Détermination de constantes cinétiques du craquage catalytique par la modélisation du test de microactivité (MAT)

The microactivity test (MAT) for cracking catalyst test works with an approximately plug flow isothermal reactor. The yields at the outlet of such a reactor is numerically computed in the case of lumped kinetic with large molecular expansion and rapid catalyst deactivation expressed versus poison concentration. The poison (coke in cracking reaction) is considered as a product formed by several reaction routes. The results are applied to catalytic cracking kinetic with a four lump model (feedstock, gasoline, gas, coke). The comparison between experimental and computed yields, permits the adjustment of kinetic constants with a set of experimental results obtained from a laboratory scale reactor derived from the MAT. The simulation of concentration profile in the reactor permits a better understanding of the reaction courses.     

Chemical inhibitors when timing is critical: a pharmacological concept for the maturation of T cell contacts

Cellular signal transduction proceeds through a complex network of molecular interactions and enzymatic activities. The timing of these molecular events is critical for the propagation of a signal and the generation of a specific cellular response. To define the timing of signalling events, we introduce the combination of high-resolution confocal microscopy with the application of small-molecule inhibitors at various stages of signal transduction in T cells. Inhibitors of Src-family tyrosine kinases and actin dynamics were employed to dissect the role of the lymphocyte-specific tyrosine kinase Lck in the formation and maintenance of T cell receptor/CD3-dependent contacts. Anti-CD3epsilon-coated coverslips served as a highly defined stimulus. The kinetics of the recruitment of the yellow fluorescent protein-tagged signalling protein ZAP-70 were detected by high-resolution confocal microscopy. The analysis revealed that at 5 min after receptor engagement, Lck activity was required for maintenance of contacts. In contrast, after 20 min of receptor engagement, the contacts were Lck-independent. The relevance of the timing of inhibitor application provides a pharmacological concept for the maturation of T cell-substrate contacts.     

Understanding aluminum behaviour in aqueous alkaline solution using coupled techniques: Part I. Rotating ring-disk study

Rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) measurements have been undertaken to study the behaviour of pure aluminum electrodes in alkaline media. The measurements did consist of linear sweep voltammetry from anodic to cathodic potentials on 4N, 5N or 5N5-aluminum samples in 4 M aqueous potassium hydroxide solution. In the potential range studied (−0.7 V versus NHE to −2.5 V versus NHE) the aluminum undergoes oxidation/dissolution into aluminates anions at high electrode potential while it yields strong hydrogen evolution at low potentials. Thanks to the RRDE technique, we show that hydrogen starts to evolve from the aluminum electrode even above the open circuit potential. Also, the oxidation state of superficial aluminum varies according to the electrode potential: whereas non-conducting aluminum oxides are present above the open-circuit potential hindering hydrogen evolution reaction (HER), they tend to disappear below the ocp, due to the strong hydrogen evolution, following the probable porous oxide layer blow up induced by the hydrogen bubbles formation. In consequence at very low potential, HER occurs on bare aluminum, HER kinetics being much faster than on oxide-covered aluminum.     

Copolymerization of norbornene with norbornene terminated polystyrene macromonomer in the presence of Ni-based/MAO catalytic systems

Copolymerization of -norbornenyl polystyrene macromonomer (NBE-PS) with norbornene (NBE) using Ni-based catalysts in combination with methylaluminoxane (MAO) was investigated. The nature of the catalyst, the of the polystyrene macromonomer as well as the [NBE-PS]/[NBE] ratio have been shown to be important parameters to obtain graft copolymers with high NBE-PS incorporation (up to 43 wt%). The compatibilization ability of these graft copolymers has been checked for PS/PNBE blends. The length of the grafts was proved not to be an important parameter to consider compatibilization of the PS/PNBE blend.     

A Flavanone and Two Phenolic Acids from Chrysanthemum morifolium with Phytotoxic and Insect Growth Regulating Activity

Leaves of Chrysanthemum morifolium cv. Ramat were extracted sequentially with hexane, ethyl acetate, and methanol. The methanol fraction, when incorporated into artificial diet was found to reduce the growth of cabbage looper (Trichoplusia ni Hubner) larvae at concentrations between 500 and 5000 ppm of diet. Fractionation of the methanol extract on a Sephadex column yielded five fractions, three of which reduced the weight of larvae relative to the control. One fraction was analyzed using high performance liquid chromatography (HPLC) and found to contain three main constituents. These compounds were purified using a combination of gel permeation chromatography on Sephadex LH20 and HPLC, and analyzed by 1H and 13CNMR as well as undergoing chemical and physical analyses. The compounds were identified as: 1, chlorogenic acid (5-O-caffeoylquinic acid); 2, 3,5-O-dicaffeoylquinic acid; and 3, 3', 4',5-trihydroxyflavanone7-O-glucuronide (eriodictyol7-O-glucuronide). At concentrations between 100 to 1000 ppm these compounds reduced both growth and photosynthesis of Lemna gibba L. with the order of efficacy being: flavanone > chlorogenic acid > 3,5-O-dicaffeoylquinic acid. Furthermore, when incorporated separately into artificial diet these compounds, at 10 to 1000 ppm, enhanced or reduced growth of the cabbage looper (Trichoplusia ni) and gypsy moth (Lymantria dispar L.).     

