2,4,6‐Triarylphosphinines versus 2,4,6‐Triarylpyridines: An Investigation of the Differences in Reactivity between Structurally Related Aromatic Phosphorus and Nitrogen Heterocycles

The novel atropisomeric pyridine derivative rac‐ 10 has been synthesized and structurally characterized. In contrast to its phosphorus analogue 3 , axially chiral 10 has a considerably lower rotational barrier as estimated by DFT calculations. However, the presence of the two enantiomers could be confirmed by means of chiral analytical HPLC analysis and by protonation experiments with a chiral acid. Compound rac‐ 10 could be further dehydrogenated by treatment with DDQ to the benzo(h)quinoline derivative rac‐ 12 . This conversion failed for the phosphorus analogue rac‐ 3 . Interestingly, although 2,4,6‐triarylphosphinines undergo facile C? H activation with [Cp*IrCl₂]₂ in the presence of NaOAc, this reaction does not proceed with the corresponding pyridine derivatives. On the other hand, the latter ones can be selectively ortho‐metalated with Pd(OAc)₂, leading to acetate‐bridged dimeric species, which could be unambiguously confirmed by means of X‐ray crystal structure analysis. The treatment of phosphinines with Pd(OAc)₂ led instead to the formation of the unusual cofacial oxidative coupling products 16 and 17 , which consist of a phosphorus‐containing cage structure.     

Pulse perturbation technique for determination of piroxicam in pharmaceuticals using an oscillatory reaction system

A simple and reliable novel kinetic method for the determination of piroxicam (PX) was proposed and validated. For quantitative determination of PX, the Bray-Liebhafsky (BL) oscillatory reaction was used in a stable non-equilibrium stationary state close to the bifurcation point. Under the optimized reaction conditions (T = 55.0°C, [H₂SO₄]₀ = 7.60×10^?2 mol L^?1, [KIO₃]₀ = 5.90×10^?2 mol L^?1, [H₂O₂]₀ = 1.50×10^?1 mol L^?1 and j ₀ = 2.95×10^?2 min^?1), the linear relationship between maximal potential shift ΔE _m , and PX concentration was obtained in the concentration range 11.2–480.5 μg mL^?1 with a detection limit of 9.9 μg mL^?1. The method had a rather good sample throughput of 25 samples h^?1 with a precision RSD = 4.7% as well as recoveries RCV ≤ 104.4%. Applicability of the proposed method to the direct determination of piroxicam in different pharmaceutical formulations (tablets, ampoules and gel) was demonstrated.      

Advances in interactive supported electrocatalysts for hydrogen and oxygen electrode reactions

Magneli phases [A. Magneli, Acta Chem. Scand. 13 (1959) 5] have been introduced as a unique electron conductive and interactive support for electrocatalysis both in hydrogen (HELR) and oxygen (OELR) electrode reactions in water electrolysis and Low Temperature PEM Fuel Cells (LT PEM FC). The Strong Metal-Support Interaction (SMSI) that imposes the former implies: (i) the hypo-hyper-d-interbonding effect and its catalytic consequences, and (ii) the interactive primary oxide (M-OH) spillover from the hypo-d-oxide support as a dynamic electrocatalytic contribution. The stronger the bonding, the more strained appear d-orbitals, thereby the less strong the intermediate adsorptive strength in the rate determining step (RDS), and consequently, the faster the facilitated catalytic electrode reaction arises. At the same time the primary oxide spillover transferred from the hypo-d-oxide support directly interferes and reacts either individually and directly to contribute to finish the oxygen reduction, or with other interactive species, like CO to contribute to the CO tolerance. In such a respect, the conditions to provide Au to act as the reversible hydrogen electrode have been proved either by its potentiodynamic surface reconstruction in a heavy water solution, or by the nanostructured SMSI Au on anatase titania with characteristic strained d-orbitals in such a hypo-hyper-d-interactive bonding (Au/TiO₂). In the same context, some spontaneous tendency towards monoatomic network dispersion of Pt upon Magneli phases makes it possible to produce an advanced interactive supported electrocatalyst for cathodic oxygen reduction (ORR). The strained hypo-hyper-d-interelectronic and inter-d-orbital metal/hypo-d-oxide support bonding relative to the strength of the latter, has been inferred to be the basis of the synergistic electrocatalytic effect both in the HELR and ORR.     

