Matrimid–polyaniline/clay mixed‐matrix membranes with plasticization resistance for separation of CO2 from natural gas

Mixed‐matrix membranes (MMMs) of Matrimid® and polyaniline/clay (PC) are investigated for CO₂/CH₄ separation and CO₂‐induced plasticization. PC particles are synthesized through in‐situ polymerization of aniline in the presence of organophilic clay and then incorporated into Matrimid by solution casting method. Chemical structure and morphology of PC powder and fabricated membranes are analyzed by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) and scanning electron microscopy (SEM). The XRD spectra of PC particles show the exfoliation of silicate layers throughout the polyaniline (PAni) matrix, and SEM images indicate flower‐petal morphology for PC particles. The permeability values of CO₂ and CH₄ increase 30–35% by incorporation of 10 wt% PC without any significant drop in selectivity. PC particles with flower‐petal morphology plays an important role in increasing the gas permeability values of both gases while Matrimid is the only phase that controls CO₂/CH₄ selectivity. The plasticization pressure was increased to 30 bar by incorporation of 10 wt% PC in the Matrimid matrix. CO₂ permeability and p_plast improved 35% and 200%, respectively, resulting in 300% enhancement in the capacity of MMM in the purification of natural gas with a selectivity of about 40. Copyright © 2016 John Wiley & Sons, Ltd.     

Kinetic study of triphenylphosphine addition to para‐benzoquinone

Kinetics of the addition reaction of triphenylphosphine to para‐benzoquinone in 1,2‐dichloroethane as solvent was studied. Initial rate method was used to determine the order of the reaction with respect to the reactants. Pseudo‐first‐order method was also used to calculate the rate constant. This reaction was monitored by UV‐vis spectrophotometry at 520 nm by variable time method. On the basis of the obtained results, the Arrhenius equation of this reaction was obtained: The activation parameters, E_a, ΔH^#, ΔG^#, and ΔS^# at 300 K were 5.701, 6.294, 19.958 kcal mol^?1 and ?45.853 cal mol^?1 K^?1, respectively. This reaction is first and second order with respect to triphenylphosphine and para‐benzoquinone, respectively. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:472–479, 2004     

Chemical composition and antimicrobial activity of the essential oil of Anthemis altissima L. var. altissima

The essential oil obtained from the flowering parts of Anthemis altissima L. var. altissima was analysed by gas chromatography and gas chromatography mass spectroscopy. In this study, 34 compounds representing 98.76% of the essential oil were identified. The main components were α-terpineol (26.42%), β-pinene (9.23%), cis-chrysanthenyl acetate (6.30%), globulol (5.36%), n-tricosane (4.41%), terpinen-4-ol (4.08%) and 1,8 cineole (3.84%). Antibacterial activities of the essential oil and its two major components (α-terpineol and β-pinene) were determined using microdilution method against both Gram-positive (Staphylococcus aureus, Bacillus subtilis, Staphylococcus epidermidis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae) bacteria. The essential oil showed a broad-spectrum antibacterial activity (MICs ranged from 3.13 to 6.25?μL?mL(-1)). It was found that α-terpineol with minimum inhibitory concentration (MIC) values of the range 0.87-1.56?μL?mL(-1) was a more potent antibacterial agent than β-pinene with MIC values of the range 1.56-6.25?μL?mL(-1). All of them, the essential oil, β-pinene and α-terpineol, were more effective against Gram-positive bacteria than Gram-negative ones.     

Determination of the stability constant and thermodynamic parameters between Tl<Superscript>+</Superscript>, Ag<Superscript>+</Superscript> and Pb<Superscript>2+</Superscript> cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand

The complexation reaction between Tl⁺, Ag⁺ and Pb²⁺ cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand in acetonitrile (ACN)–H₂O and methanol (MeOH)–H₂O binary solutions has been studied at different temperatures using conductometric method. The conductometric data show that the stoichiometry of the complexes is 1: 1 [M: L] and the stability constant of complexes changes with the binary solutions identity. Also, the structure of the resulting 1: 1 complexes was optimized using the LanL2dz basis set at the B3LYP level of theory using GAUSSIAN03 software. The results show that the change of logK_f for (DFMP.Pb)²⁺ and (DFMP.Ag)⁺ complexes with the mole ratio of acetonitrile and for (DFMP.Ag)⁺ and (DFMP.Tl)⁺ complexes with the mole ratio of methanol have a linear behavior, while the change of logK_f of (DFMP.Tl)⁺complex in ACN–H₂O binary solutions (with a minimum in X_ACN = 0.5) and (DFMP.Ag)⁺ complex in MeOH–H₂O binary solutions (with a minimum in X_MeOH = 0.75) show a non-linear behavior. The selectivity order of DFMP ligand for these cations in mol % CAN = 25 and 75 obtain Tl⁺ > Pb²⁺ > Ag⁺ but in mol % CAN = 50, the selectivity order observe Pb²⁺ > Tl⁺ > Ag⁺. Also, this selectivity sequence of DFMP in MeOH–H₂O (mol % MeOH = 75 and 100) and (mol % MeOH = 50) is obtained Pb²⁺ > Ag⁺ and Tl⁺ > Ag⁺ > Pb²⁺ respectively. The values of thermodynamic parameters show that these values are influenced by the nature and the composition of binary solution. In all cases, the resulting complexes are enthalpy stabilized and entropy destabilized. The TΔS_C^° versus ΔH_C^° plot of all obtained thermodynamic data shows a fairly good linear correlation which indicates the existence of enthalpy-entropy compensation in the complexation reactions.     

