Scaling of Shielded Sliding Discharges for Environmental Applications

Shielded sliding discharges are nanosecond streamer discharges which develop along a dielectric between metal foil electrodes, with one of the foils extended over the entire rear of the dielectric layer. The electrode configuration not only allowed rearranging discharges in parallel due to the decoupling effect of the metal layer, but also to modify the electric field distribution in such a way that components normal to the surface are enhanced, leading to an increased energy density in the discharge plasma. By varying the electrode gap, the applied voltage, and the repetition rate, it is shown that by keeping the average electric field constant, the discharge voltage can be reduced from tens of kV to values on the order of a few kV, but only at the expense of a reduced energy density of the plasma. Varying the repetition rate from 20 to 500 Hz resulted in a slightly reduced energy per pulse, likely caused by residual charges on the dielectric surface. Measurements of the NO conversion to NO₂ and ozone synthesis in dry air showed that the conversion is only dependent on the energy density of the discharge plasma. Although reducing the pulse voltage from the tens of kV range to that of few kV, and possibly even lower, causes a reduction in energy density, this loss can be compensated for by increasing the electrode gap area. This and the possibility to form discharge arrays allows generating large volume discharge reactors for environmental applications, at modest pulsed voltages.     

Essential Role of the N- and C-terminals of Laccase from Pleurotus florida on the Laccase Activity and Stability

POXA1b is the most thermostable laccase isoenzyme from Pleurotus ostreatus. POXA1b is remarkably stable at alkaline pH (the t_1/2 at pH 10 was 30 days), and its C-terminal affects its catalytic and stability properties. We cloned POXA1c from P. florida, which showed 99 % identity with POXA1b. POXA1c was functionally expressed in Pichia pastoris. The functions of the N and C termini of POXA1c were investigated using site-directed mutagenesis. Compared with POXA1c, the N-terminal R5V site effectively increased the specific activities for 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and guaiacol by 2- and 3.5-fold, respectively. A C-terminal truncated mutant, POXA1c△13, also increased the specific activities for ABTS and guaiacol by 2.3- and 3.4-fold, respectively. A double mutant, POXA1cΔ13-R5V, combined the R5V and △13 effects. The specific activity of this double mutant for ABTS was 1,321 U/mg, which indicated a 4-fold increase compared with the wild type. The role of residue V5 on laccase catalytic properties was also observed for laccases from Trametes versicolor and Rigidoporus lignosus. The specific activities of the V5R of the laccases from T. versicolor and R. lignosus were half of that of the wild type. The pH and thermal stability analysis of POXA1c and its mutants showed that the enzymes were remarkably stable because they showed 63 % residual activity after incubation for 108 h at 30 °C over a pH range of 4.5 to 9.0. Similar results were observed for POXA1cΔ13-R5V. POXA1cΔ13-R5V can be widely used in industrial biotechnology because of its excellent catalytic properties.     

Enhanced solubility of galangin based on the complexation with methylated microbial cyclosophoraoses

Methylated cyclosophoraoses (M-Cys) were synthesized by reaction using dimethyl sulfate with native Cys (unbranched cyclic β-1,2-d-glucans) isolated from Rhizobium leguminosarum biovar viciae VF-39. Its structure was proven using nuclear magnetic resonance (¹H NMR) spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Based on the enhanced hydrophobicity by methylation of Cys, we investigated the inclusion property with the water-insoluble flavonoid, galangin, through a phase solubility study using ultraviolet–visible spectroscopy. The solubility of galangin was enhanced 5.6-fold according to the added concentrations (1 mM) of M-Cys, compared to the 1.9-fold and 3.4-fold enhancements by β-Cyclodextrin (β-CD) and heptakis (2,6-di-O-methyl)-β-cyclodextrin (DM-β-CD), respectively. M-Cys was also shown to have the highest binding constant (5,534 M^?1) with galangin among the tested host molecules (β-CD, DM-β-CD, Cys, and M-Cys). From this result, we can infer that the complex of galangin with M-Cys is more stable than any of the other host molecules. The continuous variation method showed that the galangin/M-Cys complex was suitable for 1:1 stoichiometry. The formation of the complex was confirmed with ¹H NMR, FT-IR, differential scanning calorimetry, and scanning electron microscopy. Furthermore, the hypothetical molecular model of 1:1 galangin/M-Cys complex was suggested by molecular docking simulations. The cytotoxicity to the human cervical adenocarcinoma cell lines was enhanced by the galangin/M-Cys complex compared with free galangin. The obtained results indicate that M-Cys can be utilized as an effective complexing agent for galangin.     

Metal–Sulfur Linkages Achieved by Organic Tethering of Ruthenium Nanocrystals for Enhanced Electrochemical Nitrogen Reduction

Inspired by the metal–sulfur (M-S) linkages in the nitrogenase enzyme, here we show a surface modification strategy to modulate the electronic structure and improve the N₂ availability on a catalytic surface, which suppresses the hydrogen evolution reaction (HER) and improves the rate of NH₃ production. Ruthenium nanocrystals anchored on reduced graphene oxide (Ru/rGO) are modified with different aliphatic thiols to achieve M-S linkages. A high faradaic efficiency (11 %) with an improved NH₃ yield (50 μg h⁻¹ mg⁻¹) is achieved at −0.1 V vs. RHE in acidic conditions by using dodecanethiol. DFT calculations reveal intermediate N₂ adsorption and desorption of the product is achieved by electronic structure modification along with the suppression of the HER by surface modification. The modified catalyst shows excellent stability and recyclability for NH₃ production, as confirmed by rigorous control experiments including ¹⁵N isotope labeling experiments.     

