Preparation of monoglycerides by guanidine-catalyzed processes

Glycerolysis of methyl stearate and tristearin has been carried out in the presence of alkylguanidines—strong nonionic bases—as catalysts. When applied at 10 mol%, 1,5,7-triazabicyclo [4.4.0]dec-5-ene, 1,2,3-tricyclohexylguanidine, and 1,3-dicyclohexyl-2-n-octylguanidine give monoglycerides in more than 90% selectivity, in a maximum of 6 h reaction time.     

Colour assays: An inside look into Alentejo traditional limewash paintings and coloured lime mortars

A series of colour assays were conducted taking into account old bibliographic recommendations and oral testimony regarding traditional lime painting technology from the Alentejo (South Portugal) region. The main objectives were: (a) the colorimetric analysis of paintings made with different limewash preparation methods; (b) the comparison between natural processed red and yellows ochre pigments (“home made” and from industrial origin) and synthetic iron oxides in different concentrations and lime proportions; (c) the evaluation of the colorimetric CIELAB coordinates during the lime carbonation process in coloured mortars and limewashes. The results shows that the evolution of L*, a*, and b* during the carbonation process is independent of pigment concentration and paint thickness but dependent of pigment composition and finishing technique (lime painting or coloured mortar). They also emphasize the importance of surface appearance attributes and its influence on the colorimetric parameters. © 2010 Wiley Periodicals, Inc. Col Res Appl, 36, 61–71, 2011     

Selective hydrogenation of cinnamaldehyde using Pd catalysts supported on Mg/Al mixed oxides: Influence of the Pd incorporation method

A series of hydrotalcite‐like compounds was synthesized by varying Mg/Al molar ratio with values of 2, 3, and 4. After thermal treatment at 823 K, the corresponding mixed oxides were obtained and used as catalytic supports. The incorporation of a Pd metallic phase (0.5 g/g loading), was carried out by two methods: 1) in situ vapour phase thermal decomposition, and 2) impregnation by organic method. Fresh and calcined samples were characterized by XRD and N₂ sorption experiments. The basic and metal functions were analyzed by CO₂‐TPD and H₂‐TPR. The Pd‐support interaction was studied by FTIR spectroscopy using CO as a probe molecule while the morphology of Pd nanoparticles on the catalysts was studied by SEM, HRTEM, and theoretical simulation using the Fast Fourier Transform (FFT) method. Finally, the catalytic activity results showed a higher conversion towards hydrocinnamaldehyde in the cinnamaldehyde hydrogenation reaction for the catalysts prepared by vapour phase thermal decomposition, compared with those prepared by organic method, showing the significant dependence on the catalytic activity and the Pd incorporation method.     

Optical and Structural Properties of ZnO and ZnO:Cd Particles Grown by the Hydrothermal Method

Here, we examine the structural, vibrational, optical, and morphological properties of ZnO particles synthesized by the hydrothermal method, incorporating cadmium at different concentrations through the molar ratio R_m = Cd⁺²/Zn⁺² and a thermal treatment at 500°C. The X‐ray diffraction results demonstrated the high crystallinity of the ZnO compound with a wurtzite‐type hexagonal structure. The Raman scattering spectra demonstrated that the ZnO vibrational modes occur in the region between 200 and 1300 cm^?1, which is associated with different vibrational configurations characteristic of the ZnO molecule: E₂(Low), E₂(M), A₁(TO) E₁(TO), 2B₁(High), E₂(High), and TA + LO. The modes that were most affected by the incorporation of Cd²⁺ were those assigned to 2E₂(Low), E₂(M), and 2B₁(High), and this effect was associated with a greater displacement of Zn²⁺ ions. The optical study showed a reduction in the band gap and a decrease in the crystalline quality due to the substitution of Cd²⁺ in the ZnO lattice. Cadmium incorporation affected the morphology of the ZnO:Cd particles, changing the lengths and diameters of the ZnO rods; when the Cd concentration was increased, the ZnO rods shortened, forming coin‐type hexagonal structures.     

Asymmetric Intermolecular Mizoroki-Heck Reaction: From Phosphine/Phosphinite-Nitrogen to Phosphite-Nitrogen Ligands

This review discusses the latest developments in ligand design for the Pd-catalyzed asymmetric intermolecular Mizoroki-Heck reaction, from the successful phosphine/phosphinite-nitrogen ligands to the recently reported phosphite-nitrogen ligands. The presence of a biaryl phosphite group offers several advantages as a ligand scaffold for this process.     

CO(2) Adsorption on Activated Carbon Honeycomb-Monoliths: A Comparison of Langmuir and Tóth Models

Activated carbon honeycomb-monoliths with different textural properties were prepared by chemical activation of African palm shells with H(3)PO(4), ZnCl(2) and CaCl(2) aqueous solutions of various concentrations. The adsorbents obtained were characterized by N(2) adsorption at 77 K, and their carbon dioxide adsorption capacities were measured at 273 K and 1 Bar in volumetric adsorption equipment. The experimental adsorption isotherms were fitted to Langmuir and Tóth models, and a better fit was observed to Tóth equation with a correlation coefficient of 0.999. The maximum experimental values for adsorption capacity at the highest pressure (2.627-5.756 mmol·g(-1)) are between the calculated data in the two models.     

