Preparation and characterization of sulfonated polyimide ionomers via post‐sulfonation method for fuel cell applications

This paper describes our work on the synthesis of a series of sulfonated homo‐/co‐polyimides (SPI) which were obtained by post‐sulfonation method over three steps. In the first step, 4,4′‐oxydianiline (ODA) and 4,4′‐diaminodiphenylsulfone (DDS) dissolved in N‐methyl pyrrolidone (NMP) were reacted with benzophenonetetracarboxylic dianhydride (BTDA) in order to yield poly(amic acid) (PAA). Secondly, precipitated PAA was sulfonated via concentrated sulfuric acid (95–98%) at room temperature to give post‐sulfonated PAA (PSPAA). Finally, PSPAA was converted into post‐sulfonated PI (PSPI) by the thermal imidization method. PSPIs with ion exchange capacity (IEC) ranging from 0.20 to 0.67 meq/g were prepared. The thermal properties of the PSPIs were evaluated and high desulfonation temperature was found in the range of 190–350°C, suggesting the high stability of sulfonic acid groups. In water, PSPI‐5 membrane displayed similar proton conductivity to Nafion®117, whereas this membrane showed poor conductivity in dry state. All PSPIs displayed good solubility in common polar aprotic solvents such as NMP and dimethylacetamide (DMAc). Furthermore, the effects of post‐sulfonation reaction on chemical structure, thermal oxidative behavior, and physical properties of the PSPI membranes such as membrane quality/stability and water uptake were discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Homo‐ and heteropolynuclear copper(II) complexes containing a new diimine–dioxime ligand and 1,10‐phenanthroline: synthesis,characterization, solvent‐extraction studies,catalase‐like functions and DNA cleavage abilities

A series of homo‐, heterodinuclear and homotrinuclear copper(II) complexes containing a new Schiff base ligand and 1,10‐phenanthroline were synthesized. Based on results of elemental analyses, FTIR, ¹H‐ and ¹³C‐NMR spectra, conductivity measurements and magnetic susceptibility measurements, the complexes had general compositions {[Cu(L)(H₂O)M(phen)₂](ClO₄)₂ [M = Cu(II), Mn(II), Co(II)]} and {[Cu₃(L)₂(H₂O)₂](ClO₄)₂}. The metal:L:phen ratio is 2:1:2 for the dinuclear copper(II) complexes and the metal:L ratio was 3:2 for the trinuclear copper(II) complex. The liquid–liquid extraction of various transition metal cations [Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II), Hg(II)] from the aqueous phase to the organic phase was carried out using the diimine–dioxime ligand. It was concluded that the ligand can effectively be used in solvent extraction of copper(II) from the aqueous phase to the organic phase. Furthermore, catalytic activitiy of the complexes for the disproportionation of hydrogen peroxide was also investigated in the presence of imidazole. Dinuclear copper(II)–manganese(II) complex has some similarity to manganese catalase in structure and activity. The interaction between these complexes and DNA has also been investigated by agarose gel electrophoresis; we found that the homo‐ and heterodinuclear copper complexes can cleave supercoiled pBR322 DNA to nicked and linear forms in the presence of H₂O₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of Thiophenes,Azoles and Azines with Potential Biological Activity by Employing the Versatile Heterocyclic Precursor N‐Benzoycyanoacetylhydrazine

This research work is concerned with the use of N‐benzoyl cyanoacetylhydrazine ( 3 ) in synthesizing several new heterocyclic compounds with potential biological activity, via its reaction with various chemical reagents. The synthesized derivatives have actually exhibited, upon screening, antibacterial and antifungal activities.     

Theoretical studies of some sulphonamides as corrosion inhibitors for mild steel in acidic medium

Density functional theory (DFT) at the B3LYP/6‐31G (d,p) and BP86/CEP‐31G* basis set levels and ab initio calculations using the RHF/6‐31G (d,p) methods were performed on four sulfonamides (namely sulfaacetamide (SAM), sulfapyridine (SPY), sulfamerazine (SMR), and sulfathiazole (STI)) used as corrosion inhibitors for mild steel in acidic medium to determine the relationship between molecular structure and their inhibition efficiencies (%IE). The order of inhibition efficiency obtained was SMR > SPY > STI > SAM which corresponded with the order of most of the calculated quantum chemical parameters namely E_HOMO (highest occupied molecular orbital energy), E_LUMO (lowest unoccupied molecular orbital energy), the energy gap (ΔE), the Mulliken charges on the C, O, N, S atoms, hardness (η), softness (S), polarizability (α), dipole moment (μ), total energy change (ΔE_T), electrophilicity (ω), electron affinity (A), ionization potential (I), the absolute electronegativity (χ), and the fraction of electrons transferred (ΔN). Quantitative structure activity relationship (QSAR) approach has been used and a correlation of the composite index of some of the quantum chemical parameters was performed to characterize the inhibition performance of the sulfonamides studied. The results showed that the %IE of the sulfonamides was closely related to some of the quantum chemical parameters but with varying degrees/order. The calculated %IE of the sulfonamides studied was found to be close to their experimental corrosion inhibition efficiencies. The experimental data obtained fits the Langmuir adsorption isotherm. The negative sign of the E_HOMO values and other thermodynamic parameters obtained indicates that the data obtained supports physical adsorption mechanism. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Optimization of a linear function over the set of stochastic efficient solutions

In this paper we study the problem of optimization over an integer efficient set of a Multiple Objective Integer Linear Stochastic Programming problem. Once the problem is converted into a deterministic one by adapting the $2$ -levels recourse approach, a new pivoting technique is applied to generate an optimal efficient solution without having to enumerate all of them. This method combines both techniques, the L-shaped method and the combined method developed in Chaabane and Pirlot (J Ind Manag Optim 6:811–823, 2010). A detailed didactic example is given to illustrate different steps of our algorithm.     

