Na2CrO4-NaF-NaI and K2CrO4-KF-KI three-component systems

Na₂CrO₄-NaF-NaI and K₂CrO₄-KF-KI three-component systems have been studied by differential thermal analysis (DTA). The compositions and melting temperatures have been determined and the enthalpies of melting have been measured for eutectic mixtures. Phase equilibria in the title systems have been described, and phase fields have been demarcated.     

Synthese de substances macromoleculaires renfermant des motifs monomeres derives de colorants—XIX: Synthese d'oligoethers et d'oligoesters colores par structure

Oligo-oxyethylenes and oligo(oxyethylenes-Co-oxypropylenes) with hydroxy end-groups have been modified by nitration and amination of the end-groups; the modification was partial in some cases and complete in others. Amino end-groups have been diazotized and the oligomers with azo end-groups have been coupled with β oxynaphthic acid and N,N′diethylaniline. Oligomers with chromophoric and hydroxy groups in the chain have been used to prepare polyurethane foams. Structurally coloured polyesters have been synthesized similarly and used to prepare polyurethane elastomers. All these oligomers have been characterized by i.r. and visible spectroscopy, NMR, end-group titration, vapour pressure osmometry and thermal differential analysis.     

Alkaloids ofNitraria sibirica. Structure and absolute configuration of sibirinine

The chemical properties of sibirinine have been studied, its synthesis has been performed, and its¹H and¹³C NMR spectra have been analyzed. From the results obtained its structure and absolute configuration have been deduced.     

Curing of an epoxy resin modified with poly(methylmethacrylate) monitored by simultaneous dielectric/near infrared spectroscopies

Simultaneous dielectric and near infrared measurements have been performed in “real-time” to follow polymerisation reactions on blends of a diglycidyl ether of bisphenol-A epoxy resin with 4,4^′-diaminodiphenylmethane hardener and different amounts of poly(methylmethacrylate) as modifier. The effect of the modifier amount on the polymerisation reactions has been studied, as well as that of the curing temperature. Epoxy and amine conversions have been followed by near infrared spectroscopy (NIR), while changes in molecular mobility in the reaction mixture have been analysed by dielectric relaxation spectroscopy (DRS). Evolutions of ionic conductivity and α-relaxation have been analysed and vitrification times have been obtained. The relaxational behaviour has been analysed through curing in the frequency domain, being the change of the main relaxation indicative of the cure reaction advancement. DRS data are also presented as complex impedance Z(ω). Vitrification times, obtained by dielectrometry have been compared with those obtained by rheological measurements and gelation times obtained by NIR have been compared with those obtained by solvent extraction.     

Azacrownlactams Derived from Biphenyl. Study of Their Conformations, Complexation Ability and Electrochemical Behavior

Several macrolactams containing in their structure biphenyl and pyridine moieties have been synthesized. The complexation ability of these compounds has been evaluated and the results have been explained considering the existence of intramolecular hydrogen bonds. Conformational studies have been developed in some cases. Single-crystal X-ray diffraction studies have been carried out with one of the ligands. The electrochemical response of ligands 1 and 3 has been studied using cyclic and square wave voltammetry. The interaction of these ligands with Cu²⁺ ions in CH₃CN has been investigated by electrochemical techniques.     

Solution properties of poly(N-vinyl carbazole)—II. Thermodynamic properties in various solvents

Thermodynamic properties of dilute solutions of Poly-N-vinyl carbazole obtained by cationic polimerization have been studied by viscometry in various solvents. The validities of some excluded volume theories have been tested and the unperturbed dimensions have been calculated. The dependence of molecular dimensions, 〈s²〉, on molecular weight and viscometric equations have also been determined.     

A systematic approach to the AA′BB′, AA′BB′MX and derived systems in nuclear magnetic resonance

The AA′BB′ and AA′BB′MX nuclear magnetic resonance spin systems for I = ½ nuclei have been analysed. Expressions for the transition frequencies and intensities have been obtained which have the maximum accuracy consistent with practicable use. The analyses have been applied respectively to a hypothetical AA′BB′ nuclear spin system and to the two molecules para- fluoro-phenyldichlorophosphine and tris-para-fluorophenylphosphine. Inconsistencies in earlier treatments of the AA′BB′ system have been clarified.     

