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.     

The Effect of Enantiomer Elution Order on the Determination of Minor Enantiomeric Impurity in Ketoprofen and Enantiomeric Purity Evaluation of Commercially Available Dexketoprofen Formulations

In a recent study, opposite enantiomer elution order was observed for ketoprofen enantiomers on two amylose-phenylcarbamate-based chiral columns with the same chemical composition of the chiral selector but in one case with coated while in the other with an immobilized chiral selector. In the present study, the influence of this uncommon effect on method validation parameters for the determination of minor enantiomeric impurity in dexketoprofen was studied. The validated methods with two alternative elution orders for enantiomers were applied for the evaluation of enantiomeric impurity in six marketed dexketoprofen formulations from various vendors. In most of these formulations except one the content of enantiomeric impurity exceeded 0.1% (w/w).     

Synthesis and Structural Studies of 6-（2,5-Dimethyl-1H-pyrrol-1-yl）pyridin-2-amine

6-(2,5-Dimethyl-1H-pyrrol-1-yl)pyridin-2-amine (1) was synthesized and characte-rized by elemental analyses,1H-NMR and 13C-NMR,FTIR,Uv-Vis,mass spectral studies and single-crystal X-ray diffraction.All data obtained from spectral studies support the structural properties of 1.Intermolecular N-H…N hydrogen bonds produce an R22(8) ring.An extensive three-dimensional network formed by C-H…π and N-H…π-facial hydrogen bonds is responsible for the crystal stabilization.The combination of C-H…π interactions produces R33(12),R43(19) and R44(20) rings.     

Secondary metabolites from the roots of Paronychia chionaea

Two novel secondary metabolites, compounds (1-2) were isolated from the roots of Paronychia chionaea. On the basis of spectroscopic data including 1D and 2D NMR experiments (COSY, TOCSY, HSQC, and HMBC), and mass spectroscopy, their structures were established as 6-C-[alpha-L-arabinopyranosyl-( 1 --> 2)-beta-D-glucopyranosyl]-7-O-[beta-D-glucopyranosyl]-luteolin 3'-methyl ether (1), and 2-(methoxy)-2-(3,5-dimethoxy 4-hydroxyphenyl)-ethane-1,2-diol 1-O-beta-D-glucopyranoside (2).     

Numerical solution of the Rosenau–KdV–RLW equation by operator splitting techniques based on B‐spline collocation method

In the present study, the operator splitting techniques based on the quintic B‐spline collocation finite element method are presented for calculating the numerical solutions of the Rosenau–KdV–RLW equation. Two test problems having exact solutions have been considered. To demonstrate the efficiency and accuracy of the present methods, the error norms L₂ and L_∞ with the discrete mass Q and energy E conservative properties have been calculated. The results obtained by the method have been compared with the exact solution of each problem and other numerical results in the literature, and also found to be in good agreement with each other. A Fourier stability analysis of each presented method is also investigated.     

Kaluza–Klein reduction of a quadratic curvature model

Palatini variational principle is implemented on a five dimensional quadratic curvature gravity model, rendering two sets of equations, which can be interpreted as the field equations and the stress-energy tensor. Unification of gravity with electromagnetism and the scalar dilaton field is achieved through the Kaluza–Klein dimensional reduction mechanism. The reduced curvature invariant, field equations and the stress-energy tensor are obtained in the actual four dimensional spacetime. The structure of the interactions among the constituent fields is exhibited in detail. It is shown that the Lorentz force density naturally emerges from the reduced field equations and the equations of the standard Kaluza–Klein theory are demonstrated to be intrinsically contained in this model.     

Embryo viability indexing using Raman spectroscopy of spent culture media

ABSTRACT

Embryo viability quantification is an important topic for in vitro fertilization researchers. This study suggests Raman spectroscopy as a candidate method to find an objective measure of embryo viability. Raman spectra of 31 spent embryo culture samples (16 nonpregnant, 15 pregnant) from 31 patients were analyzed with band component analysis. The band area ratio of 902 to 943 cm^?1 was found to be the most discriminatory. These bands are related to glutamine, glycine, proline, aspartic acid, and valine. According to the pregnancy outcome the sensitivity and specificity of Raman analysis were found to be 93% and 77%, respectively.     

Separation of brombuterol enantiomers in capillary electrophoresis with cyclodextrin‐type chiral selectors and investigation of structure of selector‐selectand complexes using nuclear magnetic resonance spectroscopy

The major goal of this study was to determine the affinity pattern of brombuterol (BB) enantiomers toward various cyclodextrins (CD) and to evaluate the potential of NMR spectroscopy for understanding fine mechanisms of interactions between CDs and BB enantiomers. Separation of BB enantiomers was performed in a fused‐silica capillary using a phosphate buffer, pH 2.5, at the room temperature in the normal polarity mode. It was shown once again that CE in combination with NMR spectroscopy represents a very sensitive tool for studies of affinity patterns and structure of CD complexes with chiral guests. Although opposite affinity patterns of BB enantiomers were observed toward native β‐ and γ‐CDs, no significant differences between the structures of the complexes of these two CDs with BB were detected by NMR spectroscopy. In contrary to this, the opposite affinity pattern of BB enantiomers toward β‐CD and its two sulfated derivatives, heptakis (2,3‐O‐diacetyl‐6‐sulfo)‐β‐CD (HDAS‐β‐CD) and heptakis (2‐O‐methyl‐3,6‐di‐O‐sulfo)‐β‐CD (HMDS‐β‐CD) was associated with major differences in the structure of the complexes. In addition, it was shown again that HMDS‐β‐CD provides separation of enantiomers without formation of inclusion‐type complex with the chiral analyte.     

Synthesis and structure of 2-[(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalene)]-5-benzimidazole ethylcarboxylate monohydrate

As part of a program investigating the conformations of potential anticarcinogens and antioxidants, the structure of the title compound C₂₄H₂₈N₂O₂·H₂O is reported. The monohydrate crystallizes in the monoclinic space group P2/c with unit cell parameters a = 16.184(1),b = 7.937(1), c = 16.968(1), = 92.788(7)°, and Z = 4. The benzimidazole and tetrahydrotetramethylnaphthalene ring systems are inclined to one another by approximately 26°. The water molecule plays an important role in the crystal structure by hydrogen bonding to different functional groups of three organic moieties. Additional crystal stabilization is dueto – stacking of benzimidazole rings.     

Solid-phase synthesis of asymmetrically substituted "AB3-type" phthalocyanines

Synthesis of phthalocyanines with asymmetrical substitution on the periphery is often difficult due the problems in purification of the phthalocyanine mixtures obtained. Using a poly(ethylene glycol) (PEG)-based support with a Wang-type linker, we have developed the synthesis of monohydroxylated, oligoethylene glycol substituted phthalocyanines utilizing an amidine-base-promoted phthalonitrile tetramerization reaction. The use of a hydrophilic support allows symmetrical phthalocyanine product formed in solution to be readily and completely removed by washing while leaving the "AB3" product on the support. Acid cleavage with 10% trifluoroacetic acid provides the pure unsymmetrically substituted Pc. This method was applied to several metallo Pcs. Additionally, methods to avoid premature reactions on-resin that give A2B2 products are provided.