First-principle investigation of XSrH3 (X = K and Rb) perovskite-type hydrides for hydrogen storage

Hydrogen can be utilized as an energy source; therefore, hydrogen storage has received the most appealing examination interest in recent years. The investigations of hydrogen storage applications center fundamentally around the examination of hydrogen capacity abilities of recently presented compounds. XSrH₃ (X = K and Rb) compounds have been examined by density functional theory (DFT) calculations to uncover their different characteristics, as well as hydrogen capacity properties, for the first time. Studied compounds are optimized in the cubic phase, and optimized lattice constants are obtained as 4.77 and 4.99 Å for KSrH₃ and RbSrH₃, respectively. These hydrides have shown negative values of formation enthalpies as they are stable thermodynamically. XSrH₃ might be used in hydrogen storage applications because of high gravimetric hydrogen storage densities, which are 2.33 and 1.71 wt% for KSrH₃ and RbSrH₃, respectively. Moreover, electronic properties confirm the semiconductor nature of these compounds having indirect band gaps of values 1.41 and 1.23 eV for KSrH₃ and RbSrH₃, respectively. In addition, mechanical properties from elastic constants such as Young modulus and Pugh's ratio, also have been investigated, and these compounds were found to satisfy born stability conditions. Furthermore, Pugh's ratio and Cauchy pressure show that these hydrides have a brittle nature. Furthermore, thermodynamic properties such as entropy and Debye temperature have been examined using the quasiharmonic Debye model for different temperatures and pressures.     

Synthesis,anticancer, and computational studies of 1, 3, 4-oxadiazole-purine derivatives

Theophylline-7-acetic acid (acefylline) ( 3 ) and its derivatives are pharmacologically active compounds and generally recognized as bronchodilators for the treatment of respiratory diseases like acute asthma for over 70 years. In this article, synthesis of 2-((5-((1,3-dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-yl)thio)-N-arylacetamides ( 10a-j ) has been reported. All the synthesized derivatives ( 10a-j) were structurally verified by FT-IR, ¹H NMR, ¹³C NMR and evaluated for their anti-cancer (using MTT assay), hemolytic and thrombolytic potential. N-(4-Chlorophenyl)-2-(5-((1,3-dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-ylthio)acetamide ( 10g ) was found to be the most active against human liver cancer cell lines (Huh7) having cell viability 53.58 ± 1.28 using 100 μg/mL concentration of compound which was further in-silico modelled to describe the possible mechanistic insights for its anti-proliferative activity. The results of hemolytic and thrombolytic activities indicated that these derivatives were less toxic and hold considerable potential as a drug candidate. 2-(5-((1,3-Dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-ylthio)-N-(2-fluorophenyl)acetamide ( 10c ) of the series was found to be least toxic with 0.1% hemolysis relative to ABTS (95.5%) as positive control. 2-(5-((1,3-Dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-ylthio)-N-(tetrahydro-2H-pyran-4-yl)acetamide ( 10j ) exhibited potent clot lysis activity (90%) as compared to negative control DMSO (0.57%).     

Synthesis of heterocycles using nanomagnetic nickel catalysts

Abstract

Heterocyclic scaffolds are important components in the structure of many drugs and natural products. They are well-known compounds because of their broad spectrum of pharmaceutical and biological activities. In this paper, we provide an overview of the utilization of nickel complexes immobilized on magnetic nanoparticles as attractive and efficient catalytic systems for synthesis of heterocyclic molecules.     

Synthesis,Structure and Elastic Properties of a New Hybrid Perovskite Material: [C6H14N2]KBr3

A new hybrid organic-inorganic perovskite(HOIP)material,[C6H14N2]KBr3,has been synthesized via hydrothermal method and fully characterized.[C6H14N2]KBr3 has a three-dimensional perovskite structure and crystalizes in a trigonal P3121 space group.The elastic properties of[C6H14N2]KBr3 were fully calculated via the density functional theory calculations,which reveal the elastic moduli(11.54~14.07 GPa),shear moduli(4.56~5.68 GPa),Poisson’s ratios(0.18~0.32),bulk modulus(8.51 GPa)and acoustic velocity(2.57~2.74 kms^-1).Additional nanoindentation experiments in the form of single-crystals confirmed the validity of our theoretical approach.[C6H14N2]KBr3 exhibits higher stiffness and thermal stability than the well-known photovoltaic CH3NH3PbI3,which makes it worthwhile for exploring optoelectronic properties.     

Selective cytotoxicity of organotin(IV) compounds with 2,3-dihydroxybenzyldithiocarbazate Schiff bases

Research on Chemical Intermediates - A series of tridentate ONS Schiff bases were synthesised via condensation by reacting 2,3-dihydroxybenzaldehyde with S-2-methylbenzyldithiocarbazate (S2MBDTC)...     

Thermal dry reforming of methane over La2O3 co-supported Ni/MgAl2O4 catalyst for hydrogen-rich syngas production

Research on Chemical Intermediates - The excess emission of greenhouse gases (GHGs) such as CO2 and CH4 is posing an acute threat to the environment, and efficient ways are being sought to utilize...