New class of amino-phosphinite chiral catalysts for the highly enantioselective addition of arylzinc reagents to aldehydes

A new class of amino-phosphinite chiral ligands was prepared and applied in zinc-catalyzed addition of aryl boronic acids to aldehydes; the reaction furnished the diarylmethanols in excellent yields and with a high level of enantioselectivity (up to 93% ee).     

Ligand-free Suzuki-Miyaura reactions in PEG 300

In this work, we present ligand-free Suzuki cross-coupling reactions in PEG 300 under thermal conditions at 55 °C with good yields of conversion; better results were obtained with low reaction time. In 1 hour, 1-iodo-4-nitrobenzene and phenylboronic acid reached 98% of the yield and 9700 of TON. Better results were obtained with Pd(0) sources. The reaction system was recycled up to three times with good activity.     

Porous nanocomposite hydrogel of vinyled montmorillonite-crosslinked maltodextrin-co-dimethylacrylamide as a highly stable polymer carrier for controlled release systems

Nanocomposite hydrogel consisting of dispersed montmorillonite-crosslinked maltodextrin-co-dimethylacrylamide (malt-dex-co-DMAAm) as a highly stable device was developed. Carbon-carbon π-bonds issued from glycidyl methacrylate (GMA) were incorporated onto both the MMT (MMT-π) and the malt-dex (malt-dex-π) structures. The nanocomposite copolymer hydrogel was processed via radical crosslinking reaction of malt-dex-π with MMT-π in the presence of DMAAm. The radical reaction of the carbon-carbon π-bonds at the MMT-π was verified by treating the MMT-π with sodium persulfate. There was an excellent dispersion of the MMT-π at the interior of the matrix even after the nanocomposite hydrogel being swollen, demonstrating that the developed methodology can imprint stability of mineral nanoparticles into a porous polymer network preventing diffusion of water-bonded silicate platelets toward the outside matrix. The water absorption profile became more dependent on the polymer relaxation for mineral-loader nanocomposite hydrogels. Higher water absorption had an impact on reduction of elasticity modulus due to softer polymer network in swollen state.     

Al3+, Ca2+, Mg2+, and Li+ in aqueous solution: calculated first-shell anharmonic OH vibrations at 300 K

The anharmonic OH stretching vibrational frequencies, ν(OH), for the first-shell water molecules around the Li(+), Ca(2+), Mg(2+), and Al(3+) ions in dilute aqueous solutions have been calculated based on classical molecular dynamics (MD) simulations and quantum-mechanical (QM) calculations. For Li(+)(aq), Ca(2+)(aq), Mg(2+)(aq), and Al(3+)(aq), our calculated IR frequency shifts, Δν(OH), with respect to the gas-phase water frequency, are about -300, -350, -450, and -750?cm(-1), compared to -290, -290, -420, and -830?cm(-1) from experimental infrared (IR) studies. The agreement is thus quite good, except for the order between Li(+) and Ca(2+). Given that the polarizing field from the Ca(2+) ion ought to be larger than that from Li(+)(aq), our calculated result seems reasonable. Also the absolute OH frequencies agree well with experiment. The method we used is a sequential four-step procedure: QM(electronic) to make a force field+MD simulation+QM(electronic) for point-charge-embedded M(n+) (H(2)O)(y) (second?shell) (H(2)O)(z) (third?shell) clusters+QM(vibrational) to yield the OH spectrum. The many-body Ca(2+)-water force-field presented in this paper is new. IR intensity-weighting of the density-of-states frequency distributions was carried out by means of the squared dipole moment derivatives.     

Phase behaviour of binary systems of lactones in carbon dioxide

Experimental phase equilibrium data for binary systems involving ε-caprolactone, δ-hexalactone, and γ-caprolactone with carbon dioxide have been measured applying the synthetic method using a high-pressure, variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 21 MPa. For the systems investigated, (vapour + liquid) (VLE), (liquid + liquid) (LLE), and (vapour + liquid + liquid) (VLLE) equilibrium were visually recorded. It was observed that an increase in temperature or in carbon dioxide concentration led to a pronounced raise in transition pressure values. The experimental results were modelled using the Peng–Robinson equation of state with the conventional quadratic mixing rule, affording a satisfactory representation of the experimental values.     

Electrograining of aluminium in HCl: effect of the alloy for high‐speed processing lines

Electrograining of aluminium in hydrochloric acid is one of the most commonly used processes for manufacturing printing lithographic plates. Two of the main features to be taken into account are the final morphology of the electrograined surface and the susceptibility of the alloy to be processed or, more specifically, the speed of the processing line. Both issues determine the efficiency of the production in terms of quality and time. In this work, a widely used commercial aluminium alloy (1050) is compared with a new experimental one (1050 modified with Zn) and with a higher strength alloy (namely 1020). In order to analyse their response to a.c. graining in HCl for high‐speed lines, some techniques such as image analysis or interferometry have been used. In general, the alloys doped with Zn and Mg present a better response to litho processing in terms of graining activity and reduction of streakiness when treatment of lower time periods is applied due to their influence as pitting initiators. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of Hg and Pb in compact fluorescent lamp by slurry sampling inductively coupled plasma optical emission spectrometry

