CoI-Catalyzed Barbier Reactions of Aromatic Halides with Aromatic Aldehydes and Imines

The reductive Barbier coupling of aromatic halides and electrophiles has been achieved using a CoBr₂/1,10-phenanthroline catalytic system and over stoichiometric amounts of zinc. The reaction displayed a broad scope of substrates, including (hetero)aryl chlorides as pro-nucleophiles and aldehydes or imines as electrophiles, leading to diarylmethanols and diarylmethylamines in moderate to excellent yields, respectively.     

Tandem CH Activation/Arylation Catalyzed by Low‐Valent Iron Complexes with Bisiminopyridine Ligands

Tandem C?H activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox‐active non‐innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first‐row transition metals have been shown to involve substrate‐based aryl radicals, whereas our catalytic system likely involves ligand‐centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner‐sphere C?H activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble‐metal‐like behavior could be sustained by the redox‐active non‐innocent bisiminopyridine ligands.     

Inclusion complexes of a nucleotide analogue with hydroxypropyl-beta-cyclodextrin

Bis(tbutyl-S-acyl-2-thioethyl)-AraCMP (UA911) is a mononucleotide prodrug developed to overcome some of the cellular resistance to cytotoxic deoxynucleosides analogues. Its use for in vivo studies is limited due to its poor solubility in water. Thus, 2-hydroxypropyl-beta-cyclodextrin (HP-β-CD) was proposed to solubilize UA911 in water, in order to obtain concentrations needed for in vivo experiments. A molar ratio of HP-β-CD: UA911 of 3:1 was sufficient to obtain complete solubilization of the prodrug. The corresponding inclusion complex was characterized by differential scanning calorimetry and ¹H NMR spectroscopy study provided a definitive proof of the formation of the inclusion complex. The complex retained its cytotoxic activity as shown by in vitro cell survival assays on murine leukemia cells, and was evaluated in vivo. HP-β-CD is therefore suitable for the preparation of adequate solutions for the study of the antitumoral activity of nucleotide prodrugs such as UA911.     

A model for vibrational properties of the atomic interface in A/B fcc metals

The motivation of this theoretical work is to introduce a model calculation for the elastic waves scattering and coherent phonon transport at an atomic nanojunction between face-centered cubic (fcc) leads. The model system A/B consists of two perfect semi-infinite fcc leads A and B, oriented in the same direction and joined by an atomic interface. It is applied to the system Cu/Ni and its inverse Ni/Cu. A theoretical approach based on the matching method is used to study the dynamics of the system A/B.     

Production of l-menthyl acetate through kinetic resolution by Candida cylindracea lipase: effects of alkaloids as additives

Research on Chemical Intermediates - Enzymatic transesterification of dl-menthol with vinyl acetate in tert-Butyl methyl ether (TBME) catalyzed by Candida cylindracea lipase (CCL) was carried out...     

Ethanol production from AFEX-treated forages and agricultural residues

Lignocellulosic materials derived from forages, namely timothy grass, alfalfa, reed canary grass, and agricultural residues, such as corn stalks and barley straw, were pretreated using ammonia fiber explosion (AFEX) process. The pretreated materials were directly saccharified by cellulolytic enzymes. Sixty to 80% of theoretical yield of sugars were obtained from the pretreated biomasses. Subsequent ethanolic fermentation of the hydrolysates byPachysolen tannophilus ATCC 32691 resulted in 40-60% of theoretical yield after 24 h, based on the sugars present in the hydrolysates. The uptake of sugars was not complete, indicating a possible inhibitory effect onP. tannophilus during the fermentation of these substrates.     

Unsteady rheometry: can we characterize weak gels with a controlled stress rheometer?

This paper is concerned with the influence of apparatus inertia effects in controlled stress rheometry. As evidenced on creep experiments, the coexistence of apparatus inertia and viscoelasticity leads to a coupling frequency. For weak gels, this coupling frequency is typically between 1 and 100 Hz. Therefore, frequency sweeps around and above this coupling frequency also corresponds to an effective shear stress sweep evolution due to a non-trivial resonant effect. In other words, frequency sweep experiments are not made at constant shear stress. The detailed modelling and analysis of this inertia effect on a typical weak gel shows a clear and fundamental limitation for its characterization using a controlled stress rheometer. Also, alternative approaches to standard rheometer software analysis are proposed to take this coupling effect into account. This paper was presented at the 3rd Annual Rheology Conference, AERC 2006, April 27-29, 2006, Crete, Greece.     

Microstructural characterization and recrystallization kinetics of cold rolled copper

The recrystallization kinetics in pure copper deformed by cold rolling is mainly investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves show exothermic peaks corresponding to the stored energy released during recrystallization process. Variation of the heating rate and application of different methods allowed us to calculate two kinetic parameters of recrystallization: (i) the activation energy of the process was calculated using three different methods and (ii) the Avrami exponent was estimated using the Matusita method. On other hand, the microstructural evolution during recrystallization and grain growth of cold rolled copper were investigated at a temperature of 450 °C by scanning electron microscopy (SEM) and electron back scattered diffraction (EBSD).     

Impurity photovoltaic effect in silicon solar cell doped with sulphur: A numerical simulation

The impurity photovoltaic effect (IPV) has mostly been studied in various semiconductors such as silicon, silicon carbide and GaAs in order to increase infrared absorption and hence cell efficiency. In this work, sulphur is used as the IPV effect impurity incorporated in silicon solar cells. For our simulation we use the numerical device simulator (SCAPS). We calculate the solar cell performances (short circuit current density J_sc, open circuit voltage V_oc, conversion efficiency η and quantum efficiency QE). We study the influence of light trapping and certain impurity parameters like impurity concentration and position in the gap on the solar cell performances. Simulation results for IPV effect on silicon doped with sulphur show an improvement of the short circuit current and the efficiency for sulphur energy levels located far from the middle of the band gap especially at E_c-E_t=0.18 eV.