Surface Characterization of Sepiolite by Inverse Gas Chromatography

Inverse gas chromatography (IGC) was applied to characterize the surface of sepiolite. The adsorption thermodynamic parameters (the standard enthalpy (ΔH ⁰), entropy (ΔS ⁰) and free energy of adsorption (ΔG ⁰)), the dispersive component of the surface energy (γ _S ^d ), and the acid/base character of sepiolite surface were estimated by using the retention time of different non-polar and polar probes at infinite dilution region. The specific free energy of adsorption (ΔG ^sp ), the specific enthalpy of adsorption (ΔH ^sp ), and the specific entropy of adsorption (ΔS ^sp ) of polar probes on sepiolite were determined. ΔH ^sp were correlated with the donor and modified acceptor numbers of the probes to quantify the acidic K _A and the basic K _D parameters of the sepiolite surface. The values obtained for the parameters K _A and K _D indicated an acidic character for sepiolite surface.     

Heterocyclic synthesis via enaminones: Novel synthesis of (1H)‐pyridin‐2‐one,pyrazolo[1,5‐a]pyrimidine and isoxazole derivatives incorporating a N‐methylphthalimide and their biological evaluation

Novel synthesis of (1H)‐pyridin‐2‐one, pyrazolo[1,5‐a]pyrimidine and isoxazole derivatives incorporating N‐methylphthalimide moiety are reported. Reaction of enaminone 2 with malononitrile affords 4. Condensation of 2 with cyanothioacetamide or benzoylacetonitrile affords compounds 6 and 7 respectively. Reaction of 2 with hydrazine hydrate afford 2,3‐dihydrophthalazine‐1,4‐dione ( 10 ). Condensation of 2 with hydroxylamine and 3‐aminopyrazole derivatives affords compounds 12 and 15a,b respectively. Antimicrobial and antifungal activity were determined for representative compounds and most of them showed moderate activity as antimicrobial agents, while compounds 2 and 7 show strong activity against Aspergillus niger. The structure of the newly synthesized compounds was elucidated by elemental analyses and ¹H nmr spectra and some cases by ¹³C nmr investigation.     

Capillary zone electrophoresis of cationic and anionic drugs in methanol

The actual mobilities and dissociation constants of acidic and basic pharmaceuticals were determined in methanol. Actual mobilities were derived from the dependence of the effective mobilities of the analytes on the pH of the methanolic background electrolyte solution (pH(MeOH)). The pKa values of the pharmaceuticals in methanol (pK(a,MeOH)) were calculated by non-linear curve fitting to the measured mobility values. It was found that the shift in pKa value (when compounds were transferred from water to methanol) increased with the acidity of the analyte. The average pKa shift for compounds exhibiting acidic properties in water was ca. 5.5 units, and the shift for basic compounds about 2 units. As was shown for a mixture of beta-blockers, the calculated actual mobilities and pKa values can be utilised in the optimisation of pH conditions for separation. The practical value of the method was illustrated by the analysis of urine samples.     

Studies of copper(II) sulphide ion-selective electrodes

Changes in liquid junction potentials in copper(II) solutions were measured when different reference electrodes were used. The slope and intercept of a calibration curve for a copper-selective electrode will depend on the selection of reference electrode. The condition of the electrode surface of an Orion copper-selective electrode was studied microscopically and the influence of redox potential on stability of the electrode against corrosion is discussed. Oxidizing solutions will produce pits at dislocations in the material and there will be a mixed electrode potential. The slope, stability, and speed of response are much lower when the surface contains pits. Diamond-polishing was shown to improve the electrode significantly.     

NMR studies of conformations and dynamic processes—II : [26]Bicyclophanes with ethylene bridges

The conformations and dynamic processes in two bicyclophanes have been analysed on the basis of temperature-dependent ¹H NMR spectra. Both bicyclophanes are suggested to have a lowest-energy conformation of D₃ symmetry in which the substituents at all ethylene bridges are gauche⁺ (or gauche^?) oriented. The interconversion of the mirror image conformers of each bicyclophane equilibrates the two hydrogens in each methylene group, the barriers being ca 36 and 37 kJ mol^?1, respectively, as determined by line-shape analysis.     

