spectrometry to identify the possible oxidation products. Based on these experiments, it was concluded that when certain structural requirement are present, the initial electrode reaction of flavonols involves an electron delivery electrochemical step followed by a chemical step via methanol addition. The redox activity of the selected species explains the number of observed multiple methoxylation. Moreover, we identified a second two-electron, two-proton oxidation of the formed oxidation products of quercetin and myricetin for the first time. [ABSTRACT FROM AUTHOR]

It was a big surprise to see crystals of an ionic liquid (IL) forming by sublimation at room temperature. ILs are generally accepted to have negligible vapour pressures at elevated temperatures, making their sublimation or distillation very difficult. ILs that sublime easily contain silylimidazolium-based cations. In order to establish the details of the unusual behaviour of this subclass of ILs, a combined spectroscopic, X-ray crystallographic, physicochemical and theoretical characterization was performed. The results are compared with those of other easily vaporizable compounds, like ammonium chloride and naphthalene. The single-crystal X-ray structure analysis of one of these compounds, N-methyl- N′-dimethyl(phenyl)silylimidazolium chloride (monoclinic, C2/ c), clearly shows the existence of isolated ions, demonstrating that the compound is an ionic liquid. [ABSTRACT FROM AUTHOR]

Compatible solutes are small molecules that are involved in acclimation to various abiotic stresses, especially high salinity. Among the red algae, the main photosynthetic products floridoside and isofloridoside (galactosylglycerols) are known also to contribute to the osmotic acclimation of cells. However, the genes encoding (iso)floridoside biosynthetic enzymes are still unknown., To identify candidate genes, we examined the genome of the floridoside- and isofloridoside-accumulating extremophilic red alga Galdieria sulphuraria belonging to the Cyanidiales. We hypothesized that two candidate genes, Gasu_10960 and Gasu_26940, code for enzymes involved in floridoside and isofloridoside biosynthesis. These proteins comprise a sugar phosphate synthase and a sugar phosphate phosphatase domain. To verify their biochemical activity, both genes were in vitro translated into the entire proteins., The protein translation mixture containing Gasu_10960 synthesized small amounts of isofloridoside, whereas the Gasu_26940 translation mix also produced small amounts of floridoside. Moreover, the expression of Gasu_10960 in a salt-sensitive mutant of the cyanobacterium Synechocystis sp. PCC 6803 resulted in increased salt tolerance as a consequence of the presence of isofloridoside in the complemented cells., Thus, our experiments suggest that the Gasu_26940 and Gasu_10960 genes of G. sulphuraria encode the enzymatically active floridoside and isofloridoside phosphate synthase/phosphatase fusion proteins, respectively, crucial for salt acclimation. [ABSTRACT FROM AUTHOR]

Flavonols, a class of flavonoids, are present in flowers, fruits and vegetables. They are jointly responsible for antioxidant activity as free radical acceptors. The redox behaviour of myricetin, quercetin, isorhamnetin, fisetin, morin and kaempferol is investigated using cyclic and differential pulse voltammetry. Quantum chemical calculations of proton affinities and electron transfer enthalpies were performed to identify possible reactive sites and radical species to compare them with measured oxidation potentials of the flavonols. Regarding to their chemical structure, these flavonols showed an oxidation order: myricetin > quercetin > isorhamnetin > fisetin > morin > kaempferol. [ABSTRACT FROM AUTHOR]

This study is aimed at improving a protocol for measuring fatty acids in cattle hair with respect to sensitivity, repeatability, and speed to increase its applicability as a biomarker. For the investigation, 14 hair samples from German Holstein cows are used. Alternative methods for grinding the hair (mortar vs mill), lipid extraction (modified Folch vs kit extraction), and solvent evaporation before injection on a gas chromatograph (evaporated vs unevaporated extracts) are tested. Hair ground with a mill compared to that with a mortar has smaller particles and a higher concentration of total lipids after extraction (p < 0.02). The kit used for lipid extraction is faster, and the amount of extracted total lipids and individual fatty acids, especially C12:0, is increased (p = 0.001). The analysis of unevaporated methyl ester extracts using gas chromatography (GC) analysis yields 5.8 and 1.3 higher amounts of C10:0 and C12:0, respectively, than those of evaporated extracts (p < 0.001). According to the results, the protocol for determining fatty acids in cattle hair can be improved by grinding the hair with a mill, extraction of lipids with a kit, and direct loading of methyl ester extracts in a gas chromatograph. Practical Applications: The fatty acid profile of hair reflects the metabolic status of an animal for the previous 1–3 weeks, as these fatty acids are not influenced by diurnal and short‐term fluctuations. An improved protocol is developed that increases the throughput of fatty acid analysis and improves its applicability for practical use. For breeding and animal welfare, the analysis of cattle hair is possible for more efficient evaluation of the hair fatty acid profile as a robust biomarker in a larger animal population. [ABSTRACT FROM AUTHOR]