Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography-mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H-MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Bronsted acid sites on the H-MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT-rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced.

Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase immobilized on active carbon

For the first time horseradish peroxidase (HRP) immobilized on the surface of active carbon powder modified at the surface of a glassy carbon electrode has been shown to undergo a direct quasi-reversible electrochemical reaction. Its formal potential, E-o/, is -0.363 V in phosphate buffer solution (pH 6.8) at a scan rate of 100 mV/s and is almost independent of the scan rate in the range of 50-700 mV/s. The dependence of E-o/ on the pH of the buffer solution indicated that the conversion of HRP-Fe(III)/HRP-Fe(II) is a one-electron-transfer reaction process coupled with one-proton-transfer. The experimental results also demonstrated that the immobilized HRP retained its bioelectrocatalytic activity to the reduction of H2O2. Furthermore, the HRP adsorbed oil the surface of the active carbon powder can be stored at 4 degreesC for several months without any loss of the enzyme activity. The method presented for immobilizing HRP can be easily extended to immobilize and obtain the direct electrochemistry of other enzymes.

Carboxyl-cored dendrimer and toluene-assisted fabrication of uniform platinum nanodendrites at a water/oil interface and their potential application as a catalyst

Uniform platinum nanodendrites have been prepared at a water/oil interface by a facile catalyst-free method at room temperature. This is carried out by introducing NaBH4 into the platinum precursor solution in the presence of the second generation of carboxyl-cored dendrimer ([G-2]-CO2H dendrimer) and toluene to act as a protective agent and a linker, respectively. The average fractal dimension of 1.61 of the obtained platinum nanodendrites is calculated by analysing the transmission electron micrographs using the programs Fractal Dimension Version 1.1 and Fractal Dimension Calculator. Control experiments show that the fabrication of platinum nanodendrites can be operated with a wide parameter window, which undoubtedly raises the degree of control of the synthesis process. The potential application of such a nanostructure as a catalyst is investigated, and the results reveal that they show highly efficient catalytic properties for the typical redox reaction between hexacyanoferrate (III) and thiosulfate ions at 301 K.

Kinetic and electrochemical properties of icosahedral quasicrystalline Ti45Zr35Ni17Cu3 powder

Kinetic and electrochemical properties of icosahedral quasicrystalline Ti45Zr35Ni17Cu3 alloy powder as negative electrode material of Ni-MH battery have been investigated at different temperatures. The calculated results show that the apparent activation enthalpy of the charge-transfer reaction is 43.89 kJ mol(-1), and the activation energy of hydrogen diffusion is 21.03 kJ mol(-1). The exchange current density and the diffusion coefficient of hydrogen in the bulky electrode increase with increasing temperature, indicating that increasing temperature is beneficial to charge-transfer reaction and hydrogen diffusion. As a result, the maximum discharge capacity, activation property and high-rate dischargeability are greatly improved with increasing temperature. However, the charge retention and the cycling stability degrade with the increase of the temperature.

Electrochemical properties of Ti0.17Zr0.08V0.35Cr0.10Ni0.30 alloy electrode

The electrochemical properties of the Ti0.17Zr0.08V0.35Cr0.10Ni0.30 alloy electrode were investigated. This alloy has good cycle life at 303 K, 313 K, and even at 323 K, but the discharge capacity decreases gradually at 333 K with increasing cycle number. Both the charge-discharge efficiency and the charge-discharge voltage reduce. The electrochemical impendence spectra indicate that the charge-transfer resistance decreases while the exchange current density increases as temperature increases. The apparent activation energy of the charge-transfer reaction is about 50 kJ mol(-1), which is higher than that on the AB(5) type alloy electrode.

VOLTAMMETRY OF CYTOCHROME-C ENTRAPPED IN HYDROGEL MEMBRANE ON GRAPHITE ELECTRODE

The voltammetric behavior of cytochrome c entrapped in hydrogel membranes at paraffin wax-impregnated spectroscopic graphite electrodes (WISGE) was studied in this paper. A pair of well-defined peaks appeared at +70 mV (vs. Ag/AgCl). Beside these two peaks, another pair of peaks emerged at around +225 mV. Further investigations suggested that at least three states of cytochrome c existed in the membranes due to the special structure of the hydrogel. The native conformation of cytochrome c molecules was stabilized by the hydrophilic environment that was formed by the hydroxyl structure of the membranes and facilitated the cytochrome c electron transfer reaction at +70 mV. The molecules directly adsorbed on the surface of the graphite electrode were responsible for the redox peaks at around +225 mV. Whether the adsorption peaks were detectable or not was related to the thickness of membranes and the pre-retaining time before the formation of membranes.