Injection molding shrinkage of PP: Experimental progress

Injection molding shrinkage deals with dimensional differences between a molded part and the cavity. By adding an array of orthogonal marks into a mold, local shrinkage values may be obtained by comparing dimensions of this array with dimensions of the array replicated on the surface of the parts. A profilograph is employed to obtain dimensional measurements, in the parallel to flow direction and in the cross flow direction. A sensitivity analysis is conducted to determine aspects of shrinkage evaluation causing uncertainty on the results. Prominent sources of uncertainty found are mark straightness defect and part warpage. Uncertainty on shrinkage is evaluated to 0.00025 mm/mm for a distance between the marks of 6.350 mm. Shrinkages have been evaluated locally for molded plates. Different distribution forms were observed for parallel to flow and cross flow shrinkage. Important anisotropy is also observed. The effects of holding pressure and injection velocity on shrinkages have been evaluated using a 2³ factorial design of experiment for three locations on the plates. Finally, shrinkages for three mold geometries have been compared: constant thickness plate, variable in thickness symmetrical plate, and variable in thickness asymmetrical plate. Variable in thickness plates showed the importance of solidification dynamics on final shrinkages. POLYM. ENG. SCI., 46:1275–1283, 2006. © 2006 Society of Plastics Engineers     

Study of the telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol. Application to the synthesis of a new macromonomer

The telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol initiated by 2,2′-azobisisobutyronitrile was first investigated at 70 °C and the influence of the type of solvent was studied. The results showed that well-defined telomers of DMAEMA could not be synthetized via telomerization of DMAEMA in water or water/acetonitrile mixture since the telomerization reaction is in competition with the nucleophilic addition of thiol onto the monomer. Transfer constants for mercaptoethanol in benzene and acetonitrile were determined by Mayo's and O'Brien's methods. The transfer constant obtained in acetonitrile (0,6) was higher than that obtained in benzene. This difference can be explained by the fact that the thiol was consumed by two reactions: nucleophilic addition and telomerization. The influence of solvents on the polymerization kinetics was enlightened. These results were applied to the synthesis of macromonomers of DMAEMA with isocyanatoethyl methacrylate (IEM). These macromonomers were copolymerized with styrene.     

Synthesis and characterization of long-chain fatty acid cellulose ester (FACE)

Long-chain fatty acid cellulose esters (FACE) were synthesized by the acid chloride-pyridine reaction with different degrees of substitution (DS). The hydrolyzed soybean oil was used as unsaturated fatty acids, its unsaturation degree, and composition were analyzed by ¹H and ¹³C NMR methods. The chemical structures of FACE were confirmed by solid-state ¹³C NMR, and substitution reaction of fatty acid chloride on cellulose were analyzed by IR spectroscopy. FACE(s) are insoluble in common organic solvents, such as benzene, toluene, THF, etc., at refluxing temperature. As the DS increased, the tensile strength of extruded FACE films decreased, but elongation increased. © 1994 John Wiley & Sons, Inc.     

Biochemical,functional, and histochemical effects of essential fatty acid deficiency in rat kidney

The present study was designed to examine the effects of EFA deficiency (EFAD) on biochemical, functional, and structural aspects of the kidney in growing and adult rats fed a normal or EFAD diet for 9 wk after weaning. Food and fluid intake (FI), urine volume, and Na⁺ and K⁺ excretions were measured weekly from weeks 4 to 8 by placing the rats in individual metabolic cages for 24 h. At week 9, Li⁺ and a 5% water load, respectively, were administered at 14 and 1.5 h prior to glomerular and proximal tubular function studies, as assessed by 3-h creatinine (C_Cr) and Li⁺ (C_Li+) clearances. Hematocrit and urine volume; serum and urine [Cr], [Li⁺], [Na⁺], and [K⁺]; and renal FA distribution were also measured. Data [corrected to 100 g/body weight (bw) and presented as means ±SEM] were significant, at P<-0.05. Despite a similar ingestion of solids from weeks 4 to 7 (weeks 7 to 10 of life), the rats on the EFAD diet showed a decreased body weight from week 5. From weeks 4 to 8, Fl and urine volume were similar for both groups, but the Fl increased at week 6 in the EFAD group; 24-h Na⁺ and K⁺ excretions were similar at all weeks, except for an increase in the EFAD group for both ions at week 7. In the EFAD group, C_Cr and C_Li+ decreased by 27 and 56.3%, respectively (385.7±33.4 vs. 280±21.1, and 21.0±2.1 vs. 9.2±1.1 μL/min/100 g; n=9 vs. 10), the latter result suggesting increased proximal reabsorption. The 3-h Na⁺ and K⁺ excretions were similar, but the Li⁺ decreased (0.78±0.06×10⁻² vs. 0.32±0.03×10⁻² μeq/min/100 g) in the EFAD group, giving additional support to the suggestion. Renal structure was normal and similar for both groups, but the EFAD group showed a more prominent proximal tubule brush border, together with heavier periodic acid-Schiff staining in all specimens from weeks 5 to 9. In the EFAD group, FA of the n−9 and n−7 series were higher, but most of the n−6 series were lower as a percentage of total lipids in the medulla and cortex. Medullary levels of 20∶4n−6 were maintained, 22∶4n−6 declined twice, arachidonic acid was maintained, and 20∶5n−3 was lower. The EFAD diet affected glomerular function, proximal tubular structure and function, and FA distribution in the rat kidney.