Zirconium(IV)-porphyrins as novel ionophores for fluoride-selective polymeric membrane electrodes

The feasibility of using Zr(IV)-porphyrins as novel ionophores for preparing anion-selective polymeric membrane electrodes is examined. Electrodes constructed using o-nitrophenyl octyl ether plasticized poly(vinyl chloride) membranes containing Zr(IV)-octaethylporphyrin (OEP) dichloride (Zr(IV)[OEP]Cl₂) or Zr(IV)-tetraphenylporphyrin (TPP) dichloride (Zr(IV)[TPP]Cl₂) were found to exhibit enhanced potentiometric selectivity toward fluoride compared to electrodes based on a typical anion-exchanger (e.g. tridodecylmethylammonium chloride). At pH 5.5, the electrodes displayed the following selectivity sequences: ClO₄⁻ > SCN⁻ > I⁻ > F⁻ > NO₃⁻ > Br⁻ > NO₂⁻ > Cl⁻ and F⁻ > ClO₄⁻ > SCN⁻ > I⁻ > NO₂⁻ > NO₃⁻ > Br⁻ > Cl⁻ for membranes doped with Zr(IV)[OEP]Cl₂) and Zr(IV)[TPP]Cl₂, respectively. Both ionophores are shown to operate via a charged carrier mechanism, with 10 mol% of lipophilic tetraphenylborate derivative in the membrane phase required to achieve optimal selectivity. Electrodes prepared with both metalloporphyrin species display super-Nernstian response toward fluoride with slopes typically greater than −100 mV per decade. It is shown, via UV-VIS spectroscopy of the membrane phase, that this behavior occurs due to spontaneous formation of hydroxide ion bridged porphyrin dimers in the membrane in the presence of the lipophilic anionic additive. The dimers are easily converted to monomeric species upon increasing the concentration of fluoride in the sample solution. Decreasing the pH of sample buffer background solution (from pH 5.5 to pH 3) decreases the lower detection limit (DL) of the electrode response toward fluoride (by two-order of magnitude) and improves the electrodes’ selectivity.     

Gibbs functions for transfer of divalent metal cations from water to water + methanol mixtures using potentiometry, polarography and solubility measurements

Gibbs functions for transfer from water to methanol and to a full range of water + methanol mixtures were obtained for Cu²⁺, Cd²⁺, Pb²⁺, Hg²⁺, Zn²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ using potentiometric or polarographic measurements in these solvents. In addition, data were obtained from the solubility products of the alkaline-earth iodates. From values obtained by the different methods and literature data, a table of selected values is given.     

Novel species in the electrochemical reduction of a metalmetal bond bridged by a bidentate fluorophosphine

The purple bridged bimetallic complex [CH₃N(PF₂)₂]₃Co₂(CO)₂ undergoes successive chemically and electrochemically reversible one-electron reductions to the corresponding green radical anion and pale-yellow dianion. The radical anion is relatively unreactive towards oxygen and methyl iodide. The dianion is not only reactive towards oxygen and methyl iodide but also captures small positively charged species (e.g. Li⁺ and H⁺) with significant alteration of its chemical properties.     

The use of Omega Chrome Fast Blue 2G in the microdetermination of some metals

Summary Omega Chrome Fast Blue 2G has been found to be a suitable indicator for the detection of the equivalence point of calcium, magnesium and manganese in the presence of cadmium, nickel, and aluminium, when they are masked by the addition of cyanide or triethanolamine. It is also a suitable indicator for the back titration of aluminium using calcium or magnesium as a back titrant.This dye has also been found to be a suitable reagent for the colorimetric determination of calcium, magnesium, manganese and thorium.     

Synthesis of Some Novel 2‐Anilinothiophene, 2,3′‐Bithienyl and Thienylthiopyridine Derivatives Resistance to Penicillium Digitatum Effect the Fruit

Reaction of benzotriazol‐1‐yl acetone 1 with phenyl isothiocyanate followed with α‐chloroacetone or ethyl‐α‐chloroacetate afforded 2‐anilinothiophenes 3 or 4 , respectively. Treatment of 3 with malononitrile at different reaction conditions afforded 6 or 7 . Reaction of 1 with CS₂ in DMF and phenacylbromide afforded S‐alkylated thiophene 10 . Reactions of the latter compound with different active methylene nitriles afforded thienylthiopyridine derivatives 14 and 15 . Condensation of 10 with hydrazine hydrate afforded hydrazon derivative 16 . Reaction of thiophene 17 with formamide in DMF afforded 19 which converted to N‐thienylpyrimidine 20 when treated with malononitrile. The structure of the newly synthesized compounds has been established on the basis of their analytical and spectral data. The compounds were also investigated for antibacterial and antifungal activities.     

Influence of the peak height distribution on separation performances: Discrimination factor and effective peak capacity

Summary A new index of performance of the chromatographic separation between two adjacent peaks, the discrimination factor, d₀, is defined. It is normalized between 0 and 1 and is directly and easily determined from the chromatogram. It does not depend on any assumption regarding peak shape, except that the peak profiles of individual sample components have a single mode. Its value depends on the relative heights of the two peaks as well as on their separation. The separation power of a chromatographic system is classically measured by its peak capacity, defined on the basis of constant resolution between adjacent peaks. A previously developed statistical theory of the composition of mixtures makes it possible to extend the concept of peak capacity by taking into account the peak height distribution in typical average chromatograms. A new parameter, the effective peak capacity, is defined for this purpose on the basis of a constant discrimination factor between adjacent peaks. It allows to take into account the distribution of peak heights in statistical theories of the evaluation of complex chromatograms and in the measurement of the limit of determination in quantitative analysis. The characteristics of the two new parameters, the discrimination factor and effective peak capacity, are discussed and compared with those of their classical homologs, resolution and peak capacity, in the case of gaussian component peaks of equal widths.     