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF SOME NITRO-CONTAINING BIFUNCTIONAL AROMATIC-COMPOUNDS - LOCATION OF PROTONATION SITE

It is found that the nitro substituent of some aromatic bifunctional compounds shows unusual reactivity towards protonation. In the chemical ionization mass spectra of nitrobenzoic acids and their esters and amides, and of nitrophenols and their ethers, protonations on the carboxyl, ester, amide, hydroxyl or alkoxyl groups are highly suppressed by that on the nitro group. As a result, fragmentations based on protonation on these groups unexpectedly become negligible. Ortho effects were observed for all the ortho isomers where the initial protonation on the nitro group is followed by an intramolecular proton transfer reaction, which leads to the expected 'normal' fragmentations. Protonation on the nitro substituent is much more favourable in energy than on any of the other substituents. The interaction of the two substituents through the conjugating benzene ring is found to be responsible for this 'unfair' competitive protonation. The electron-attracting nitro group strongly destabilizes the MH+ ions formed through protonation on the other substituent; although the COR (R = OH, OMe, OEt, NH2) groups are also electron-withdrawing, their effects are weaker than that of NO2; thus protonation on the latter group produces more-stable MH+ ions. On the other hand, an electron-releasing group OR (R = H, Me, Et) stabilizes the nitro-protonated species; the stronger the electron-donating effect of this group the more stable the nitro-protonated ions.

REDOX THERMODYNAMICS OF CYTOCHROME-C AT THE BARE GLASSY-CARBON ELECTRODE

Investigation of the redox thermodynamics of horse heart cytochrome c at bare glassy carbon electrodes has been performed using cyclic voltammetry with a nonisothermal electrochemical cell. The thermodynamic parameters of the electron-transfer reaction of cytochrome c have been estimated in different component buffer solutions. The change DELTAS(re)-degrees in reaction center entropy and the formal potential E-degrees' (at 25-degrees-C, vs. standard hydrogen electrode (SHE)) for cytochrome c are found to be -64.1 J K-1 mol-1 and 0.251 V in phosphate buffer, -64.8 J K-1 mol-1 and 0.257 V in Tris + HCl buffer, -65.6 J K-1 mol-1 and 0.261 V in Tris+CH3COOH buffer (pH 7.0, ionic strength 100 mM). The temperature dependence of the formal potential obtained in phosphate buffer with or without NaCl in the range 5-55-degrees-C shows biphase characteristics in an alkaline solution with an intersection point at ca. 44-degrees-C or 42-degrees-C, which should be due to a structural change in the protein moiety of cytochrome c. However, in acidic and neutral solutions only a monotonic relationship between E-degrees' and temperature is observed. The effect of the buffer component on E-degrees' for cytochrome c is also discussed.

STRUCTURE AND PROPERTIES OF SEQUENTIALLY POLYMERIZED PROPYLENE-B-[ETHYLENE-CO-PROPYLENE]-B-PROPYLENE COPOLYMERS

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using delta-TiCl3-Et2AlCl as a catalyst system. The results indicate that the intrinsic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP / EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.

CHARACTERIZATION, MORPHOLOGY AND THERMAL-PROPERTIES OF ETHYLENE PROPYLENE BLOCK COPOLYMERS

Characterization, morphology and thermal properties of commercial ethylene-propylene block copolymers have been studied by C-13 nuclear magnetic resonance (n.m.r.) spectroscopy, differential scanning calorimetry (d.s.c.), dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM). The results obtained show that there exists some ethylene-propylene random copolymer in the block copolymers extractable by n-heptane. The possibility of forming PP-b-PE diblock copolymer is questionable on the basis of the effects of residual propene and the chain-transfer reaction in the sequential copolymerization. A difference in the thermal properties between commercial ethylene-propylene block copolymers and PP/PE blends was noticed, which cannot be used to identify PP-b-PE diblock copolymer. The multiphase structure has been confirmed by d.m.a. and SEM, with ethylene-propylene random copolymer and polyethylene forming the domains in the matrix of polypropylene.