Thermomechanical behaviors and dielectric properties of polyaniline‐doped para‐toluene sulfonic acid/epoxy resin composites

Composites based on conductive organic/inorganic fillers dispersed in insulating matrix have been widely investigated because of their widespread applications such as electromagnetic shielding, electrostatic discharge, and sensors. In this context, novel composite materials based on epoxy resin matrix charged with polyaniline (PANI)‐doped para‐toluene sulfonic acid were elaborated. Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy were used to check the structure and the morphology of the samples. Viscoelastic behavior and thermal stability of the composites were explored by dynamic mechanical thermal analysis and thermogravimetric analysis. It was shown that the PANI particles exhibited a partial crystalline structure and were homogeneously dispersed in epoxy matrix. Consequently, this structure affected the thermal stability and viscoelastic properties of the composites. Furthermore, the dielectric and electrical properties were investigated up to 1 MHz. Measurements of dielectric properties revealed that with loading fillers in matrix, the dielectric parameters increased to high values at low frequency then decreased at values around 40 and 32 of real and imaginary parts, respectively, at 1 MHz with 15% of PANI content. Copyright © 2011 John Wiley & Sons, Ltd.     

Influence of peak measurement parameters on the quality of chiral electrophoretic separations

The effect of nine peak measurement/analysis parameters on chiral capillary electrophoresis (CE), followed by UV detection, was studied. The parameters pertained UV-detection (detection wavelength, reference wavelength, and wavelength bandwidths), signal processing (data acquisition rate, type and amount of filtering) and peak detection (detection threshold and peak width). The influence of these factors on the chiral separation of dimethindene enantiomers was studied at two different concentrations (i.e., at high and low signal-to-noise (S/N) ratio) by the means of experimental designs. The electropherogram characteristics considered were the resolution between the two enantiomers, the peak areas, and the S/N ratio. A D-optimal design was first used as screening design to identify the most critical parameters. Afterwards, a modelling of the different responses as a function of these critical parameters was performed based on the results of a face-centered central composite design. The results showed that the signal-processing parameters should be carefully selected when developing a CE separation since very important variations in the separation, the S/N ratio and the peak area of the substances can occur by setting these parameters at different levels. The detection wavelength should also be carefully chosen for optimal peak area measurement. The role of these parameters becomes more important with decreasing concentration of the analytes (i.e., low S/N ratio). This study showed that the peak measurement/analysis parameters should be optimized as the chemical and physical parameters of a method. They also should always be well specified in order to allow a good transfer of a method from one instrument to another.     

Molybdenum amido complexes with single Mo-N bonds: synthesis,structure, and reactivity

Reactions of the complex [MoCl(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1) (phen=1,10-phenanthroline) with potassium arylamides were used to synthesize the amido complexes [Mo(N(R)Ar)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (R=H, Ar=Ph, 2 a; R=H, Ar=p-tolyl, 2 b; R=Me, Ar=Ph; 2 c). For 2 b the Mo-N(amido) bond length (2.105(4) A) is consistent with it being a single bond, with which the metal attains an 18-electron configuration. The reaction of 2 b with HOTf affords the amino complex [Mo(eta(3)-C(3)H(4)-Me-2)(NH(2)(p-tol))(CO)(2)(phen)]OTf (3-OTf). Treatment of 3-OTf with nBuLi or KN(SiMe(3))(2) regenerates 2 b. The new amido complexes react with CS(2), arylisothiocyanates and maleic anhydride. A single product corresponding to the formal insertion of the electrophile into the Mo-N(amido) bond is obtained in each case. For maleic anhydride, ring opening accompanied the formation of the insertion product. The reaction of 2 b with maleimide affords [Mo(eta(3)-C(3)H(4)-Me-2)[NC(O)CH=CHC(O)](CO)(2)(phen)] (7), which results from simple acid-base metathesis. The reaction of 2 b with (p-tol)NCO affords [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(eta(2)-MoO(4))] (8), which corresponds to oxidation of one third of the metal atoms to Mo(VI). Complex 8 was also obtained in the reactions of 2 b with CO(2) or the lactide 3,6-dimethyl-1,4-dioxane-2,5-dione. The structures of the compounds 2 b, 3-OTf, [Mo(eta(3)-C(3)H(4)-Me-2)[SC(S)(N(H)Ph)](CO)(2)(phen)] (4), [Mo(eta(3)-C(3)H(4)-Me-2)[SC(N(p-tol))(NH(p-tol))](CO)(2)(phen)] (5 a), and [Mo(eta(3)-C(3)H(4)-Me-2)[OC(O)CH=CHC(O)(NH(p-tol))](CO)(2)(phen)] (6), 7, and 8 (both the free complex and its N,N'-di(p-tolyl)urea adduct) were determined by X-ray diffraction.     