Capillary electrochromatography with monolithic stationary phases: 1. Preparation of sulfonated stearyl acrylate monoliths and their electrochromatographic characterization with neutral and charged solutes

A novel monolithic stationary phase having long alkyl chain ligands (C17) was introduced and evaluated in capillary electrochromatography (CEC) of small neutral and charged species. The monolithic stationary phase was prepared by the in situ copolymerization of pentaerythritol diacrylate monostearate (PEDAS) and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in a ternary porogenic solvent consisting of cyclohexanol/ethylene-glycol/water. While AMPS was meant to support the electroosmotic flow (EOF) necessary for transporting the mobile phase through the monolithic capillary, the PEDAS was introduced to provide the nonpolar sites for chromatographic retention. Monolithic columns at various EOF velocities were readily prepared by conveniently adjusting the amount of AMPS in the polymerization solution as well as the composition of the porogenic solvent. The monolithic stationary phases thus obtained exhibited reversed-phase chromatography behavior toward neutral solutes and yielded a relatively strong EOF. For charged solutes (e.g., dansyl amino acids), nonpolar as well as electrostatic interaction/repulsion with the monoliths were observed in addition to electrophoretic migration. Therefore, for charged solutes, selectivity and migration can be readily manipulated by changing various parameters including the nature of the monolith and the composition of the mobile phase (e.g., pH, ionic strength and organic modifier). Ultrafast separation on the time scale of seconds of 17 different charged and neutral pesticides and metabolites were performed using short capillary columns of 8.5 cm x 100 microm ID.     

Characterization of the new Bi∼6.2Cu∼6.2O8(PO4)5 oxyphosphate; a disordered compound containing 2- and 3-O(Bi, Cu)4 tetrahedra—wide polycationic ribbons

The present work is dedicated to the XRD, ED and HREM characterization of a new bismuth copper oxyphosphate Bi_∼6.2Cu_∼6.2O₈(PO₄)₅ (a=11.599(2)Å, , c=37.541(5)Å, R₁=0.0755, Rw₂₌0.174, G.S Pn2₁a). The relatively long size of its c parameter is due to the arrangement along this direction of two kinds of ribbon-like polycations formed by edge sharing O(Bi, Cu)₄ tetrahedra. The existence of such cations is characterized by the b∼5.2 Å value intrinsic to the ribbons structure and commonly found in bismuth oxyphosphate materials. In the title compound, 2-tetrahedra wide [Bi_∼2.4Cu_∼3.6O₄]^6.4+ and 3-tetrahedra wide [Bi_∼5Cu_∼3O₆]⁹⁺ ribbons are isolated by phosphate groups and alternate along c. The interstitial site created between two different sizes ribbons is occupied by Cu²⁺ cations disordered over several close crystallographic sites. The mixed Bi³⁺/Cu²⁺ nature of certain edge-of-ribbons positions induces a disorder over several configurations of the phosphate groups. The concerned oxygen atoms form the environment of the disordered interstitial Cu²⁺ cations which occupy tunnels formed by the phosphate anions. The high-resolution electron microscope study enables a precise correlation between the observed images and the refined crystal structure, evidencing the polycations visualization. Furthermore, this material being the second example of partially disordered compound similar chemical system, some topological rules can be deduced. The b-axis doubling was observed by ED and HREM and is assigned to the ordering of interstitial Cu²⁺ within tunnels cations. A partial intra-tunnel ordering was also observed.     

Fused quinoline heterocycles VI: Synthesis of 5H‐1‐thia‐3,5,6‐triazaaceanthrylenes and 5H‐1‐thia‐3,4,5,6‐tetraazaaceanthrylenes

Ethyl 3‐amino‐4‐chlorothieno[3,2‐c]quinoline‐2‐carboxylate ( 4 ) is a versatile synthon, prepared by reacting an equimolar amount of 2,4‐dichloroquinoline‐3‐carbonitrile ( 1 ) with ethyl mercaptoacetate ( 2 ). Ethyl 5‐alkyl‐5H‐1‐thia‐3,5,6‐triazaaceanfhrylene‐2‐carboxylates 9a‐c , novel perianellated tetracyclic heteroaro‐matics, were prepared by refluxing 4 with excess of primary amines 7a‐c to yield the corresponding amino‐thieno[3,2‐c]quinolines 8a‐c . Subsequent reaction with an excess of triethyl orthoformate (TEO) furnished 9a‐c . Reaction of 4 with TEO in Ac₂O at reflux, gave the simple acetylated compounds, thieno[3,2‐c]‐quinolines 12 and 13 . Refluxing 4 with benzylamine ( 7d ) gave 10 , and subsequent treatment with TEO gave the tetracyclic compound 11 . Refluxing 13 with an excess of alkylamines 7a‐d gave the fhieno[3,2‐c]quino‐lines 15 . Refluxing the aminothienoquinolines 8b with an excess of triethyl orthoacetate gave thieno[3,2‐c]quinoline 17 , while heating with Ac₂O gave 18 and 19 , with small amounts of 16 . Reaction of 8a,b with ethyl chloroformate and phenylisothiocyanate generated the new 1‐thia‐3,5,6‐triazaaceanthrylenes 20a,b and 21a,b , respectively. Diazotization of 8a‐c afforded the novel tetracyclic ethyl 5‐alkyl‐5H‐1‐fhia‐3,4,5,6‐tetraazaaceanthrylene‐2‐carboxylates 22a‐c in good yields.