Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

On-line preconcentration of mercury by sorption on an anion-exchange resin loaded with 1,5-bis[(2-pyridyl)-3-sulphophenyl methylene] thiocarbonohydrazide and determination by cold-vapour inductively coupled plasma atomic emission

1,5-Bis[(2-pyridyl)-3-sulphophenyl methylene] thiocarbonohydrazide (PSTH) immobilized on an anion-exchange resin (Dowex) has been used for the on-line preconcentration of mercury from biological samples and waters prior to its determination by inductively coupled plasma atomic emission spectroscopy. The metal was eluted from the column using a solution of 2 M HNO(3) and mixed on-line with SnCl(2). The optimum experimental conditions were evaluated for the continuous preconcentration of Hg, the direct generation of mercury vapour and the final determination of this element by ICP-AES. The enrichment, together with low blank levels of the optimized procedure, allow the simple determination of this toxic element at concentrations down to a few nanograms per milliliter. The proposed method has a linear calibration range 5-1000 ng ml(-1) of mercury, with a detection limit of 4 ng ml(-1) (S/N=3) and a sampling rate of 40 h(-1), investigated with a 9 ml sample volume. The precision of the method (evaluated as the relative standard deviation obtained after analyzing ten series of ten replicates) was +/-3.6% at the 10 ng ml(-1) level of Hg(II) and +/-1.3% at the 100 ng ml(-1) level. The accuracy of the method was examined by the analysis of certified reference materials.     

Cyclohexylethynyl complexes of CoII and FeII

This paper deals with the synthesis of six σ-cyclohexylethynyl complexes of Co^II and Fe^II and their characterization by chemical analysis, infrared and ¹H NMR spectra, and magnetic measurements. Four of them are six-coordinate complexes, unsubstituted or substituted, namely K₄[M(C≡C—C₆H₁₁)₆] nNH₃(M = Co, n = 2; M = Fe, n = 0), K₂[Co(C≡C₆H₁₁)₄(NH₃)₂] and K₄[Fe(CN)₄-(C≡C—C₆H₁₁)₂]. Two are four-coordinate complexes of formula [(Ph₃P)₂M-(C≡C₆H₁₁)₂] (M = Co, Fe). All are low-spin complexes, the magnetic moment for the six-coordinate Co(II) complexes, measured at various temperatures, being intermediate between low- and high-spin values.     

Thermal and structural properties of commercial dental resins light-cured with blue emitting diodes (LEDs)

We have investigated the thermal and structural properties of different commercial dental resins: Filtek^TM Z-350, Grandio^®, Tetric Ceram^®, and TPH Spectrum^®. The purpose of the present study was to evaluate quantitatively the photo-polymerization behavior and the effect of filler contents on the kinetic cures of the dental resins by using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. We have successfully obtained the low and high glass transition T _g values of the dental composite resins from DSC curves. It was also observed a good agreement between the both T _g values, activation energies from thermal degradation, and the degree of conversion obtained for all samples. The results have shown that Tetric Ceram^® dental resin presented the higher T _g values, activation energy of 215 ± 6 KJ mol^?1, and the higher degree of conversion (63%) when compared to the other resins studied herein.     

Fractal Characterization of Silica Sol Prepared by the Sol-Gel Method: From the Sol Formation to the Flocculation Process

The fractal characterization of silica particles prepared by the sol-gel method was obtained; from the beginning of the sol-gel synthesis to the aggregation process of these particles by adding metal ions in solution, the fractal dimension was determined. At the beginning of the sol-gel process, unstable structures were formed due, essentially, to the auto-catalytic nature of the sol-gel condensation reactions; these particles are fractal structures with a fractal exponent corresponding to a reaction limited aggregation regime. As the time proceeds, the reactants are consumed approaching the system to equilibrium, stabilizing the size of the silica particles. The silica sol can be flocculated by adding metal ions in solution. The fractal exponent for the aggregation process was determined, obtaining a value corresponding to a diffusion limited aggregation regime.     

Surface energy properties of lignin particles studied by inverse gas chromatography and interfacial adhesion in polyester composites with electromagnetic transparency

We introduce a simple spray drying method for the scaleup production of spherical organic (lignin) particles with sizes between 0.85 and 1.57 µm. We assess the surface energy of the lignin particles by inverse gas chromatography to reveal their role in composites synthesized with unsaturated polyester. Such nanocomposites are shown to be transparent to electromagnetic irradiation (millimeter wave bands). The permittivity and tanδ of the composite material reached values 3.01 and 0.01 at 28 GHz with 10% lignin content. Vinyl groups were introduced on the surface of the particles to achieve enhanced interfacial adhesion, and resulted in a reduced relative permittivity (2.75). Together with wave interactions, the mechanical and thermal properties of the composites are put in perspective, opening new opportunities in the development of bio-based devices for 5G high-speed communication.

