Membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene–perfluorovinyl ether)

Some properties of the membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene-perfluorovinyl ether) copolymer (PFA) films have been investigated. The dimensional change caused by grafting and swelling behavior, water uptake, electrical conductivity, and mechanical properties of the grafted films were found to increase as the grafting proceeds. The influence of the preparation conditions (such as preirradiation dose, monomer concentration, grafting temperature, and film thickness) on those properties was studied. These properties were found to be dependent mainly on the degree of grafting regardless of grafting conditions, except at higher monomer concentration (>40 wt %). The electric conductivity and mechanical properties for the membranes obtained at higher AAc concentrations were lower than those obtained at lower ones. Analysis by x-ray microscopy of the grafted films revealed that the grafting begins at the part close to the film surface and proceeds into the central part with progressive diffusion of monomer to give finally homogeneous distribution of the electrolytes in the whole bulk of the polymer. The membranes show good electrochemical and mechanical properties which make them acceptable for practical use as cation-exchange membranes.     

Determination of camptothecin in biological fluids using reversed-phase high-performance liquid chromatography with fluorescence detection

Camptothecin, a plant alkaloid with antitumor activity, is a potent and rapidly acting inhibitor of DNA synthesis. The objective of this study was to develop a sensitive high-performance liquid chromatographic (HPLC) method for the detection and estimation of the camptothecin concentration in biological fluids. Using HPLC coupled with fluorescence detection, at an excitation wavelength of 370 nm and an emission wavelength of 434 nm, we found that the lower limits of detection for camptothecin in aqueous, plasma and urine samples were 0.5, 1 and 10 ng/ml, respectively. The ideal mobile phase used was methanol-10 mM potassium phosphate (75:25, v/v, pH 4.0). To determine the utilization of the method in a biological system, we studied the pharmacokinetics of camptothecin in mice. Elimination of camptothecin from mice blood was triphasic and followed first-order kinetics. The half-life of camptothecin in mouse blood was 25.7 min. Our studies indicate that HPLC with fluorescence detection for the determination of camptothecin in different media is a simple, rapid, sensitive and reproducible method.     

Dichotenone-a and -b: two new enones from the marine brown alga Dictyota dichotoma (Hudson) Lamour

Marine brown alga Dictyota dichotoma (Dictyotaceae) collected from Karachi coast of Arabian Sea yielded two new (1 and 2) enones (dolastane-diterpenoids) named: dichotenone-A and -B along with an olide (loliolide, 3) as a new source. Their structures have been characterized with the aid of 2D-NMR spectroscopic techniques.     

Viscoelasticity,mechanical properties,and in vivo biocompatibility of injectable polyvinyl alcohol/bioactive glass composite hydrogels as potential bone tissue scaffolds

Abstract

An injectable composite hydrogel composed of polyvinyl alcohol (PVA) and bioactive glass (BG) particles were synthesized by a physical crosslinking approach. The morphology, mechanical properties, and viscoelasticity of the PVA/BG composite hydrogel were characterized. Scanning electronic microscopy (SEM) showed uniform and homogeneous distribution of BG particles throughout the composite hydrogel. The incorporation of 2.5?wt% of BG particles in the composite hydrogel formulations, enhanced the static compressive strength and static elastic modulus by 325% and 150%, respectively. The storage molds (G′) was greater than the loss modules (G′′) at all the frequency range studied, which revealed a self-standing elastic composite hydrogel with a smooth injectability. The PVA/BG composite hydrogel was also implanted subcutaneously in the dorsal region of adult male rats. After 4?weeks of implantation, no inflammatory cells were seen within and around the implant, which indicated that the composite hydrogel was biocompatible. The properties of the synthesized injectable PVA/BG composite hydrogel demonstrate its capability toward bone regeneration.     

Inhibition of Pb-Leaching from Lead Crystal Glass by Coating with Films Prepared by the Sol-Gel Method

The chemical durability of lead glass tumblers (24% PbO) in a 4% (v/v) acetic acid solution before and after coating with sol-gel derived SiO2 films was assessed to determine the extent of reduction in Pb-leaching that can be achieved. It was found that by coating the internal surface of the glass tumblers with 1 ml of 10% TEOS solutions at 100°C and densifying the coating formed at 500°C for 1 h, it was possible to reduce Pb-leaching to about one quarter of that of the uncoated glass.     