Fluorine in optics

Fluorine occupies an original and strategic position in modern optics. The F₂ excimer lasers are unrivaled sources of deep UV light for semiconductors, microphotolithography and micromachining which has brought on the development of single crystal calcium fluoride optics. Due to the weak polarisability of the fluoride ion, fluoride materials have low refractive index suitable for thin film antireflective coatings specially in IR optics. Transparent magnesium fluoride ceramics, prepared by fine grains hot pressing, are transparent in the mid IR where the transparency windows of the atmosphere are located. They are used as IR domes for missiles guidance. Fluoride glasses when elaborated as optical fibers or channel waveguides and when doped with appropriate lanthanides, are original optical devices for laser operations lying from the mid IR to the UV region where light emission is characterized by up-conversion phenomena. The same devices have also found industrial applications in telecommunications as a new generation of optical amplifiers operating in the ultra-transparency window of the silica fiber.     

Pd-catalyzed one-pot coupling of allylamines, activated alkenes, and unsaturated halides (or triflate): an atom efficient synthesis of highly functionalized pyrrolidines

A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate).     

Crassiflorone, a new naphthoquinone from Diospyros crassiflora (Hien)

A new naphthoquinone, 11-hydroxy-1,9-dimethyl-6H-naphtho[2′,3′:4,5]furo[3,2-c]chromene-6,7,12-trione, named crassiflorone, was isolated from the stem bark of Diospyros crassiflora together with the known compounds plumbagin, cyclocanaliculatin, gerberinol, lupeol, lupenone and betulinic acid. The structures of the compounds were established on the basis of 1D and 2D NMR spectroscopic data, as well as co-TLC with authentic samples. Some of the above compounds exhibited significant antimicrobial activity against bacteria and yeasts.     

Highlights on the Binding of Cobalta-Bis-(Dicarbollide) with Glucose Units

Metalla-bis-dicarbollides, such as the cobalta-bis-dicarbollide (COSAN) anion [Co(C₂B₉H₁₁)₂]⁻, have attracted much attention in biology but a deep understanding of their interactions with cell components is still missing. For this purpose, we studied the interactions of COSAN with the glucose moiety, which is ubiquitous at biological interfaces. Octyl-glucopyranoside surfactant (C8G1) was chosen as a model as it self-assembles in water and creates a hydrated glucose-covered interface. At low COSAN content and below the critical micellar concentration (CMC) of C8G1, COSAN binds to C8G1 monomers through the hydrophobic effect. Above the CMC of C8G1, COSAN adsorbs onto C8G1 micelles through the superchaotropic effect. At high COSAN concentrations, COSAN disrupts C8G1 micelles and the assemblies become similar to COSAN micelles but with a small amount of solubilized C8G1. Therefore, COSAN binds in a versatile way to C8G1 through either the hydrophobic or superchaotropic effect depending on their relative concentrations.     

Afzeliixanthones A and B, two new prenylated xanthones from Garcinia afzelii ENGL. (Guttiferae)

Two new prenylated xanthones, afzeliixanthones A (1) and B (2), together with three known xanthones (3-5) and two phytosterols, beta-sitosterol and stigmasterol, were isolated from the CH2Cl2/MeOH (1:1) extract of the stem bark of Garcinia afzelii ENGL. collected in the South West Province of Cameroon. Structures were mainly established using one and two-dimensional NMR and mass spectroscopies. The antioxidant activities of the crude extracts as well as the new compounds (1) and (2) were evaluated.     

Static secondary ion mass spectrometry (S-SIMS) for the characterization of surface components in mineral particulates

The feasibility of static secondary ion mass spectrometry (S-SIMS) for the detection of molecule specific information from complex materials, such as natural clay and soil samples, has been investigated. Ion trap (IT), as well as triple quadrupole (TQ) instruments, have been used for mass analysis. Secondary ion images have been acquired using time-of-flight (TOF) S-SIMS. The generation of molecular adduct ions from thin and thick layers on the mineral substrates has been investigated using KBr as a simple model system. Results show that molecular adducts of KBr can be indeed detected from the spiked materials. However, the concentrations of the spiking solutions have to be significantly larger than expected from the surface area measured by gas adsorption techniques. In addition imaging analysis has evidenced that the detection of adduct ions in the mass spectra directly relates to the presence of local micro-crystallites.