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.     

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.     

Vibrational and electronic absorption spectra of 4-chloro 2-methyl, 4-chloro 3-methyl and 6-chloro 3-methyl phenols

The infrared spectra of 4-Cl 2-Me, 4-Cl 3-Me and 6-Cl 3-Me phenols have been recorded. The vibrational spectrum has been analysed assuming that the molecules belong toC _s point group and a tentative assignment of the observed frequencies to various modes of vibration has been proposed. The near ultraviolet absorption spectrum of these compounds has also been recorded. Assuming the transition to be electronically allowed the strongest band on the longer wavelength side has been assigned as the (0, 0) band in each case. The spectrum has been analysed in terms of several excited state frequencies which have been correlated with the ground state frequencies observed in the infrared spectrum.     

Crystallization Processes in Composite Biomaterials

The crystallization processes in composite biomaterials containing fluorapatite (FA) and gel glasses (GG) have been investigated. Using the sol-gel method three gel-glasses have been synthesized: ZnO·SiO₂, ZnO·Al₂O₃·2SiO₂ and ZnO·CaO·2SiO₂. The composites have been prepared from GG and FA in different mole ratios and each of them treated at 950°C, 1050°C, 1150°C and 1250°C. From the XRD analysis of the composites it has been established that fluorapatite is present as a major crystalline phase. The XRD patterns and the IR spectra of the pure GG systems have been studied at 200°C, 600°C and 800°C. The surface of the samples has been analyzed before and after the in vitro experiments using SEM. An amorphous layer has been observed on the surface of each of the treated samples. The element concentration and the solubility of the samples have been analyzed after the in vitro experiments by Atomic Absorption Spectroscopy (AAS).     

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.     

Synthesis,crystal and spectroscopic characterization of [RuHCl(CO)(PPh3)2(pyrazine)]

The reaction of [RuHCl(CO)(PPh₃)₃] with pyrazine has been examined and a ruthenium(II) complex – [RuHCl(CO)(PPh₃)₂(C₄H₄N₂)] -- has been obtained. The compound has been studied by IR, UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagram of the complex has been calculated with density functional theory (DFT). The spin-allowed singlet--singlet electronic transitions of the complex have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the compound has been discussed on this basis.     

Restricted rotations and stereodynamics of aziridine-2-methanol derivatives

‘Gear-like’ rotations of simple C-C bonds have been observed in some aziridine methanol derivatives. These restricted rotations have been studied by dynamic and multinuclear magnetic resonance experiments, and the barrier for rotations of Csp³-Csp³ and Csp³-Csp² bonds have been calculated. The role of an intramolecular hydrogen bond on the stereodynamics has also been demonstrated.     

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.     

Cycloaliphatic-aromatic polyimides based on diamines with azobenzene unit

A new family of functionalized semiaromatic polyimides has been developed. Cycloaliphatic-aromatic polyimides, derived from the polycondensation of 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA) with various diamines bearing azobenzene group, have been prepared and characterized. Molecular structural characterization for the resulting polymers has been achieved by ¹³C NMR, ¹H NMR, FTIR and UV-visible spectroscopies. Light-induced optical anisotropy, in novel azobenzene functionalized polyimides, has been studied by holographic polarization grating recording performed at 514.5 nm line of Ar⁺ laser. Two-wave mixing technique has been employed to inscribe the gratings in these polymers. Formation of gratings has been investigated with two s-s and s-p polarized writing beams. The kinetics of grating recording observed within the studied polymers is discussed in relation to their structure.     

A convenient palladium catalyzed synthesis of symmetric biaryls, biheterocycles and biaryl chiral diamides

A series of symmetrical diamido biaryls has been synthesized in good yield by direct homocoupling of iodoarylbenzamides by palladium-catalysis. No cross product has been isolated from the reaction mixture of two different iodoarylbenzamides under similar conditions. However, only in the case of 2-iodo-N-phenylbenzamide, the intramolecularly coupled product phenanthridone has been isolated as a minor product along with the major intermolecularly coupled product. Biphenyl chiral diamides have been synthesized by this coupling method. This coupling reaction also works well with the reductive dimerization of functionalized heterocyclic compounds. Thus 6,6′-dipivaloylamino-3,3′-bipyridine and 6,6′-dimethyl-2,2′-bipyridine have been efficiently synthesized. In two cases, the X-ray crystal structures have been solved to establish the structures of symmetrical and chiral diamido biaryls and their supramolecular networks.     

Thermal Studies on Ionic Derivatives of Hafnium(IV) Involving Maltol Ligand

A number of ionic chelate complexes of maltol(A) and hafnium(IV) the type[(η₅−C₅H₅)₂HfL]⁺[MCl3]⁻ (B) [HL=maltol; M=Zn(II), Cd(II), Hg(II), Cu(II)]have been synthesized and characterized by spectral studies (IR, UV, ¹H NMR and ¹³C NMR). The stoichiometry of the complexes has been confirmed by conductance measurements. Thermogravimetric (TG) and differential thermal analytical (DTA) studies have been carried out for these complexes and from TG curves, the order, apparent activation energy and apparent activation entropy of the thermal decomposition reactions have been elucidated .The order in each case has been determined to be one and the degree of spontaneity and lability have been inferred from the apparent activation energy and entropy, respectively. Thermal parameters have been correlated with some structural aspects of the complexes concerned. From differential thermal analysis curves, the heat of reaction has been calculated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of fluoroquinolones in urine and serum by using high performance liquid chromatography and multiemission scan fluorimetric detection

A high performance liquid chromatography (HPLC) method has been developed for the simultaneous determination of four fluoroquinolones. The studied compounds have been enoxacin (ENO), norfloxacin (NOR), ofloxacin (OFLO) and enrofloxacin (ENRO). An isocratic elution method, using a mixture of tetrahydrofuran (8%) and phosphate buffer (pH 3.00, 30.0 mM, 92%) as mobile phase, has been developed. Fluorimetric detection, exciting at 277 nm, and multiemission scan (407 nm for ENO, 444 nm for both NOR and ENRO and 490 nm for OFLO) has been used. Detection limits of 500, 14.7, 25.2 and 15.0 ng mL⁻¹ for ENO, NOR, OFLO and ENRO, respectively, have been obtained. The proposed method has been satisfactorily applied to analyze NOR, OFLO and ENRO in human urine and serum samples.     

