Effect of orientation of lateral methyl substituent on the thermal behaviour of the mesophase in binary systems of 4-substituted phenyl 4ʹ-(4”-alkoxy phenylazo) benzoates

Several binary systems made from two laterally substituted azo/ester isomers, namely 2?- (and 3?-) methyl-4-substituted phenyl 4?-(4?-alkoxyphenylazo) benzoates, where the length of the terminal alkoxy group = 8 and 16 carbons, while the other terminal substituent, X, varies between CH₃O, CH₃, H, Br and CN groups, were investigated using differential scanning calorimetry (DSC) and phases identified by polarised light microscope (PLM). For the sake of comparison, two another binary systems made from 2?- (or 3?-) methyl-4-substituted phenyl 4?-(4?-alkoxyphenylazo) benzoates (n = 8 and X = CH₃) each was mixed with its laterally neat analogue and similarly investigated. Results were discussed on the basis of constructed phase diagrams whereby various mesomorphic properties were observed dependent on X, n, and position of the lateral methyl group. In most of the cases, the mixtures exhibited eutectic compositions, while linear or nearly linear nematic and smectic A-composition temperature dependence were observed.     

Electrical and electrochemical characteristics of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>CoO<Subscript>3-δ</Subscript> cathode materials synthesized by a modified citrate-EDTA sol-gel method assisted with activated carbon for proton-conducting solid oxide fuel cell application

The electrical conductivity and electrochemical performance of a La_0.6Sr_0.4CoO_3-δ (LSC) cathode produced by a modified citrate-EDTA sol-gel method assisted with activated carbon are characterized for a proton-conducting solid oxide fuel cell (H⁺??SOFC) application at intermediate temperature. Thermogravimetric analysis revealed that the decomposition of the unrequired intermediate compounds in the precalcined powder was completed at 800?°C. A single LSC perovskite phase was formed at a calcination temperature of 900?°C, as confirmed by X-ray diffraction analysis. The particle size, crystallite size, and BET-specific surface area of the powder are 219–221?nm, 18?nm, and 9.87?m²?g^?1, respectively. The high index value of the extent of agglomeration (5.53) showed that the powder was barely agglomerated. Bulk LSC sintered at 1200?°C for 2?h showed the highest direct-current electrical conductivity (σ_d.c) compared to that of bulk LSC sintered at 1000?°C and 1100?°C. The value of σ_d.c was affected by the density and porosity of the sintered samples. The area specific resistance (ASR) of screen-printed LSC working on a proton conductor of BaCe_0.54Zr_0.36Y_0.1O_2.95 (BCZY) decreased from 5.0?Ω?cm²–0.06?Ω?cm² as the temperature increased from 500?°C to 800?°C with an activation energy of 1.079?eV. Overall, in this work, the LSC material produced with the aid of activated carbon meet the requirements for the application as a cathode in an intermediate temperature H⁺-SOFC.

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Dispersion of polymeric-coated–silica aerogel particles in unsaturated polyester composites: Effects on thermal-mechanical properties

The thermal-mechanical properties of unsaturated polyester (UP) composite were enhanced by the dispersion of silica aerogel (SA) with preserved pores. Low-cost SA was prepared from rice husk via the sol-gel process and ambient pressure drying. A new method was proposed to encapsulate the hydrophobic aerogel surface pores with hydrophilic polyvinyl alcohol (PVA) film using the fluidized-bed coating process. The dispersion of PVA-coated aerogel with preserved pores in the polyester matrix resulted in an increase of specific compressive strength (44.1?MPa?·?cm³?g^?1), thermal insulation (0.23?W?m^?1?K^?1), and thermal stability (T_onset?=?310°C), but decreased the glass transition temperature (T_g?=?260°C).     

Human Health Risk Surveillance Through the Determination of Organochlorine Pesticides by High-Performance Liquid Chromatography in Water,Sediments, and Fish from the Chenab River,Pakistan

The current study assessed the spatiotemporal variations and human health surveillance associated with organochlorine pesticide (OCP) contamination in water, sediments, and fish from Chenab River, Pakistan. The OCP determinations were performed using high-performance liquid chromatography with a reverse-phase C18 column. The total OCP levels ranged from 13.33 to 274.59?ng/L in water, 4.63 to 239.11?ng/g in sediments, and 23.79 to 387.12?ng/g in fish species. The overall pattern of mean OCP concentrations followed the order as ΣDDTs?>?Σendosulfan?>?aldrin and OCP pollution pattern among the headworks were Khanki Barrage?>?Qadirabad Barrage?>?Trimmu Barrage?>?Marala Barrage in all three environmental matrixes during both seasons. The estimated daily intake (EDI) for ∑OCPs was found to be 22.44?ng/kg/day. The hazard ratios calculated to assess the carcinogenic risk indicated that the values for ∑DDT and aldrin at the 95th percentile concentrations were greater than one, indicating the probability of carcinogenic risk occurrence of one in million populations due to fish consumption. Therefore, these high levels of OCPs and carcinogenic risk through fish consumption highlight the needs of immediate elimination of OCPs from riverine environment of Chenab River and we recommend long-term monitoring-based freshwater ecological studies to be conducted in the study area.     

