Kinetics of hydroformylation of 1-octene in ionic liquid-organic biphasic media using rhodium sulfoxantphos catalyst

Biphasic hydroformylation of 1-octene was performed using rhodium sulfoxantphos catalyst dissolved in [BuPy][BF4] ionic liquid. Preliminary experiments proved this system to retain the catalytic complex within the ionic liquid phase and to maintain a high selectivity towards the linear aldehyde (n:iso ratio of 30) over several cycles. Process parameter investigation showed a first order dependence of the initial rate with respect to the catalyst and 1-octene concentrations, but a more complex behavior with respect to hydrogen (fractional order) and carbon monoxide partial pressures (inhibition at high pressures). Different mathematical models were selected based on the trends observed and evaluated for data fitting. Also, rate models were derived from a proposed mechanism, using Christiansen matrix approach. To calculate concentrations of substrates in the catalytic phase as required by this kinetic modeling, solubility measurements were preformed for the gases (pressure drop technique), as well as for 1-octene and n-nonanal (thermogravimetry analysis)

Corporate voluntary greenhouse gas reporting: stakeholder pressure and the mediating role of the chief executive officer

The study sheds light on the extent to which various stakeholder pressures influence voluntary disclosure of greenhouse gas (GHG) emissions and how the impact is explained and moderated Chief executive office (CEO) characteristics of 215 FTSE350 listed United Kingdom (UK) companies for the year 2011. The study developed a classification of GHG emission disclosure based on the guidelines of GHG Protocol, DEFRA and Global Framework for Climate Risk Disclosure using content analysis. Evidence from the study suggests that some stakeholder pressure (regulatory, creditor, supplier, customer, board control) positively impacts on GHG disclosure information by firms. We found stakeholder pressure in the form of regulatory, mimetic and shareholders pressure positively influenced the disclosure of GHG information. We also found creditor pressure also had a significant negative relationship with GHG disclosure. While CEO age had a direct negative effect on GHG voluntary disclosure, its moderation effect on stakeholder pressure influence on GHG disclosure was only significant on regulatory pressure

Orbital frustration at the origin of the magnetic behavior in LiNiO2

We report on the ESR, magnetization and magnetic susceptibility measurements performed over a large temperature range, from 1.5 to 750 K, on high-quality stoichiometric LiNiO2. We find that this compound displays two distinct temperature regions where its magnetic behavior is anomalous. With the help of a statistical model based on the Kugel'-Khomskii Hamiltonian, we show that below T_of ~ 400 K, an orbitally-frustrated state characteristic of the triangular lattice is established. This then gives a solution to the long-standing controversial problem of the magnetic behavior in LiNiO2.Comment: 5 pages, 5 figures, RevTex, accepted in PR

Ultrasound to Enhance a Liquid–Liquid Reaction

Liquid–liquid mass transfer with ultrasound was investigated experimentally during the hydrolysis of n-amyl acetate. Power ultrasound is supposed to improve the yield and kinetics of such multiphase chemical reactions thanks to the mechanical effects of cavitation. Indeed, implosion of micro-bubbles at the vicinity of the liquid– liquid interface generates disruption of this surface, and enhances mixing in the liquid around the inclusion, thus improving mass transfer between the two phases. This effect has been demonstrated here on the hydrolysis of n-amyl acetate by sodium hydroxide, a rather slow reaction but influenced by mass transfer; the reaction is carried out in a glass jacketed reactor, 500 mL of volume, equipped with a Rushton turbine and a 20 kHz sonotrode dipping in the solution. The ester is initially pure in the organic dispersed phase, and sodium hydroxide has an initial concentration of 300 mol/m3; one of the products, pentanol partitions between the two phases and the sodium salt stays in the aqueous phase. The initial apparent reaction rate is measured from the record of the conductivity giving the concentration of alkali versus time. The reaction rate was always found to increase when ultrasound is superimposed to mechanical stirring (at 600 rpm), with a positive influence of input power (20 and 50 W). When varying initial concentration (300 and 600 mol/m3), temperature (36 and 45°C) and ultrasound emitter (sonotrode or cuphorn), the benefit of ultrasound over mechanical agitation was systematic. The only case of a weak influence of ultrasound was the sonication of a dense medium, containing 23% of organic phase and impeding the propagation of ultrasound

Localized versus itinerant magnetic moments in Na0.72CoO2

Based on experimental 59Co-NMR data in the temperature range between 0.1 and 300 K, we address the problem of the character of the Co 3d-electron based magnetism in Na0.7CoO2. Temperature dependent 59Co-NMR spectra reveal different Co environments below 300 K and their differentiation increases with decreasing temperature. We show that the 23Na- and 59Co-NMR data may consistently be interpreted by assuming that below room temperature the Co 3d-electrons are itinerant. Their magnetic interaction appears to favor an antiferromagnetic coupling, and we identify a substantial orbital contribution corb to the d-electron susceptibility. At low temperatures corb seems to acquire some temperature dependence, suggesting an increasing influence of spin-orbit coupling. The temperature dependence of the spin-lattice relaxation rate T1-1(T) confirms significant variations in the dynamics of this electronic subsystem between 200 and 300K, as previously suggested. Below 200 K, Na0.7CoO2 may be viewed as a weak antiferromagnet with TN below 1 K but this scenario still leaves a number of open questions.Comment: 8.7 pages, 6 Figures, submitted to Phys. Rev.

Résultats de trois méthodes pour la détection de la mutation précore G1896A du virus de l’hépatite B chez les donneurs de sang français : PCR temps réel, séquençage et test Inno-LIPA

AIM: To screen hepatitis B virus (HBV) genotypes and associated basal core promoter (BCP; T1762A/A1764) and precore (PC; A1896) mutations among the 100 HBV surface antigen (HBsAg) positive voluntary blood donors in France. METHODS: HBV genotypes were determined by using direct sequence analysis. Three methods were used to detect G1896A mutation: non-commercial real-time PCR (PCRTR°, line probe assay (InnoLiPA HBV PreCore, INNOGENETICS(®)) and direct sequencing of precore gene. HBV viral load was quantified with two commercial real-time PCR (COBAS(®) AmpliPrep/COBAS(®) TaqMan(®) HBV Test/Roche and Real Time HBV/M2000/Abbott). RESULTS: The mean age of donors was 30 (18-64). Patients were from Africa (42%), Europa (50%), and Asia (8%). HBV/D was the most predominant (37%) genotype followed by HBV/A (31%) and HBV/E (22%). PC and BCP mutants were found in 57% with Inno-LIPA HBV test and 59% with both PCRTR and sequencing methods. A significant difference in the viral load of blood donors with wild and PC mutants was observed with the Taqman Cobas real time PCR (3,19 Log(10) UI/ml versus 4,93 Log(10) UI/ml, p < 0.05). Precore phenotype determination was in agreement with the three PC mutation detection methods in 56% of cases. CONCLUSIONS: Non-Caucasian genotype E was present in the French blood donors. PC mutation was more common than BCP mutations in this study. As HBV infected blood donors were more often asymptomatic carriers, we could speculate that the G1896A mutation may favour the asymptomatic state, supporting previous observations

IC immunity modeling process validation using on-chip measurements

International audienceDeveloping integrated circuit (IC) immunity models and simulation flow has become one of the major concerns of ICs suppliers to predict whether a chip will pass susceptibility tests before fabrication and avoid redesign cost. This paper presents an IC immunity modeling process including the standard immunity test applied to a dedicated test chip. An on-chip voltage sensor is used to characterize the radio frequency interference propagation inside the chip and thus validate the immunity modeling process