Inroads to Predict in Vivo Toxicology-An Introduction to the eTOX Project

There is a widespread awareness that the wealth of preclinical toxicity data that the pharmaceutical industry has generated in recent decades is not exploited as efficiently as it could be. Enhanced data availability for compound comparison ("read-across"), or for data mining to build predictive tools, should lead to a more efficient drug development process and contribute to the reduction of animal use (3Rs principle). In order to achieve these goals, a consortium approach, grouping numbers of relevant partners, is required. The eTOX ("electronic toxicity") consortium represents such a project and is a public-private partnership within the framework of the European Innovative Medicines Initiative (IMI). The project aims at the development of in silico prediction systems for organ and in vivo toxicity. The backbone of the project will be a database consisting of preclinical toxicity data for drug compounds or candidates extracted from previously unpublished, legacy reports from thirteen European and European operation-based pharmaceutical companies. The database will be enhanced by incorporation of publically available, high quality toxicology data. Seven academic institutes and five small-to-medium size enterprises (SMEs) contribute with their expertise in data gathering, database curation, data mining, chemoinformatics and predictive systems development. The outcome of the project will be a predictive system contributing to early potential hazard identification and risk assessment during the drug development process. The concept and strategy of the eTOX project is described here, together with current achievements and future deliverables.     

Drag Reduction by Wormlike Micelles of a Biodegradable and Non-Biodegradable Surfactants

This study describes the effects of wormlike micelles formed by the commercial surfactants tallowalkylamidopropyl dimethylamine oxide (Aromox APA-TW) and oleyl methyl bis(2-hydroxyethyl) ammonium chloride (Ethoquad O/12) as drag reducers. Ethoquad O/12 is immune to degradation by heat and microorganisms. Conversely, Aromox APA-TW is biodegradable in the environment, and its susceptibility to heat-induced degradation was previously assessed. This work considers the effects of temperature, salt, and time on the drag-reduction capacity (in different Reynolds number) of wormlike micelles of these two surfactants. Wormlike micelles formed by Aromox APA-TW are able to reduce drag at higher temperatures compared to wormlike micelles formed by Ethoquad O/12. However, Aromox APA-TW can degrade after being heated to 80 °C and also after storage of the wormlike micelle solutions. Ethoquad O/12 does not undergo degradation after being heated or stored. These surfactants have the potential to be used as additives in industrial operations, as the wormlike micelles formed are able to reduce drag in systems with long pumping distances or recirculation, even in solutions with high salt concentrations (brine) and high temperatures.     

Synthesis and structure-activity relationship of the isoindolinyl benzisoxazolpiperidines as potent,selective, and orally active human dopamine D4 receptor antagonists

A new class of potent dopamine D(4) antagonists was discovered with selectivity over dopamine D(2) and the alpha-1 adrenoceptor. The lead compound was discovered by screening our compound collection. The structure-activity relationships of substituted isoindoline rings and the chirality about the hydroxymethyl side chain were explored. The isoindoline analogues showed modest differences in potency and selectivity. The S enantiomer proved to be the more potent enantiomer at the D(4) receptor. Several analogues with greater than 100-fold selectivity for D(4) over D(2) and the alpha-1 adrenoreceptor were discovered. Several selective analogues were active in vivo upon oral or intraperitoneal administration. A chiral synthesis starting from either D- or L-O-benzylserine is also described.     

Vitrification and further structural relaxation in the isothermal curing of an epoxy resin

Isothermal curing of an epoxy resin based on diglycidyl ether of bisphenol A, using a hardener derived from phthalic anhydride, has been performed at curing temperatures between 30 and 130°C. Samples were cured isothermally at various intervals of time and analyzed by differential scanning calorimetry (DSC), the glass transition temperature T_g, and the conversion degree being determined by the residual enthalpy technique. The vitrification phenomenon and a further structural relaxation process, occurring at curing temperatures (T_c) lower than the maximum T_g (109°C), at which T_g equalizes T_c, have been studied at curing temperatures between 30 and 100°C. The structural relaxation process is analyzed by the endothermic peak that appears superposed on T_g in dynamic DSC scans. The area of this peak (Q) is a measure of the recovery enthalpy, and thus of the extent of the relaxation process. This process begins at higher curing times (t_c) when T_c decreases because the vitrification of the system starts later. Both the enthalpy recovery (Q) and the temperature of the endothermic peak (T_m) increase with the annealing time (t_a), calculated as the difference between t_c and the time in which vitrification occurs, and tend to have a limiting value due to the fact that the system loses mobility when the free volume decreases during its asymptotic approach toward the metastable equilibrium state. Furthermore, the dependence of Q and T_m on t_a at different T_c shows that the relaxation process in partially cured resins depends on the conversion degree of the system and consequently on the crosslinking density of the network.