Utility of N‐[4‐(N‐Substituted Sulfamoyl)Phenyl] Cyanothioformamides in the Synthesis of Heterocyclic Compounds

The novel cyanothioformamides 2a‐d were prepared by treatment of isothiocyanatosulfonamides 1a‐d with potassium cyanide at room temperature. Cyclocondensation of compounds 2b,c with phenyl isocyanate as electrophile furnished the corresponding imidazolidines 3a,b . The reactivity of compound 3a towards some nitrogen nucleophiles was investigated. Thus, the thiosemicarbazone 4 and imidazo[4,5‐b]quinoxaline 6 were synthesized by condensation of compound 3a with thiosemicarbazide and o‐phenylenediamine, respectively. Treatment of 3a with hydrochloric acid afforded compound 7 . Our investigation was extended to include the reactivity of cyanothioformamide 2 towards o‐aminophenol, anthranilic acid, and o‐phenylenediamine and yielded the corresponding heterocycles 9 , 11 and 13 derivatives, respectively. Structures of the synthesized compounds were established by their elemental analysis and spectral data.     

N-substituted phenothiazines as redox indicators in bromatometry

Diethazine hydrochloride, butaperazine dimaleate, trifluoperazine hydrochloride, promethazine hydrochloride, prochlorperazine maleate and chlorpromazine hydrochloride have been studied as indicators in bromate titration of quinol, metol and ascorbic acid. They give a very sharp reversible colour change at the equivalence point. Their formal potentials have been determined. A simple but accurate method for the estimation of quinol and metol is reported.     

Mimicking transition metals in borrowing hydrogen from alcohols

Borrowing hydrogen from alcohols, storing it on a catalyst and subsequent transfer of the hydrogen from the catalyst to an in situ generated imine is the hallmark of a transition metal mediated catalytic N-alkylation of amines. However, such a borrowing hydrogen mechanism with a transition metal free catalytic system which stores hydrogen molecules in the catalyst backbone is yet to be established. Herein, we demonstrate that a phenalenyl ligand can imitate the role of transition metals in storing and transferring hydrogen molecules leading to borrowing hydrogen mediated alkylation of anilines by alcohols including a wide range of substrate scope. A close inspection of the mechanistic pathway by characterizing several intermediates through various spectroscopic techniques, deuterium labelling experiments, and DFT study concluded that the phenalenyl radical based backbone sequentially adds H⁺, H˙ and an electron through a dearomatization process which are subsequently used as reducing equivalents to the C–N double bond in a catalytic fashion.

An efficient method is developed for harvesting hydrogen, its storage and catalytic transfer by an odd alternant hydrocarbon. The strategy is reminiscent of transition metals in borrowing hydrogen mediated processes.     

In situ assembled ZIF superstructures via an emulsion-free soft-templating approach

Assembling well-defined MOF superstructures remains challenging as it requires easily removable hard templates or readily available immiscible solutions for an emulsion-based soft-template approach. In this work, a single-step emulsion-free soft templating approach is reported to spontaneously prepare hollow ZIF-8 and ZIF-67 colloidosomes with no further purification. These superstructures can load different enzymes regardless of the size and charge with a high encapsulation efficiency of 99%. We envisage that this work will expand the repertoires of MOF superstructures by the judicious selection of precursors and the reaction medium.

An emulsion-free approach for the preparation of hollow ZIF-8 superstructures in a single step is established based on metal sulfate hydrates in methanol.     

Spectral and magnetic properties of phenylazo-6-aminouracil complexes

Complexes of Co(II), Ni(II) and Cu(II) with substituted phenylazo-6-aminouracils containing (-H, p-OH, p-CH(3), p-OCH(3) p-COOH) have been synthesized and characterized by elemental analysis, magnetic measurements and spectral measurements (IR, UV-Vis, ESR). Infrared spectra assigned the fundamental bands of the major groups, O-H, N-H, C-H, C=O, C=N, N=N, C-N and C-O (nu, delta and gamma modes of vibrations). The absence of nu(OH) and the appearance of nu(C=O) in the infrared spectra of the free ligands of 5-(p-tolyl and p-anisylazo)-6-aminouracil, assigned the keto structure, whereas in cases of 5-(phenyl, p-hydroxyphenyl and p-carboxyphenylazo)-6-aminouracil ligands, the data showed strong nu(OH) and nu(C=O) bands to assign keto-enol tautomerisms. The modes of interactions between the ligands and the metals were discussed, where oxygen and nitrogen atoms (of amino-amide groups) are involved in chelation. The azo group was not involved in chelation for all the prepared complexes except those of copper complexes derived from 5-(phenyl, p-tolyl, p-hydroxyphenyl and p-carboxyphenylazo)-6-aminouracils. The room temperature effective magnetic moment values, the Nujol mull spectra and ESR proved that all the prepared complexes were of octahedral geometry, except the nickel complex derived from 5-(phenylazo)-6-aminouracil and cobalt complex derived from 5-(p-carboxy-phenylazo)-6-aminouracil were square planar.