Mercury and lead were determined in an extraction solution applied to compact fluorescent lamps by axial view inductively coupled plasma optical emission spectrometry (ICP OES). The solution contained 50% v/v HNO₃ and 10% v/v H₂O₂. The compact fluorescent lamps were treated by removing the socket and breaking the rest of the lamp inside the solution, followed by placing the mixture in an ultrasonic bath for 1 h. The mixture was filtrated in a coarse paper filter and the resulting extraction slurry was analyzed. The determination of Pb in the slurry required calibration by the analyte addition technique, while for Hg, external calibration was adequate. The quantification limits (10 s, n = 7), for Hg (194.164 nm) and Pb (220.353 nm) were, respectively, 10 and 30 µg per lamp. Analysis of spiked samples demonstrated reasonable accuracy of the method, with recoveries in the range from 99 to 120% for Hg and from 91 to 107% for Pb. Fifteen analyzed samples showed Hg masses per lamp in the range from 1.6 to 27 mg, and six samples were above the limit allowed by the European Community that is 5 mg per compact lamp. The values for Pb were between 0.07 and 0.75 mg per lamp. By filtrating the slurry in a membrane filter, and analyzing the resulting solution, it was found that all Hg was extracted to the liquid phase of the slurry, while a fraction of about 40% m/v of Pb is retained in the solid particles. The lamp cover glass, after extraction of the phosphor layer, was also analyzed for Hg and Pb. The concentration of Hg in the glass is quite low; however, the Pb content is high.     

Screening and Production Study of Microbial Xylanase Producers from Brazilian Cerrado

Hemicelluloses are polysaccharides of low molecular weight containing 100 to 200 glycosidic residues. In plants, the xylans or the hemicelluloses are situated between the lignin and the collection of cellulose fibers underneath. The xylan is the most common hemicellulosic polysaccharide in cell walls of land plants, comprising a backbone of xylose residues linked by β-1,4-glycosidic bonds. So, xylanolytic enzymes from microorganism have attracted a great deal of attention in the last decade, particularly because of their biotechnological characteristics in various industrial processes, related to food, feed, ethanol, pulp, and paper industries. A microbial screening of xylanase producer was carried out in Brazilian Cerrado area in Selviria city, Mato Grosso do Sul State, Brazil. About 50 bacterial strains and 15 fungal strains were isolated from soil sample at 35 °C. Between these isolated microorganisms, a bacterium Lysinibacillus sp. and a fungus Neosartorya spinosa as good xylanase producers were identified. Based on identification processes, Lysinibacillus sp. is a new species and the xylanase production by this bacterial genus was not reported yet. Similarly, it has not reported about xylanase production from N. spinosa. The bacterial strain P5B1 identified as Lysinibacillus sp. was cultivated on submerged fermentation using as substrate xylan, wheat bran, corn straw, corncob, and sugar cane bagasse. Corn straw and wheat bran show a good xylanase activity after 72 h of fermentation. A fungus identified as N. spinosa (strain P2D16) was cultivated on solid-state fermentation using as substrate source wheat bran, wheat bran plus sawdust, corn straw, corncob, cassava bran, and sugar cane bagasse. Wheat bran and corncobs show the better xylanase production after 72 h of fermentation. Both crude xylanases were characterized and a bacterial xylanase shows optimum pH for enzyme activity at 6.0, whereas a fungal xylanase has optimum pH at 5.0–5.5. They were stable in the pH range 5.0–10.0 and 5.5–8.5 for bacterial and fungal xylanase, respectively. The optimum temperatures were 55C and 60 °C for bacterial and fungal xylanase, respectively, and they were thermally stable up to 50 °C.     

New complexes of the fac-{(CO)3Re} fragment bearing a diaminediphosphine ligand

The mono- and binuclear hydride compounds fac-[ReH(CO)₃L] (1a) and [{ReH(CO)₄}₂(μ-L)] (1b) have been prepared by reaction of [ReH(CO)₅] with Ph₂PN(CH₃)(CH₂)₂N(CH₃)PPh₂ (L) under UV light. Protonation reactions of the hydride compound 1a with equimolar amounts of HSO₃CF₃ or HCl yielded the triflato or the chlorido compounds fac-[Re(OSO₂CF₃)(CO)₃L] (2) and fac-[ReCl(CO)₃L] (3), respectively. The compounds have been characterised by elemental analysis, IR and NMR spectroscopic data, and mass spectrometry. Their structures have been confirmed by X-ray crystallography.     

Complexation of metal ions with the novel azathia crown ethers carrying anthracene pendant in acetonitrile–dichloromethane

A series of crown ethers carrying an anthracene group with nitrogen–sulfur donor atom, which differ in having three, four and five sulfur atoms in the macrocycle was designed and synthesized by the reaction of the corresponding macrocyclic compound and 9-chloromethyl-anthracene. The influence of metal cations such as Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ on the spectroscopic properties of the ligands was investigated in acetonitrile–dichloromethane (1:1) by means of absorption and emission spectrometry. Absorption spectra show isosbestic points in the spectrophotometric titration of Al³⁺, Zn²⁺, Fe²⁺, Fe³⁺, Cu²⁺, Hg²⁺ and Pb²⁺ the results of which disclosed the complexation compositions and complex stability constants of the novel ligands with these cations. The monoazapentathia crown ether showed sensitivity for Al³⁺ with linear range and detection limit of 2.6 × 10⁻⁶ M–2.6 × 10⁻⁵ M and 8.1 × 10⁻⁷ M, respectively.