Spectroscopy with sound on superfluid 3He B

Collective modes of superfluid ³He B have been studied by means of sound attenuation and sound velocity studies. A new sound attenuation peak has been observed in superfluid ³He B at ?ω ≈ Δ(T). This peak has been identified with the real squashing mode. Pulse time of flight methods has been used in these studies. At high sound amplitudes, interesting transient effects have been observed which have been tentatively identified with solitonlike behavior.     

Synthesis,characterization, and organocatalytic application of chiral ionic liquids derived from (S,R)-noscapine

(S,R)-Noscapine, a phthalideisoquinoline alkaloid has been used as precursor for the synthesis of chiral ionic liquids (CILs). Noscapine based CILs have been synthesized from reaction between (S,R)-noscapine and methyl iodide in acetonitrile at room temperature. The synthesized CILs have been characterized by ¹H NMR, ¹³C NMR, EI-MS, and polarimetry techniques. These CILs have been used as organocatalysts in the enantioselective reduction of prochiral ketones to produce optically active secondary alcohols. The optically active secondary alcohols have been obtained with excellent yields and low to moderate enantiomeric excess (ee); also the complete enantiomeric excess (100% ee) has been achieved in some cases.     

Pressurized liquid extraction and liquid chromatography–tandem mass spectrometry applied to determine iodinated X-ray contrast media in sewage sludge

Pressurized liquid extraction (PLE) has been successfully applied for the first time to the extraction of five iodinated X-ray contrast media from sludge. Once optimized all PLE parameters, the extract has been analyzed by liquid chromatography–tandem mass spectrometry, being the method developed sensible enough to reach limit of quantifications (LOQs) of 25 μg kg⁻¹ (d.w.). The developed method has been applied to the analysis of sludge from urban sewage treatment plants and although some compounds such as iopromide, diatrizoic acid and iopamidol have been identified, their concentrations have been lower than their LOQs.     

Thiophene separation from aliphatic hydrocarbons using the 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid

The ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate has been tested as solvent for the separation of thiophene from aliphatic hydrocarbons. Liquid–liquid equilibrium data have been determined for ternary systems containing the ionic liquid, thiophene and C₆, C₇, C₁₂ or C₁₆ alkanes at T = 298.15 K. The performance of the ionic liquid as solvent in such systems has been evaluated. The experimental data were correlated using the NRTL and UNIQUAC equations, and the binary interaction parameters have been reported. The phase diagrams for the ternary mixtures including both the experimental and calculated tie-lines have been presented.     

Volumetric studies and thermodynamics of viscous flow of hydroxamic acids in acetone + water solvent at temperatures 303.15 and 313.15 K

Densities ρ and viscosities η of two hydroxamic acids, N-phenyl-2-chlorobenzo- and N-o-tolyl-4-chlorobenzo-, have been determined as a function of their concentration in aqueous acetone solution at temperatures 303.15 and 313.15 K. Apparent molar volumes, standard-state partial molar volumes and relative viscosities have been calculated. The viscosity data have been analyzed using Jones-Dole equation. The activation thermodynamic parameters of viscous flow have been evaluated using Feakins equation. These were obtained to throw light on the mechanism of viscous flow. Thermodynamic interactions in solutions have been studied in terms of a number of excess functions calculated from the experimental data. The effect of hydroxamic acid concentration and temperature on these parameters has been discussed. The results were interpreted in the light of solute-solvent interactions in aquo-organic media.     

Fungicidal and bactericidal activity of metal diethyldithiocarbamate fungicides

Copper diethyldithiocarbamate, cadmium diethyldithiocarbamate, lead diethyldithiocarbamate, nickel diethyldithiocarbamate and zinc diethyldithiocarbamate have been synthesized. They have been characterized using TG, DTA, IR spectroscopy, X-ray and atomic absorption spectrophotometry. The thermal conversion of the compounds is 54.36–88% at 1000°C. Their solubility in sodium hydroxide, mineral acids, organic solvents, distilled water and salts solution has been measured. Fungicidal activity of the dithiocarbamates has been tested by well or cup diffusion method using five fungi species. Their activity has also been tested by broth dilution method using six bacterial species. Minimum Inhibitory Concentration (bactericidal) is 6.25–25.00 μg mL⁻¹.     

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.     

Precision high-speed neutron activation analysis via very short-lived activities

An automated, highly reproducible fast-transfer system (0.36±0.01 sec) has been developed, an oscillator/multichannel-scaling system has been developed to follow rapidly-changing spectrometer dead-times, the mathematics has been developed, and the data processing steps have been computerized. Three induced activities have been studied in some detail:^207mPb (0.80 sec),^38mCl (0.70 sec) and²⁰F (11.03 sec). Both steady-state and high-intensity pulsed reactor irradiations, with and without a Cd liner, have been used. The dead-time correction method has been carefully checked, and the overall method has been tested by the analysis of two NBS Standard Reference Materials: orchard leaves (for Cl and Pb) and bovine liver (for Cl). This paper represents a portion of the Ph. D. thesis of D. A. MILLER.