Substituted 2-Phenacylbenzoxazole Difluoroboranes: Synthesis,Structure and Properties

Novel fluorescent dyes such as benzoxazole-boron complexes, bearing β-ketoiminate ligands, have been synthesized and characterized with a focus on the influence of a substituent on the basic photophysical properties. ¹H, ¹¹B, ¹³C, ¹⁵N, and ¹⁹F nuclear magnetic resonance (NMR) spectra of substituted 2-phenacylbenzoxazole difluoroboranes have been recorded and discussed. It is worth mentioning that a high correlation coefficient was found between ¹⁵N-NMR parameters and substituent constants. The photophysical properties of these new dyes have been investigated by fluorescence and ultraviolet-visible (UV-Vis) absorption spectroscopy. The geometry optimization, vibrational spectra, and the HOMO and LUMO energies were calculated based on density functional theory with the use of the B3LYP functional and 6-311++G(d,p) basis set.     

Production of Verbascoside,Isoverbascoside and Phenolic Acids in Callus,Suspension, and Bioreactor Cultures of Verbena officinalis and Biological Properties of Biomass Extracts

Callus, suspension and bioreactor cultures of Verbena officinalis were established, and optimized for biomass growth and production of phenylpropanoid glycosides, phenolic acids, flavonoids and iridoids. All types of cultures were maintained on/in the Murashige and Skoog (MS) media with 1 mg/L BAP and 1 mg/L NAA. The inoculum sizes were optimized in callus and suspension cultures. Moreover, the growth of the culture in two different types of bioreactors—a balloon bioreactor (BB) and a stirred-tank bioreactor (STB) was tested. In methanolic extracts from biomass of all types of in vitro cultures the presence of the same metabolites—verbascoside, isoverbascoside, and six phenolic acids: protocatechuic, chlorogenic, vanillic, caffeic, ferulic and rosmarinic acids was confirmed and quantified by the HPLC-DAD method. In the extracts from lyophilized culture media, no metabolites were found. The main metabolites in biomass extracts were verbascoside and isoverbascoside. Their maximum amounts in g/100 g DW (dry weight) in the tested types of cultures were as follow: 7.25 and 0.61 (callus), 7.06 and 0.48 (suspension), 7.69 and 0.31 (BB), 9.18 and 0.34 (STB). The amounts of phenolic acids were many times lower, max. total content reached of 26.90, 50.72, 19.88, and 36.78 mg/100 g DW, respectively. The highest content of verbascoside and also a high content of isoverbascoside obtained in STB (stirred-tank bioreactor) were 5.3 and 7.8 times higher than in extracts from overground parts of the parent plant. In the extracts from parent plant two iridoids—verbenalin and hastatoside, were also abundant. All investigated biomass extracts and the extracts from parent plant showed the antiproliferative, antioxidant and antibacterial activities. The strongest activities were documented for the cultures maintained in STB. We propose extracts from in vitro cultured biomass of vervain, especially from STB, as a rich source of bioactive metabolites with antiproliferative, antioxidant and antibacterial properties.     

Proficiency assessment of laboratories undertaking hard coal analysis

The Institute for Chemical Processing of Coal in Zabrze, Poland, organized a proficiency testing round to determine the mass fraction of ash, total sulfur and total carbon and the value of gross calorific value. Forty-four participants from Polish heat and power plants, research entities and independent laboratories reported results. The performance of the participants was evaluated using z and E _n scores. Over 85 % of the participants reported satisfactory results indicating the high level of proficiency of the Polish laboratories in the field.     

A novel method for the detection of plasma jet boundaries by exploring DNA damage

The coupled-channel optical method (CCOM) is implemented in this work to study the scattering of electron on rubidium atom at 20 eV. In order to provide a realistic calculation, the continuum effect of the scattering system is accounted by incorporate an ab initio optical potential into the CCOM calculation. The differential cross sections (DCS), as well as the reduced Stokes parameters of 5p excitation are reported and compared to the available experimental and theoretical data.     

Empirical wavelet analysis of tail and memory properties of LARCH and FIGARCH models

Using computationally efficient wavelet methods, we study two nonlinear models of financial returns {r _t }: linear ARCH (LARCH) and fractionally integrated GARCH (FIGARCH). We estimate the tail index α and the long memory parameter d of the squared returns X_t = r_t²{X_t= r_t^2} of LARCH, and of the powers X _t = |r _t | ^p of FIGARCH. We find that the X _t have infinite variance and long memory, and show how the estimates of α and d depend on the model parameters. These relationships are determined empirically, as the setting is quite complex, and no suitable theory has been developed so far. In particular, we provide empirical relationships between the estimates [^(d)]{\hat d} and the difference parameters in LARCH and FIGARCH. Our computational work uncovers tail and memory properties of LARCH and FIGARCH for practically relevant parameter ranges, and provides some guidance on modeling returns on speculative assets including FX rates, stocks and market indices.     

Highly sulfurated heterocycles via dithiiranes and trithietanes as key intermediates

2,2,4,4-Tetramethyl-3-thioxocyclobutanone (8b) easily reacts with gaseous chlorine to yield the stable alpha-chloro sulfenyl chloride 10. The same product was obtained when 8b was treated either with phosphorus pentachloride (PCl(5)) or sulfuryl chloride (SO(2)Cl(2)) in CCl(4) solution. Sulfur dichloride (SCl(2)) reacts with 8b to give the alpha-chloro thiosulfenyl chloride 12 along with an almost equimolar amount of the trisulfide 13b. The less reactive disulfur dichloride (S(2)Cl(2)) was shown to react slowly with 8b and the symmetrical tetrasulfide 15 was found as the exclusive product. The pure thiosulfenyl chloride 12 added to adamantanethione (8c) yielded the unsymmetrical trisulfide 13c. When 12 was treated with thioacetic acid, the acetylated trisulfide 17 was formed in high yield. "Unzipping" reactions with the acetylated disulfide 16 and trisulfide 17 with morpholine in THF at -40 degrees C led to the formation of mixtures of two sulfur-rich heterocycles identified as the pentathiepane 6b and the hexathiepane 7b. A mixture of analogous products was obtained when alpha-chloro sulfenyl chloride 10 was treated with sodium sulfide in anhydrous THF at -40 degrees C. The formation of 6b and 7b is believed to occur via the intermediate dithiirane 1b and/or the isomeric thiosulfine 2b. In the case of 17 the reaction starts probably with the formation of a nonisolable tetrathiane 18b as presented in Scheme 5.