Formation Mechanism of the First Carbon–Carbon Bond and the First Olefin in the Methanol Conversion into Hydrocarbons

The elementary reactions leading to the formation of the first carbon–carbon bond during early stages of the zeolite‐catalyzed methanol conversion into hydrocarbons were identified by combining kinetics, spectroscopy, and DFT calculations. The first intermediates containing a C?C bond are acetic acid and methyl acetate, which are formed through carbonylation of methanol or dimethyl ether even in presence of water. A series of acid‐catalyzed reactions including acetylation, decarboxylation, aldol condensation, and cracking convert those intermediates into a mixture of surface bounded hydrocarbons, the hydrocarbon pool, as well as into the first olefin leaving the catalyst. This carbonylation based mechanism has an energy barrier of 80 kJ mol^?1 for the formation of the first C?C bond, in line with a broad range of experiments, and significantly lower than the barriers associated with earlier proposed mechanisms.     

Phenolic compounds in field horsetail (Equisetum arvense L.) as natural antioxidants

In this paper, the study of antioxidant activity and phenolic composition of three different extracts (EtOAc, n-BuOH and H(2)O) of field horsetail (Equisetum arvense L.) is presented. The antioxidant activity has been evaluated measuring the total reducing power (expressed by Ascorbate Equivalent Antioxidant Capacity - AEAC), inhibition of lipid peroxidation, and free radical scavenging capacity (RSC) towards 2,2-diphenyl-1-picrylhydrazyl (DPPH radical) and nitric oxide (NO), respectively. In addition, the total flavonoid content (TFC) and phenolic constituents of each extract have been determined. The results obtained show that the highest RSC regarding both DPPH and NO radicals is expressed by EtOAc extract (EC(50)=2.37 microg/mL and EC(50)=90.07 microg/mL, respectively), and the lowest by H(2)O extract (EC(50)=37.2 microg/mL and EC(50)>333.33 microg/mL, respectively). n-BuOH extract showed the highest total reducing power (AEAC=13.40 microg/mL). Differences in the phenolic composition of examined extracts are found comparing the HPLC chemical profiles. Although, isoquercitrin is the main flavonoid in both EtOAc and n-BuOH extracts, a considerable amount of di-E-caffeoyl-meso-tartaric acid was presented in the n-BuOH extract. In H(2)O extract high content of phenolic acids and low percentage of flavonoids were detected.     

Nano-biopower supplies for biomolecular motors: the use of metabolic pathway-based fuel generating systems in microfluidic devices

We report fuel generation systems for molecular motors based on pyruvate kinase, or for the first time, mitochondria, implemented within microfluidic devices. Intact organelles acted as bio-nanopower supplies for molecular motors, using isolated mitochondria to convert chemical energy from succinate to ATP, harnessing nature's enzymatic transformation cascades directly. Motors were activated essentially equally by ATP produced by pyruvate kinase, mitochondria, or direct addition of ATP.     

Comparison of the contents of various antioxidants of sea buckthorn berries using CE

The increased interest in sea buckthorn (Hippophae rhamnoides L.) made it possible to investigate the antioxidant content in it. To address this issue, the presence of following antioxidant compounds were analyzed: trans-resveratrol, catechin, myricetin, quercetin, p-coumaric acid, caffeic acid, L-ascorbic acid (AA), and gallic acid (linear range of 50-150 micromol/L) in six different varieties of sea buckthorn berries extracts (sea buckthorn varieties: "Trofimovskaja (TR)," "Podarok Sadu (PS)," and "Avgustinka (AV),") received from two local Estonian companies. Trans-Resveratrol, catechin, AA, myricetin, and quercetin were found in extracts of sea buckthorn. Moreover, AA, myricetin, and quercetin contents were quantified. The biggest average AA content was found in TR (740 mg/100 g of dried berries, respectively). Furthermore, the same varieties gave the biggest quercetin content 116 mg/100 g of dried berries, respectively. For analysis, CZE was used and the results were partly validated by HPLC. Statistically no big differences in levels of antioxidants were consistently found in different varieties of sea buckthorn extracts investigated in this work.     