Graphene Quantum Dots Incorporated into β-cyclodextrin: a Novel Polymeric Nanocomposite for Non-Enzymatic Sensing of L-Tyrosine at Physiological pH

Graphene quantum dot-β-cyclodextrin modified glassy carbon electrode was used as a new nanosensor for determination of L-tyrosine (L-Tyr). It was found that graphene quantum dot-β-cyclodextrin has been stably electrodeposited on glassy carbon electrode modified by simple technique. The cyclic voltammograms of the modified electrode in an aqueous solution displayed a pair of well-defined, stable and irreversible reductive/oxidation redox systems. The apparent electron transfer rate constant (k_s) and transfer coefficient (α) determined by cyclic voltammetry were approximately equal to 8.0 s^–1 and 0.7, respectively. The modified electrode showed excellent catalytic activity towards the oxidation of L-Tyr at positive potential in buffer solution. The nanosensor also displayed fast response time, high sensitivity, low detection limit and a remarkably positive potential oxidation of L-Tyr that decreased the effect of interferences in analysis.     

Synthesis of New 2-Aryl Substituted 2,3-Dihydroquinazoline-4(1H)-ones Under Solvent-Free Conditions,Using Molecular Iodine as a Mild and Efficient Catalyst

A simple, inexpensive, and efficient one-pot synthesis of 2,3-dihydroquinazoline-4(1H)-one derivatives under solvent-free conditions using a catalytic amount of iodine with excellent product yields is reported. This methodology provides easy, quantitative access to various 2,3-dihydroquinazoline-4(1H)-one derivatives, using commercially available iodine as a catalyst.     

Asymptotically Nonexpansive Mappings in Modular Function Spaces

In this paper, we prove that if ρ is a convex, σ-finite modular function satisfying a Δ₂-type condition, C a convex, ρ-bounded, ρ-a.e. compact subset of L_ρ, and T: C → C a ρ-asymptotically nonexpansive mapping, then T has a fixed point. In particular, any asymptotically nonexpansive self-map defined on a convex subset of L¹(Ω, μ) which is compact for the topology of local convergence in measure has a fixed point.     

Regioselective cis-trans isomerization of arachidonic double bonds by thiyl radicals: the influence of phospholipid supramolecular organization

Trans unsaturated fatty acids in humans may be originated by two different contributions. The exogenous track is due to dietary supplementation of trans fats and the endogenous path deals with free-radical-catalyzed cis-trans isomerization of fatty acids. Arachidonic acid residue (5c,8c,11c,14c-20:4), which has only two out of the four double bonds deriving from the diet, was used to differentiate the two paths and to assess the importance of a radical reaction. A detailed study on the formation of trans phospholipids catalyzed by the HOCH2CH2S* radical was carried out on L-alpha-phosphatidylcholine from egg lecithin and 1-stearoyl-2-arachidonoyl-L-alpha-phosphatidylcholine (SAPC) in homogeneous solution or in large unilamellar vesicles (LUVET). Thiyl radicals were generated from the corresponding thiol by either gamma-irradiation or UV photolysis, and the reaction course was followed by GC, Ag/TLC, and 13C NMR analyses. The isomerization was found to be independent of cis double bond location (random process) in i-PrOH solution. In the case of vesicles, the supramolecular organization of lipids produced a dramatic change of the isomerization outcome: (i) in egg lecithin, the reactivity of arachidonate moieties is higher than that of oleate and linoleate residues, (ii) in the linoleate residues of egg lecithin, the 9t,12c-18:2 isomer prevailed on the 9c,12t-18:2 isomer (3:1 ratio), and (iii) a regioselective isomerization of SAPC arachidonate residues occurred in the 5 and 8 positions. This effect of "positional preference" indicates that thiyl radicals entering the hydrophobic region of the membrane bilayer start to isomerize polyunsaturated fatty acid residues having the double bonds nearest to the membrane surfaces. We propose that arachidonic acid and its trans isomers can function as biomarkers in membranes for distinguishing the two trans fatty acid-forming pathways.     

Application of MCM‐41‐SO3H as an Advanced Nanocatalyst for the Solvent Free Synthesis of Pyrano[3,2‐c]pyridine Derivatives

MCM‐41‐SO₃H, an ordered mesoporous silica material in which MCM‐41 with covalently anchored sulfonic acid groups was used as an acidic catalyst for the rapid and ‘green’ synthesis of pyrano[3,2‐c]pyridine derivatives under solvent‐free conditions. Reusability of the catalyst, high yields, short reaction times, simplicity and easy workup are advantages of this novel synthetic procedure compared to the conventional methods reported in the literature.