Non-symmetrical discotic liquid crystalline dimers: molecular design,synthesis and mesomorphic properties‡

The synthesis and mesomorphic properties of novel non-symmetrical discotic dimers have been investigated. Dimers have been prepared by the combination of electron-deficient (n-type) anthraquinone and electron-rich (p-type) triphenylene discotic monomers. The mesophases have been characterised using polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. Most of the dimers have been shown to exhibit a rectangular columnar mesophase and one has a nematic columnar mesophase also. Charge transfer behaviour has been studied by UV–Vis spectroscopy.     

Preparation and testing for homogeneity of spiked strawberry and cabbage candidate reference materials

Strawberry and cabbage candidate reference materials (RMs) have been prepared by our laboratory during 1992–1993. Fresh materials have been homogenized and spiked with known concentrations of pesticides representing compounds commonly used for strawberries and cabbages. The candidate RMs have been then freeze-dried, homogenized, bottled under a stream of nitrogen and stored frozen at –20°C. Homogeneity and stability of the candidate RMs have been studied during the storage period. Homogeneity of the candidate RMs for 5 g samples has been within 10%. Homogeneity and stability studies have been carried out using the conventional multiresidue method of Luke et al. [1]. Instrumental analysis have been performed by gas chromatography mass spectrometry (GC-MS) employing selected ion monitoring (SIM).     

Synthesis and properties of glasses in the PbCl<Subscript>2</Subscript>-MoO<Subscript>3</Subscript>-TeO<Subscript>2</Subscript> system

The boundaries of tellurite glasses in the PbCl₂-MoO₃-TeO₂ system have been determined. Glass samples have been synthesized, and their spectroscopic (IR) and electrophysical (resistance versus temperature) properties have been studied.     

The laser Raman and infrared spectra of crystalline dibenzyl

The Raman spectrum of crystalline dibenzyl has been excited with a 50-mw He-Ne laser (6328 Å) and thirty one Raman bands have been recorded. The far infrared spec trum which reveals six absorptions in the 10–270 cm⁻¹ region and the infrared spectrum from 300–3200 cm⁻¹ have been observed, and correlations with the Raman frequencies have been established. Assignments of some of the characteristic frequencies have been made, and the implications of the data regarding the geometry of the molecule are discussed.     

Thermodynamic properties of DCl in D2O solution from 5 to 50°C

The themodynamic properties of solutions of deuterium chloride (DCl) in deuterium oxide (D₂O) have been determined from emf measurements of the electrochemical cell without transference from 5 to 50°C, and from 0.002 to 1.0 mol-kg^–1. The standard potential of the silver/silver chloride electrode relative to the platinum/deuterium electrode has been determined. An equation for the Gibbs energy as a function of temperature has been derived from which the enthalpy, entropy, and heat capacity have been computed. Equations for the activity coefficient and the osmotic coefficient of DCl in D₂O have been developed. The excess Gibbs energy of the solution and the excess partial molar free energy as a function of temperature have been calculated, from which the other excess thermodynamic properties have been computed. The values for the heat capacity and the apparent molar heat capacity have been compared with calorimetric data in the literature. The relative partial molar enthalpy has been calculated. The solvent isotope effect on the excess thermodynamic functions is discussed.     

Physicochemical foundations of synthesis of new ferromagnets from chalcopyrites A<Superscript>II</Superscript>B<Superscript>IV</Superscript>C<Stack><Subscript>2</Subscript><Superscript>V</Superscript></Stack>

The results of studying phase equilibria of ternary A^IIB^IVC^V systems have been reported. Physicochemical foundations have been developed for the synthesis of new ferromagnets with Curie temperatures above room temperature structurally compatible with basic semiconducting materials. Methods of synthesis and physicochemical properties of manganese-doped A^IIB^IVC₂^V ferromagnets have been described. The results of theoretical simulation of magnetic properties have been considered and basic approaches to the explanation of the emergence of ferromagnetism in A^IIB^IVC₂^V doped with 3d metals have been surveyed. The most promising ways to produce and study dilute magnetic semiconductors as spintronics materials have been presented.     

