On the rate of heterogeneous catalytic reactions with ionic intermediates

A facile way to compute the rate law of a catalytic reaction with ionic intermediates is proposed, based on the theory of complex reactions. When the ionic nature of intermediates is taken into account it is necessary to add balance equations which correspond to the electroneutrality of the catalyst. Several mechanisms of the olefin hydrogenation were considered as examples.     

Quantification of clay dispersion in nanocomposites of styrenic polymers

Polymer‐clay nanocomposites are materials with many interesting structures, properties, and potential applications. Microstructural evaluation of a nanocomposite is not an easy task, as clay may form hierarchical structures which may look different when observed at various magnifications under a microscope, and also as the concepts of “intercalation” and “exfoliation” are not self‐sufficient to describe its morphology. In this work polymer‐clay nanocomposites of polystyrene and two styrene‐containing block copolymers (styrene‐butadiene‐styrene and styrene‐ethylene/butylene‐styrene) were prepared using three different techniques. Clay dispersion was evaluated by a recently developed microscopy image analysis procedure, combining the analysis of optical and transmission electron micrographs, and the characterization was complemented by X‐ray diffraction and rheological measurements. The results showed better clay dispersion for both block copolymers nanocomposites, mainly due to their molecular architectures. Moreover, the techniques which showed the best results involved mixing the materials in a solvent medium. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Hydrogenation of but-1-yne on platinum catalyst: Role of reversible adsorbed hydrocarbon deposit

By using rectangular pulses of but-1-yne carried by H₂ or H₂-He mixtures over a platinum catalyst, it was possible to visualize the build-up of an adsorbed hydrocarbon deposit which is a necessary condition for getting a selective catalyst (on platinum, but-1-ene selectivity is 90%). Such a deposit is reversibly adsorbed since it desorbs as hydrogenated butyne molecules when the butyne pressure drops at the end of the pulse. Moreover it was shown, during stationary phase, that the sudden fall in the selectivity at high but-1-yne conversion, is due to the desorption of such reversibly adsorbed molecules.     

Structure-cytotoxicity studies on alkyl lysophospholipids and some analogs in leukemic blasts of human origin in vitro

Eleven lipids have been tested for cytotoxic (trypan blue dye exclusion) activity in cells from eight freshly explanted human leukemias in vitro. 4-Aminomethyl-1-[2,3-(di-N-decyloxy)N-propyl]-4-phenylpiperidine (CP-46,665), 1-mercapto-hexadecyl-2-methoxymethyl-rac-glycero-3-phosphocholine (BM 41.440), the 2-acetamide analog of platelet-activating factor (PAF) and 1-O-octadecyl-2-O-methyl-rac-glycero-3-phosphocholine (ET-18-OCH₃) were found among the most active compounds. 2-Lysophosphatidylcholine (2-LPC) showed the lowest activity. However, in addition there was variation among the results regarding the activity of the 1-octadecyl-rac-glycero-3-phosphocholine (ET-18-OH) and its D- and L-forms, but a significantly higher cytotoxic activity of D-ET-18-OH compared with L-ET-18-OH on the basis of 2-LPC as control after an incubation time of 48 hr. We conclude that with the limited number of structures available, this type of study is not sufficient to yield further information about the mode of the accumulation and toxicity of this type of lipids.     

Modification of the gold electrode for the electrochemical study of cytochrome c

The modification of the gold electrode by some nitrogen hetero-cycles is used for electrochemically studying cytochrome c. Fifteen molecules are tested, but only six are active. The prominent characteristics of the active molecules are defined, and the competition between cytochrome c, 4,4′-bipyridine, 1,2-bis(4-puridyl)ethylene and aldrithiol-4 for the adsorption at the gold electrode has been studied in particular.     

Preparation and characterization of Pd-Pb catalysts for selective hydrogenation

The preparation of Pd/-Al₂O₃ and Pd-Pb/-Al₂O₃ catalysts using Pd-acetylacetonate and tetrabutyl-lead (TBPb) has been studied. In the monometallic catalyst the precursor decomposition in air leads to a well dispersed Pd phase. Reacting the Pd/-Al₂O₃ (0.19%) catalyst with TBPb in the presence of adsorbed hydrogen, produces one mol of hydrocarbons (mainly butane) per mol of Pb fixed, suggesting the formation of a surface intermediate; Pd-Pb(C₄H₈)₃. In the absence of hydrogen, the reaction is slower and the evolution of hydrocarbons (mainly butenes) decreases by a factor of 2. As the amount of Pb fixed by both procedures is the same, Pb/Pd₃ = 1.3, other surface compounds must be involved. Characterization by H₂ and CO chemisorption and FTIR spectroscopy of adsorbed CO shows that Pb addition produces a dilution of the surface Pd atoms, preventing the dissociative adsorption of H₂ and inducing the adsorption of CO in the linear form. The XPS spectra of Pd/-Al₂O₃ and Pd-Pb/-Al₂O₃ (0.19 %– 0.27%) indicate a Pb 4f/Pd 3d ratio of 1.4 and a decrease in the Pd 3d/Al 2s intensity ratio with Pb addition. These results suggest that Pb is well dispersed and in close contact with the Pd surface.     

Linear viscoelastic behavior of compatibilized PMMA/PP blends

In this work, the morphology and linear viscoelastic behavior of PMMA/PP blends to which a graft copolymer PP‐g‐PMMA has been added was studied. The copolymer concentration varied from 1 to 10 wt % relative to the dispersed phase concentration. The rheological data were used to infer the interfacial tension between the blended components. It was observed that PP‐g‐PMMA was effective as a compatibilizer for PMMA/PP blends. For PP‐g‐PMMA concentration added below the critical concentration of interface saturation, two rheological behaviors were observed depending on the blend concentration: for 70/30 blend, the storage modulus, at low frequencies, increased as compared to the one of the unmodified blend; for 90/10 blend, it decreased. For 90/10 blend, the relaxation spectrum presented an interfacial relaxation time related to the presence of the compatibilizer (τ_β). For PP‐g‐PMMA concentrations added above the critical concentration of interface saturation, the storage modulus of all blends increased as compared with the one of the unmodified blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of ageing and annealing on the mechanical behaviour and biodegradability of a poly(3‐hydroxybutyrate) and poly(ethylene‐co‐methyl‐acrylate‐co‐glycidyl‐methacrylate)blend

Poly(3‐hydroxybutyrate) (PHB) undergoes an ageing process that contributes to its remarkable fragility. Blending it with an elastomer is a possibility to increase toughness. In this work, the mechanical properties of a 70/30 wt% blend of PHB and poly(ethylene‐co‐methyl‐acrylate‐co‐glycidyl‐methacrylate) were studied over time. The phenomenon of ageing affected the blend, which lost its ductility and became fragile days after its processing. Differential scanning calorimetry and small angle X‐ray scattering analyses showed that this drop in mechanical properties was due to changes in the crystalline structure of the matrix. Annealing reduced fragility, increased toughness and prevented a re‐ageing of the blend. Biodegradation in soil was also more intense for annealed samples. © 2013 Society of Chemical Industry