Application of liquid chromatography-electrospray ionisation mass spectrometry for determination of dietary folates: effects of buffer nature and mobile phase composition on sensitivity and selectivity

A sensitive and reliable liquid chromatography-mass spectrometry (LC-MS) method to determine dietary folates was developed and validated. Folates were detected and quantified using positive electrospray ionisation (ESI) with selective ion monitoring of protonated ions [M+H]+. The effects of buffer nature and mobile phase composition on separation, peak shape and intensity of MS signal were investigated. The acidic-basic properties of folates were successfully used to predict possible ionisation patterns, but they were not sufficient to predict the intensity of MS signal and the proportion of different ionisation products, which indicated that other parameters, such as gas phase acidity/basicity of analytes and ion evaporation mechanisms might be important. The use of aqueous acetic acid as volatile buffer was found to be preferable compared to formic acid due to considerable gain in intensity of MS signal for all folate forms studied. Limits of quantifications were 0.3 ng/mL for 5-methyltetrahydrofolate and 0.6 ng/mL for tetrahydrofolate, 10-formylfolic acid, 5-formyltetrahydrofolate and folic acid when using 20 microL injection. For 10-formylfolic acid, 5-formyltetrahydrofolate and folic acid the MS detection was found to be superior over commonly used fluorescence and UV detection in terms of selectivity and sensitivity. The method was successfully applied to analysis of folates in baker's yeast.     

Parenchyma cell wall structure in twining stem of <Emphasis Type="Italic">Dioscorea balcanica</Emphasis>

Anatomical adaptation of liana plants includes structural changes in cell walls of different tissues: fibers, vessel elements and tracheids. However, the contribution of parenchyma cells to stem twining in liana plants is mostly unknown. The aim of this investigation is to determine changes in stem parenchyma cell walls that are correlated with the twinning process in liana plants. Parenchyma cell wall structure was studied on the stem cross sections of straight and twisted internodes of monocotyledonous liana Dioscorea balcanica, by different microscopy techniques: light microscopy, scanning electron microscopy, fluorescence detected linear dichroism microscopy and Fourier transform infrared microspectrometry. In addition, chemical analysis of the entire stem internodes was performed using photometric and chromatographic methods. Parenchyma cell walls of twisted D. balcanica internodes are characterized by: lower amounts of cellulose (obtained by FTIR microspectrometry) with different cellulose microfibril orientation (shown by Scanning electron microscopy), but no changes in “cellulose fibril order” (obtained by Differential polarization laser scanning microscopy); lower amounts of xyloglucan, higher amounts of xylan, higher amounts of lignin with modified organization—less condensed lignin (obtained by FTIR microspectrometry). At the same time, chemical analysis of the entire internodes did not show significant differences in lignin content and cell wall bound phenols related to stem twining, except for the presence of diferulate cross-links exclusively in twisted internodes. Our results indicate that adaptations to mechanical strain in D. balcanica stems involve modifications in parenchyma cell wall structure and chemistry, which provide decreased stiffness, higher strength and increased elasticity of twisted internodes.     

Eco-friendly rapid synthesis of 3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones in choline chloride based deep eutectic solvent

A series of 3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones and 6-iodo-3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones were synthesized in choline chloride/urea deep eutectic solvent. Substituted 2-mercapto-4(3H)-quinazolinones were synthesized from anthranilic acid or 5-iodoanthranilic acid and appropriate isothiocyanates in good to excellent yields. Isolation of final product was easy and required no further purification. Synthesis of these compounds was rapid, selective, and catalyst free, while preparation of deep eutectic solvent was easy, components are readily available, cheap, and environmentally friendly.