Physicochemical studies on the micellization behavior of cetylpyridinium chloride and triton X-100 binary mixtures in aqueous medium

Physicochemistry of micellization of binary mixtures of cetylpyridinium chloride (CPC) and Triton X-100 (TX-100) have been investigated and the data collected have been analyzed and correlated. Tensiometric, conductometric, spectrophotometric, calorimetric and polarographic methods have been employed in the study. Parameters like critical micellar concentration (CMC), counter-ion binding, energetics of micellization, interfacial surfactant adsorption and minimum area of amphiphile head groups at CMC have been determined. The diffusion coefficients of pure and mixed micelles in solution have been determined by the polarographic method. The regular solution theory of Rubingh has been considered to get information on the micellar composition and their mutual interaction (synergistic for the studied system) in solution. The packing of the monomer in micelle has been estimated to witness spherical geometry for CPC and its mixtures with TX-100, whereas the later has been found to be spheroidal. Polarographic measurements have evidenced comparable diffusion coefficients of CPC and TX-100 micelles whereas their mixed micelles have shown lower values with a minimum, at equimolar composition.     

Cyclohexene-sulfur bichloride adducts.: Stereochemical considerations.

The reaction of sulfur dichloride with cyclohexene produces two isomeric trans-adducts of meso and dl configurations. Derivatives of both series have been obtained and configurations have been assigned by means of pseudoasymmetry. General principles for the conformational analysis of systems which contain two inverting 6-membered rings have been discussed and the positions of conformational equilibria have been evaluated. The new conformational effect-stabilization of “heteroconformer”—has been found in the case of dl-bis(2-chlorocyclohexyl) sulfoxide.     

Erratum

Abstract

1,3-oxathianes and 1,3-dithianes, with and without p-bromophenyl group in position 2, have been oxidized to sulphoxides. Both starting materials and oxidation products have been resolved by chromatography, and CD spectra have been recorded. Absolute configuration for the p-bromophenyl compounds have been assigned on the basis of known absolute configurations for analogous 1,3-oxathiolanes.     

Solution properties of poly(N-vinyl carbazole)—III: Excluded volume theories and theta temperature

Thermodynamic properties of dilute solutions of poly-N-vinylcarbazole have been studied by viscometry in chlorobenzene and nitrobenzene at several temperatures. The validities of some excluded volume theories have been tested and the unperturbed dimensions have been calculated; for two of these theories in particular, no dependence of unperturbed dimensions on temperature and solvent has been found. The viscometric equations have also been determined. The theta temperatures for PNVC in chlorobenzene and nitrobenzene are ? 36.5 and ? 20.4°C respectively.     

Ab initio studies of the structures and force fields of ketenimine and related molecules

Theoretical equilibrium geometries for ketenimine, aminoacetylene and ethynol have been obtained using the MP3/6-31G** ab initio method. Empirical scaling factors have been introduced to estimate the rotational constants A_o, B_o and C_o. In addition the complete harmonic force fields for ketenimine, ketene and diazomethane have been computed, normal coordinate analyses have been performed and the quartic centrifugal distortion constants estimated.     

Stereochemical characterization of some mono- and diaryl substituted ethylene oxides by NMR spectroscopy

NMR spectra of several styrene, stilbene and stilbazole oxides have been determined, and chemical shifts and coupling constants have been correlated with cis-and trans-configurations. Assignments have been made for all protons, and double resonance technique and ¹³C? H coupling constants have been used in some particular cases. An explanation is proposed for the observation that chemical shifts of oxirane protons are higher for cis than for trans isomers.     

Amarantholidols and amarantholidosides: new nerolidol derivatives from the weed Amaranthus retroflexus

Seven new sesquiterpenes, with nerolidol skeleton, have been isolated and characterized from the plant Amaranthus retroflexus, one of the major weeds of the world. The structures have been elucidated on the basis of spectroscopic data. The compounds have been characterized by the presence of hydroxyl groups or a glucopyranosyl moiety in the molecules. The configurations have been determined using Mosher's method. The compounds have been tested for their phytotoxicity on the test species Lactuca sativa. The bioassays showed an inhibitory effect on seed germination for all of compounds at the lowest concentrations.