Stress development during drying of calcium carbonate suspensions containing carboxymethylcellulose and latex particles

Stress development during drying of coatings produced from aqueous dispersions of calcium carbonate particles in the presence and absence of organic binders was studied using a controlled-environment stress apparatus that simultaneously monitored drying stress, weight loss, and relative humidity. Specifically, the influence of two organic binders on drying stress evolution was investigated: (1) carboxymethylcellulose, a water-soluble viscosifying aid, and (2) a styrene-butadiene latex emulsion of varying glass transition temperature. The stress histories exhibited three distinct regions. First, a period of stress rise was observed, which reflected the capillary tension exerted by the liquid on the particle network. Second, a maximum stress was observed. Third, it was followed by a period of either stress decay or rise depending on the organic species present. Significant differences in stress histories were observed between coatings containing soluble and nonsoluble binders. Maximum drying stresses (sigmamax) of 0.2-0.5 MPa were observed for coatings produced from pure calcium carbonate or calcium carbonate-latex suspensions, whereas coatings with carboxymethylcellulose exhibited substantially higher sigmamax values of 1-2 MPa. Upon drying, these coatings were quite hygroscopic, such that cyclic variations in relative humidity induced large cyclic changes in residual stress.     

Novel dye-attached macroporous films for cadmium, zinc and lead sorption: Alkali Blue 6B-attached macroporous poly(2-hydroxyethyl methacrylate)

Alkali Blue 6B-attached poly(2-hydroxyethyl methacrylate) (poly(HEMA)) microporous films were investigated as chelate forming sorbents for heavy metal removal. Poly(HEMA) microporous films were prepared by UV-initiated photo-polymerization of HEMA in the presence of an initiator (azobisisobutyronitrile (AIBN)). Alkali Blue 6B was attached covalently. These films with a swelling ratio of 58%, and carrying 14.8 mmol Alkali Blue 6B m(-2) which were then used in the removal of Cd(II), Zn(II) and Pb(II) from aqueous media. Adsorption rates were very high, equilibrium was achieved in about 30 min. The maximum adsorption of heavy metal ions onto the Alkali Blue 6B-attached films were 41.4 mmol m(-2) for Cd(II), 52.4 mmol m(-2) for Zn(II), and 64.5 mmol m(-2) for Pb(II). When the heavy metal ions competed during the adsorption from a mixture the adsorption values for Cd(II), Zn(II) and Pb(II) were quite close. Heavy metal ions were desorbed by using 0.1 M HNO(3). A significant amount of the adsorbed heavy metal ions (up to 95%) could be desorbed in 30 min. Repeated adsorption/desorption cycles showed the feasibility of these novel dye-attached microporous films for heavy metal removal.     

Micellar electrokinetic capillary chromatography using polymeric hollow fibers

Summary In this paper, polymeric hollow fibers prepared from pH-stable polypropylene were used as columns for micellar electrokinetic capillary chromatography (MECC). The electroosmotic flow (EOF) for polypropylene hollow fibers was evaluated in the pH range of 5.0–12.0. With untreated polypropylene hollow fibers a stabilized but enhanced EOF was achieved when SDS was used in the buffer, decreasing the separation window for uncharged substances in MECC to impractical levels. Uncharged acrylamide and charged 2-acryloylamido-2-methylpropane sulfonic acid surface modifications were used to lower the strength of the EOF, increase the separation window and prevent local overheating that could melt the column wall.     

Air microwave-induced plasma: Relation between ion density and atomic oxygen density

Electron temperature and ion density are measured in an air microwave-induced plasma (2450 MHz) by means of a floating double probe. A 'cinetic scheme for ion formation and decay is set up, and a relationship between atomic oxygen and ion densities is obtained. From this relationship an order-of-magnitude of atomic oxygen concentration in the discharge is derived and compared with results obtained by optical actinometry in another work.     

Prospects of thermal analysis in polymer research

A survey and an analysis of the publications concerned in thermal analysis (TA) published in four renowned journals during the years 1965–1974 were performed. The published data were evaluated from three points of view: TA methods used for polymers, properties and phenomena studied by TA methods, types of polymers investigated by TA methods. From the statistical data were derived the future trends for the application of particular TA methods in polymer science.