O‐Ethyl and O‐methyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d‐glucopyranosyl)thiocarbamate

In both the title structures, O‐ethyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d ‐gluco­pyran­osyl)­thio­carbam­ate, C₁₇H₂₅NO₁₀S, and O‐methyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d ‐gluco­pyran­osyl)­thiocar­bam­ate, C₁₆H₂₃NO₁₀S, the hexo­pyran­osyl ring adopts the ⁴C₁ conformation. All the ring substituents are in equatorial positions. The acetoxy­methyl group is in a gauche–gauche conformation. The S atom is in a synperi­planar conformation, while the C—N—C—O linkage is antiperiplanar. N—H?O intermolecular hydrogen bonds link the mol­ecules into infinite chains and these are connected by C—H?O interactions.     

Bis­(O,O′‐di‐p‐tolyldithiophosphato‐S,S′)(1,10‐phenanthroline‐N,N′)nickel(II)

The title coordination complex, [Ni(C₁₄H₁₄O₂PS₂)₂(C₁₂H₈N₂)] or [Ni(pMePh‐dtp)₂(phen)] (phen is 1,10‐phenanthroline; dtp is di­aryl­di­thio­phosphate), has a non‐crystallographic twofold axis of symmetry through the Ni atom and the phen moiety. Two O,O‐di‐p‐tolyl­di­thio­phosphate (dtp) ions act as bidentate ligands. The central metal atom is coordinated by four S atoms from two dtp groups and two N atoms from the phen ligand. The title compound displays distorted octahedral geometry around the central Ni atom.     

Cohirsine - a novel isoquinolone alkaloid from

A novel alkaloid, cohirsine (1) was isolated from . Its structure has been investigated by extensive NMR studies including 2D NMR experiments. Its stereochemistry has been determined by 2D NOESY and NOE difference measurements.     

Reductive Alkylation Causes the Formation of a Molten Globule-Like Intermediate Structure in <Emphasis Type="Italic">Geobacillus zalihae</Emphasis> Strain T1 Thermostable Lipase

A thermostable lipase from Geobacillus zalihae strain T1 was chemically modified using propionaldehyde via reductive alkylation. The targeted alkylation sites were lysines, in which T1 lipase possessed 11 residues. Far-UV circular dichroism (CD) spectra of both native and alkylated enzyme showed a similar broad minimum between 208 and 222 nm, thus suggesting a substantial amount of secondary structures in modified enzyme, as compared with the corresponding native enzyme. The hydrolytic activity of the modified enzymes dropped drastically by nearly 15-fold upon chemical modification, despite both the native and modified form showed distinctive α-helical bands at 208 and 222 nm in CD spectra, leading us to the hypothesis of formation of a molten globule (MG)-like structure. As cooperative unfolding transitions were observed, the modified lipase was distinguished from the native state, in which the former possessed a denaturation temperature (T _m) in lower temperature range at 61 °C while the latter at 68 °C. This was further supported by 8-anilino-1-naphthalenesulfonic acid (ANS) probed fluorescence which indicated higher exposure of hydrophobic residues, consequential of chemical modification. Based on matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis, a small number of lysine residues were confirmed to be alkylated.     

Preparation and characterization of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>0.2</Subscript>Fe<Subscript>0.8</Subscript>O<Subscript>3-δ</Subscript> thin-film membrane on porous support by dip-coating method

Perovskite-type La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF6428) thin-film membrane prepared by modified Pechini sol–gel process, was successfully deposited on porous support of similar composition using dip-coating method. Fine grain and crack-free film with perovskite structure was obtained at sintering temperature of 800 °C and dwelling time of 60 min. The cross-sectional image indicated that LSCF6428 thin-film membrane coated on the porous support showed excellent adhesion to the support with uniform thickness. The minimum dense layer thickness obtained by dip-coating method was around 0.5 μm. It was found that the oxygen permeability of the supported thin film was lower than that of the perovskite support, which indicated that the pores of the support were reduced by thin-film deposition on the support surface. The reduction in the pore size led to the more selective permeation mechanism contributes to the overall permeation. Successful deposition of LSCF6428 thin-film membrane on porous support can be considered as a promising technique for the preparation of oxygen separation membrane.     

2,3-Unsaturated allyl glycosides as glycosyl donors for selective α-glycosylation

In the presence of NBS and a catalytic amount of a Lewis acid, 2,3-unsaturated allyl glycosides [6-(allyloxy)-3,6-dihydro-2-(hydroxymethyl)-2H-pyran-3-ol] have been successfully used as versatile glycosyl donors for the stereoselective α-glycosylation of a variety of alcohols comprising sensitive functions such as acetonide, keto, nitro, and ester in 50-90% yields. The methodology offers an equally facile alternative to 4-pentenyl replacement in unsaturated sugars.