Nanostructured Silicon Oxide–Nickel Oxide Sol–Gel Films with Enhanced Optical Carbon Monoxide Gas Sensitivity

Sol–gel derived silica (SiO₂) films doped with nickel oxide (NiO) nanocrystals were fabricated. A bifunctional ligand was used, bearing amine groups capable of coordinating the nickel ions and hydrolysable siloxane groups for anchoring the metal complex moiety to the silicate matrix. Nickel oxide nanocrystals precipitated at 500°C while the film was still porous. The nanocomposite films showed a reversible change in the optical transmittance in the VIS-NIR range when exposed to carbon monoxide gas. The effects of residual porosity, testing temperature, and carbon monoxide gas concentration on optical transmittance were studied.     

1H nuclear magnetic resonance study of polyurethane prepolymers from toluene diisocyanate and polypropylene glycol

Polyurethane prepolymers prepared from toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, and polypropylene glycol with a ratio between the isocyanate and hydroxyl groups equal to 2 were analyzed by ¹H nuclear magnetic resonance (NMR) spectroscopy in acetone‐d₆. Different temperatures and concentrations were used. Toluene 2,4‐dimethylurethane and toluene 2,6‐dimethylurethane were synthesized and used as model compounds to assign prepolymers signals. Measurements of spin–lattice relaxation time T₁ by “inversion recovery” experiments were carried out on toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, toluene 2,4‐dimethylurethane, toluene 2,6‐dimethylurethane, and polyurethane prepolymers. Differences in T₁ times were used to interpret prepolymers spectra, by means of the strong observed effect on protons due to the presence of adjacent isocyanate groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 347–357, 2003     

The binding mode of progesterone to its receptor deduced from molecular dynamics simulations

An unambiguous understanding of the binding mode of human progesterone to its receptor still eludes experimental search. According to the X-ray structure of the ligand-binding domain, only one (O3) of the two keto groups at the ligand ends (O3 and O20) should play a role. This result is in conflict with chemical intuition and the results of site-directed mutagenesis experiments. Herein, we report classical molecular dynamics simulations that reveal the dynamic nature of the binding in solution, elucidate the reasons why X-ray studies failed to determine the role of O20, and clarify the effects of the mutations. The predictive power of the force field is ensured by the consistent introduction of a first-principles representation of the ligand.     

Polyamides incorporating furan moieties. 5. Synthesis and characterisation of furan-aromatic homologues

2,2′-Bis (5-chloroformyl 2-furyl) propane and various aromatic diamines were used as monomers in the study of their interfacial polycondensation and the properties of the ensuing furanic-aromatic polyamides. The effects of such variables as the nature of the organic phase, the temperature, the reaction time, and the type and concentration of the catalyst were investigated as well as the properties of the polyamides in terms of structure, average chain length, T_g, T_m and thermal stability.     

Recycled poly(ethylene terephthalate) and its short glass fibres composites: effects of hygrothermal aging on the thermo-mechanical behaviour

This paper reports on the effects of hygrothermal aging at 70 °C in water and at 80% relative humidity, on the thermo-mechanical properties, molar mass and microstructure of recycled poly(ethylene terephthalate) (rPET) and its short glass fibres composites.For all the investigated materials, the elastic mechanical properties (tensile and storage moduli) determined at low strain levels resulted practically unaffected by hygrothermal aging under the selected conditions. On the other hand, a marked reduction of the tensile strength and apparent fracture toughness has been observed for rPET matrix and its composites during hygrothermal aging, more markedly for materials immersed in water than for those aged at 80% RH. Both properties resulted to be related on the molar mass of the rPET matrix, that decreased during hygrothermal aging as a consequence of the hydrolysis process.The materials glass transition, evaluated as the temperature of the loss factor peak, increased during hygrothermal aging due to the progressively restricted mobility of the amorphous phase caused by a concurrent crystallinity increase. This crystallization process (chemicrystallization) is favoured by temperature, by the plasticizing effect of water and by the reduction of molar mass.Consistently with the mechanical measurements, the morphology of fracture surfaces exposed to hygrothermal aging in water revealed a reduction of plastic deformation of the rPET matrix and a weakening of the fibre-matrix interface for rPET composites.     

Urethanes and polyurethanes based on oxypropylated cork: 1. Appraisal and reactivity of products

The reaction of various polyols derived from the oxypropylation of cork with aliphatic and aromatic mono‐ and diisocyanates was studied in solution at room temperature. In all instances, good second‐order kinetics were observed and the corresponding rate constant determined. The reactivity of the aromatic isocyanate was found to be much higher than that of aliphatic counterparts. The ensuing urethanes and polyurethanes were characterised by FTIR and ¹H NMR spectroscopy, DSC and sol/gel distribution. © 2001 Society of Chemical Industry     

Oxygen Storage Behavior of Ceria–Zirconia-Based Catalysts in the Presence of SO2

This paper investigates the effect of the presence of SO₂ in the dynamics of oxygen storage on ceria and ceria–zirconia. The introduction of SO₂ under reaction conditions at T<873 K negatively affects CO conversion under oscillating conditions on all the supports studied, owing to the formation of sulfate species. Deactivation is observed on all supports and activity is recovered only after desorption of SO₂, which occurs at 950<T<1000 K, depending on catalyst composition (Ce/Zr ratio) and treatment atmosphere. The amount of sulfur adsorbed is higher over solid solutions, reaching a maximum with Ce _x Zr_1–x O₂ (0.5<x<0.68). However this does not adversely affect activity compared to ceria. In the presence of Rh and Pd, reactivation is favored under reaction conditions. More generally, it appears that the removal of sulfates is facilitated in reductive atmospheres (both hydrogen and CO) over mixed oxides. No differences are observed following regeneration under oxidizing conditions.     

Experimental design of the kinetic resolution of a key precursor of high‐value bioactive myo‐inositols by an immobilized lipase

BACKGROUND: The response surface methodology was successfully applied to the optimization of the reaction variables for the kinetic resolution of a precursor of high‐value myo‐inositols, ( ± )‐1,2‐O‐isopropylidene‐3,6‐di‐O‐benzyl‐myo‐inositol (( ± )‐1), by Novozym 435. The resolutions were run separately, with two acylating agents, ethyl acetate and vinyl acetate, in a solvent‐free system. The variables analyzed were reaction temperature, substrate concentration, water concentration and enzyme activity. A statistical model was employed for the evaluation of the influence of the variables on conversion and enantiomeric excess (ee). RESULTS: The optimal conditions for this resolution using vinyl acetate as acylating agent were 45 °C, 5 mg mL^?1 of substrate, 71 U of enzyme activity and 0%w/w of water concentration. The high conversion (49.2 %) and ee (>99%) reached in the chemoenzymatic synthesis of acylated product, L‐(?)‐5‐O‐Acetyl‐3,6‐di‐O‐benzyl‐1,2‐O‐isopropylidene‐myo‐inositol, secure the efficient synthesis of the D enantiomorph present in the original racemic mixture (( ± )‐1) as well. CONCLUSIONS: The use of the experimental design strategy was productive, leading to a 14‐fold increase in the productivity of the reaction compared with the non‐optimized conditions. Both derivative L‐(?)‐2 and remaining substrate D‐(+)‐1 were obtained at high ee. © 2012 Society of Chemical Industry