     

A Titration Microcalorimetric Study of the Effects of Halide Counterions on Vesicle-Forming Aggregation in Aqueous Solution of Branched-Chain Alkylpyridinium Surfactants

Titration microcalorimetry is used to study the influences of iodide, bromide, and chloride counterions on the aggregation of vesicle-forming 1-methyl-4-(2-pentylheptyl)pyridinium halide surfactants. Formation of vesicles by these surfactants was characterised using transmission electron microscopy. When the counterion is changed at 303 K through the series iodide, bromide, to chloride, the critical vesicular concentration (cvc) increases and the enthalpy of vesicle formation changes from exo- to endothermic. With increase in temperature to 333 K, vesicle formation becomes strongly exothermic. Increasing the temperature leads to a decrease in enthalpy and entropy of vesicle formation for all three surfactants. However the standard Gibbs energy for vesicle formation is, perhaps surprisingly, largely unaffected by an increase in temperature, as a consequence of a compensating change in both standard entropy and standard enthalpy of vesicle formation. Interestingly, standard isobaric heat capacities of vesicle formation are negative, large in magnitude but not strikingly dependent on the counterion. We conclude that the driving force for vesicle formation can be understood in terms of overlap of the thermally labile hydrophobic hydration shells of the alkyl chains. Copyright 2000 Academic Press.     

On-line preconcentration and determination of mercury in biological samples by flow injection vapour generation inductively coupled plasma atomic emission spectrometry

An FI-ICP-AES method for the determination of trace levels of mercury in biological samples has been described, which is based on the extraction of the mercury complex with 1,5-bis (di-2-pyridyl)methylene thiocarbonohydrazide (DPTH) on-line into isobuthyl-methyl ketone (IBMK). The organic phase (containing the complex) has been mixed on-line with SnCl₂ in N,N-dimethylformamide. Thus, mercury vapour can be generated directly from the organic phase and separated in a gas-liquid separation device. The detection limit for mercury is 4 ng/ml and the calibration curve is linear at least from 10 to 2500 ng/ml. The relative standard deviation for 10 replicate measurements is ±1% for 100 ng/ml of Hg(II). Results from the analysis of some certified biological reference materials are given.     

Chemogenomic discovery of allosteric antagonists at the GPRC6A receptor

GPRC6A is a Family C G protein-coupled receptor recently discovered and deorphanized by our group. This study integrates chemogenomic ligand inference, homology modeling, compound synthesis, and pharmacological mechanism-of-action studies to disclose two noticeable results of methodological and pharmacological character: (1) chemogenomic lead identification through the first, to our knowledge, ligand inference between two different GPCR families, Families A and C; and (2) the discovery of the most selective GPRC6A allosteric antagonists discovered to date. The unprecedented inference of?pharmacological activity across GPCR families provides proof-of-concept for in?silico approaches against Family C targets based on Family A templates, greatly expanding the prospects of successful drug design and discovery. The antagonists were tested against a panel of seven Family A and C G protein-coupled receptors containing the chemogenomic binding sequence motif where some of the identified GPRC6A antagonists showed some activity. However, three compounds with at least ～3-fold selectivity for GPRC6A were discovered, which present a significant step forward compared with the previously published GPRC6A antagonists, calindol and NPS 2143, which both display ～30-fold selectivity for the calcium-sensing receptor compared to GPRC6A. The antagonists constitute novel research tools toward investigating the signaling mechanism of the GPRC6A receptor at the cellular level and serve as initial ligands for further optimization of potency and selectivity enabling future ex?vivo/in?vivo pharmacological studies.     

In situ physical or covalent trapping of phthalocyanine macrocycles within porous silica networks

An effective way of trapping phthalocyanines inside porous silica has been achieved when an aqueous solution of these macrocyclic species is reacted in situ with silicon alkoxide. The resultant porous gel network can encapsulate a myriad of metal phthalocyanine molecules at relatively high concentrations and, most importantly, in a disaggregated way. By employing this method metal sulfophthalocyanines of Fe, Co, Ni, Cu, Al, Eu or Sm can be encapsulated within SiO₂ xerogels. Here, the chemical entrapment of phthalocyanines inside silica gel pore networks is accomplished by the attachment of bifunctional groups to the walls of these substrates; while one of these moieties is directly linked to the macrocycle end groups, the other one is covalently bonded to the silanol groups resting on the SiO₂ walls. Furthermore, when the proper concentrations of phthalocyanine species, H₂O, silicon alkoxide, and HCl are reacted together, it is possible to obtain monolithic translucent silica xerogels. This latter property provides straightforward evidence of the innate fluorescence of the trapped macrocycles. The average size of the cavities encapsulating the macrocyclic molecules range from 2.0 to 3.6 nm; the precise size depends on the cation present in the complex and on the identity and position of the substituent groups at the periphery of the macrocycle. When the silica network is prepared from standard and/or organo-substituted alkoxides, the aggregation, degradation or stability of the macrocyclic species trapped in silica cavities depends on the nature of the alkyl group attached to the pore walls.