Thermal behaviour of a polyhedral oligomeric silsesquioxane with epoxy resin cured by diamines

A new material belongs to the family of polyhedral oligomeric silsesquioxanes, the 1-(3-glycidyl) propoxy-3,5,7,9,11,13,15-isobutylpentacyclo-[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane (glycidylisobutyl-POSS) is characterized by differential scanning calorimetry, thermogravimetric analysis and atomic force microscopy. Epoxy systems based on diglycidyl ether of bisphenol A (DGEBA) cured with the diamines, 4,4'-diamine-diphenylmethane (DDM) and 1,4-phenylenediamine (pPDA), were kinetically studied by differential scanning calorimetry in isothermal and dynamic modes. The thermal behaviour of these systems as the glycidylisobutyl-POSS was added, is discussed later. This revised version was published online in July 2006 with corrections to the Cover Date.     

Evidence against the hopping mechanism as an important electron transfer pathway for conformationally constrained oligopeptides

The rate constant of intramolecular electron transfer through oligopeptides based on the alpha-aminoisobutyric acid residue was determined as a function of the peptide length and found to depend weakly on the donor-acceptor separation. By measuring the electron-transfer activation energy and estimating the energy gap between donor and bridge, we were able to discard the electron hopping mechanism.     

Determination of coumarins by voltammetric techniques in micellar and emulsified media

An electroanalytical study of the oxidation processes of umbelliferone and hymecromone at a glassy carbon electrode in micellar solution and emulsified medium by different voltammetric techniques is described. The non-ionic surfactant Triton X-405 in acetate-buffered medium at pH 4.8 was found to be the most suitable. Different ranges of linearity were obtained in the micellar solutions, depending on the technique used; the limits of determination for differential pulse voltammetry (DPV) at a stationary electrode were 2.9×10^?6 mol l^?1 and 3.3×10^?6 mol l^?1 for umbelliferone and hymecromone, respectively. In the emulsified medium formed with a mixture of toluene and ethyl acetate (3:2), the oxidation processes yielded similar results. With DPV, linear calibration plots were obtained in the ranges 1.0×10^?5–9.0×10^?7 mol l^?1 umbelliferone and 1.0×10^?5–2.0×10^?6 mol l^?1 hymecromone. The media used are predominantly aqueous so that special reference electrodes and solvent purification are not needed.     

HPLC-Electrochemical detection with graphite-poly (tetrafluoroethylene) electrode Determination of the fungicides thiram and disulfiram

The suitability of composite graphite-poly(tetrafluoroethylene) (Teflon) electrodes as amperometric indicator electrodes in HPLC detection is demonstrated. The determination of the fungicides thiram and disulfiram in the presence of ziram has been chosen as an analytical problem. The optimization of working conditions, such as the choice of the organic solvent used in the mobile phase as well as its percentage, the potential applied to the composite electrode, and the time elapsed between mixing the carbamates and the injection, has been accomplished by using the wall-jet flow-cell configuration. The effect of the acetonitrile percentage used in the mobile phase on the retention of thiram, disulfiram, ziram and phenol was evaluated. Resolution up to the baseline can be achieved with 45% acetonitrile. The sensitivity of the determination of thiram and disulfiram in the presence of a constant concentration of ziram is slightly better when using a wall-jet cell; however, the background current is higher, as well as the baseline noise and the time necessary to achieve stabilization of the baseline before the injection. Lower limits of detection for both fungicides, as well as a better repeatability, were obtained when using a thin-layer flow cell configuration. As an application, the determination of thiram in spiked apple samples, at a level of 0.5 mg thiram kg(-1) apple, has been carried out with a mean recovery of 97 +/- 3% for a significance level of 0.05.     

Electroanalytical study of diethyl and dibutyl phthalate in micellar and oil-in-water emulsified media

A polarographic study was carried out of the reduction processes of diethyl and dibutyl phthalate in micellar solutions with the cationic surfactant Hyamine 1622, and in an emulsified medium from aliquots of the phthalates dissolved in a diethyl ether: ethyl acetate (1:9) mixture and Hyamine 1622 as emulsifying agent. The characteristics of the reduction processes in both media were established. The number of electrons involved was higher for the base form of the electroactive species. Using dpp at E=–50 mV, the detection limits obtained in the emulsified medium were 6.7×10^–8 and 7.4×10^–7 moll^–1 for diethyl phthalate and dibutyl phthalate, respectively. Interferences between the two phthalates were studied, and the possibility of carrying out the overall determination of both phthalates was demonstrated. Good results were obtained when applying the polarographic method developed in the emulsified medium to determine diethyl phthalate by dpp in spiked milk after extraction of the analyte with diethyl ether: ethyl acetate (1:9).     

A short synthesis of C-glycosyl pyrazoles and pyrroles

The sodium salt of TOSMIC reacted with (E)-3,4,5,6,7-penta-O-acetyl-1,2-dideoxy-1-C-nitro-D-galacto- (1) and -D-manno-hept-1-enitol (2) to give 3-(D-galacto- (3) and 3-(D-manno-penta-O-acetylpentitol-1-yl)-4-nitropyrrole (4) , respectively. Compound 1 reacted with diaryl nitrile imines, affording 1,3-diaryl-4-(1,2,3,4,5-penta-O-acetyl-D-galacto-pentitol-1-yl)pyrazoles 5 and 6 .     

Photochemistry of Dihydrido(hydrotris(3,5-dimethylpyrazolyl)borato)(Z-cyclooctene)iridium. Synthetic Intermediates and Mechanism of the Photochemical Formation of Hydridophenyl(hydrotris(3,5-dimethylpyrazolyl)borato)(trimethyl phosphite)iridium

The photolysis of a benzene solution of [Tp(Me2)IrH(2)(COE)], 1 (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate, COE = Z-cyclooctene), in the presence of P(OMe)(3), gives the stable novel complex [Tp(Me2)IrH(C(6)H(5))(P(OMe)(3))], 3a. The photochemical syntheses of [Tp(Me2)IrH(2)(P(OMe)(3))], from 1 and P(OMe)(3) in diethyl ether, and [Tp(Me2)IrH(2)(CH(2)=CHCOO(t)Bu)], from 1 in tert-butyl acrylate, are also reported. The above reactions and several experiments using C(6)D(6) and P(OCD(3))(3) show that, in all cases, the primary photoproduct is the 16-electron, five-coordinate iridium(III) intermediate {Tp(Me2)IrH(2)}, 6a, produced by loss of COE from 1. The above experiments also allow the postulation of a mechanistic pathway for the formation of 3a which involves the oxidative addition of an aromatic C-H bond by 6a. Furthemore, the photochemical reaction of 1 in the presence of P(OCD(3))(3) shows that, under the reaction conditions used, oxidative addition of C-H bonds of P(OMe)(3) and of coordinated Tp(Me2)-ligands, presumably, to the intermediates 6a and {Tp(Me2)IrH(C(6)H(5))}, also occurs. Thus, coordinatively unsaturated iridium(III) species readily activate C-H bonds.     

Spin polarisation in dual catalysts for the oxygen evolution and reduction reactions

Strongly correlated catalysts can be understood from precise quantum approximations. Incorporating properly electronic correlations thus let’s define Spin rules in catalysis, opening a new door towards optimum compositions for the most important reactions for a sustainable future.