The generalized trust region subproblem: solution complexity and convex hull results

Mathematical Programming - We consider the generalized trust region subproblem (GTRS) of minimizing a nonconvex quadratic objective over a nonconvex quadratic constraint. A lifting of this...     

Limoniastrum monopetalum–Mediated Nanoparticles and Biomedicines: In Silico Study and Molecular Prediction of Biomolecules

An in silico approach applying computer-simulated models helps enhance biomedicines by sightseeing the pharmacology of potential therapeutics. Currently, an in silico study combined with in vitro assays investigated the antimicrobial ability of Limoniastrum monopetalum and silver nanoparticles (AgNPs) fabricated by its aid. AgNPs mediated by L. monopetalum were characterized using FTIR, TEM, SEM, and DLS. L. monopetalum metabolites were detected by QTOF–LCMS and assessed using an in silico study for pharmacological properties. The antibacterial ability of an L. monopetalum extract and AgNPs was investigated. PASS Online predictions and the swissADME web server were used for antibacterial activity and potential molecular target metabolites, respectively. Spherical AgNPs with a 68.79 nm average size diameter were obtained. Twelve biomolecules (ferulic acid, trihydroxy-octadecenoic acid, catechin, pinoresinol, gallic acid, myricetin, 6-hydroxyluteolin, 6,7-dihydroxy-5-methoxy 7-O-β-d-glucopyranoside, methyl gallate, isorhamnetin, chlorogenic acid, 2-(3,4-dihydroxyphenyl)-5,7-dihydroxy-4-oxo-4H-chromen-3-yl 6-O-(6-deoxy-β-l-mannopyranosyl)-β-d-glucopyranoside) were identified. The L. monopetalum extract and AgNPs displayed antibacterial effects. The computational study suggested that L. Monopetalum metabolites could hold promising antibacterial activity with minimal toxicity and an acceptable pharmaceutical profile. The in silico approach indicated that metabolites 8 and 12 have the highest antibacterial activity, and swissADME web server results suggested the CA II enzyme as a potential molecular target for both metabolites. Novel therapeutic agents could be discovered using in silico molecular target prediction combined with in vitro studies. Among L. Monopetalum metabolites, metabolite 12 could serve as a starting point for potential antibacterial treatment for several human bacterial infections.     

Anti-Quorum Sensing and Anti-Biofilm Activity of Pelargonium × hortorum Root Extract against Pseudomonas aeruginosa: Combinatorial Effect of Catechin and Gallic Acid

HPLC-UV was used to compare the major constituents of two Pelargonium × hortorum cultivars and Pelargonium sidoides root extract. It revealed the presence of catechin and gallic acid in high concentrations and the absence of umckalin in P. × hortorum root extracts. The antibacterial activity of these extracts was screened against 19 Pseudomonas aeruginosa clinical isolates. P. × hortorum root extracts showed the lowest MIC values (512–1024 µg/mL). This activity was concluded to be attributable to the high concentrations of catechin and gallic acid. The anti-biofilm activity of catechin, gallic acid, and their combination was examined by a crystal violet assay. The combination reduced the percentage of strong and moderate biofilm-forming isolates from 52.63% to 5.26%. The impact on lasI and lasR genes expression using qRT-PCR and simultaneous docking against LasR protein was explored. The combination downregulated lasI and lasR gene expression in eight and six P. aeruginosa isolates, respectively, and showed the greatest docking score. Additionally, the in vivo protection capability of this combination in infected mice showed enhancement in the survival rate. Our study revealed the potential biofilm and quorum-sensing-inhibitory activity of the catechin and gallic acid combination as a novel alternative to inhibit bacterial pathogenicity.     

Micelle‐catalyzed reaction of ninhydrin with DL‐valine in the absence and presence of organic solvents

Kinetics of the DL ‐valine‐ninhydrin reaction has been studied spectrophotometrically under varying conditions of [CTAB], [ninhydrin], [DL ‐valine], pH, temperature, and %(v/v) organic solvents (solvents used: 1‐propanol, methylcellosolve, acetonitrile, and dimethyl sulfoxide). Addition of CTAB and increase in the proportion of organic solvents, both showed catalyzing effect on the reaction. The effect of simultaneous presence of CTAB and DMSO in the reaction mixture has also been seen. The rate profiles obtained for solutions containing from 10% to 70% DMSO exhibited clear maxima that shifted progressively to higher concentrations of CTAB. The experimental results are explained in terms of specific solvent effects and the formation of stoichiometric hydrate DMSO · 2H₂O and the inhibitory effect of DMSO on micelle formation. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 634–642, 2006     

Perturbations Results for Some Classes Related to Browder Linear Relations and Applications

This paper is devoted to the investigation of the perturbation problem of right (left) Browder linear relations and lower (upper) semi-Browder linear relations under commuting compact linear relations. Further, our results are used to show the invariance of Browder’s spectrum.