Probing the basicity of regular and defect sites of alkaline earth metal oxide surfaces by BF3 adsorption: a theoretical analysis.

The basicity of regular and low-coordinate (LC) sites (steps, edges and corners) at the surface of alkaline earths with NaCl structure (MgO, CaO, SrO, and BaO) has been investigated by using BF3 as a probe molecule. B-O and B-F distances; O-B-F bond angles; B-F asymmetric stretching frequencies; O, B and F 1s core-level binding energies; and the interaction energy of adsorbed BF3 were determined by means of DFT calculations on cluster models. These adsorption properties were compared with those of complexes of BF3 with molecules with various basicities (water, ammonia, phosphine, etc.). We show that many properties of adsorbed BF3, and in particular the experimentally accessible shifts in vibrational frequency, in B and F 1s core levels, and in BF3 desorption temperature, exhibit a linear correlation with the surface basicity as measured by the vertical ionization potential of the oxide anions. On the other hand, shifts of the O 1s core level binding energy do not provide a simple way to detect surface basicity. On a given oxide surface, the differing basicities of various sites result in measurable differences in adsorption properties. This suggests the potential use of BF3 as a probe molecule for titrating LC sites on the surface of ionic oxides.     

Identification of N,N-dimethyltryptamine and beta-carbolines in psychotropic ayahuasca beverage

Recently many people have shown great interest in traditional indigenous practices and popular medicine, involving the ingestion of natural psychotropic drugs. We received a request to analyze and determine the nature of a dark green liquid with a dark brown plant sediment, which the police had seized at an airport and inside the home of a person belonging to the 'Santo Daime' religious movement. Gas chromatography/mass spectrometry analysis of the extract identified N,N-dimethyltryptamine, a potent hallucinogen, and the beta-carboline alkaloids harmine and harmaline, revealing monoamine oxidase A-inhibiting properties. These substances are typical components of Ayahuasca, a South American psychotropic beverage obtained by boiling the bark of the liana Banisteriopsis caapi together with the leaves of various admixture plants, principally Psychotria viridis.     

Stable isotope ratios of carbon and hydrogen to distinguish olive oil from shark squalene‐squalane

Squalene and its hydrogenated derivate squalane are widely used in the pharmaceutical and cosmetic fields. The two compounds are mainly produced from the liver oil of deep sea sharks and from olive oil distillates. Squalene and squalane from shark cost less than the same compounds derived from olive oil, and the use of these shark‐derived compounds is unethical in cosmetic formulations. In this work we investigate whether ¹³C/¹²C and ²H/¹H ratios can distinguish olive oil from shark squalene/squalane and can detect the presence of shark derivates in olive oil based products. The ¹³C/¹²C ratios (expressed as δ¹³C values) of bulk samples and of pure compounds measured using isotope ratio mass spectrometry (IRMS) were significantly lower in authentic olive oil squalene/squalane (N: 13; ?28.4 ± 0.5‰; ?28.3 ± 0.8‰) than in shark squalene/squalane samples (N: 15; ?20.5 ± 0.7‰; ?20.4 ± 0.6‰). By defining δ¹³C threshold values of ?27.4‰ and ?26.6‰ for olive oil bulk and pure squalene/squalane, respectively, illegal addition of shark products can be identified starting from a minimum of 10%. ²H/¹H analysis is not useful for distinguishing the two different origins. δ¹³C analysis is proposed as a suitable tool for detecting the authenticity of commercial olive oil squalene and squalane samples, using IRMS interfaced to an elemental analyser if the purity is higher than 80% and IRMS interfaced to a gas chromatography/combustion system for samples with lower purity, including solutions of squalane extracted from cosmetic products. Copyright © 2010 John Wiley & Sons, Ltd.     

Ultraviolet Radiation Induces Filamentation in Bacterial Assemblages from North Andean Patagonian Lakes

Through laboratory experiments, we tested whether UV radiation (UVR) induces filamentation in natural bacteria assemblages from North Andean Patagonian lakes. We incubated water from three different lakes for 72 h in four separate treatments: (1) UVR + PAR (photosynthetically active radiation), (2) 50% UVR + PAR, (3) PAR and (4) 50% PAR. The irradiance levels used in the experiments were equivalent to those registered at the epilimnion of the lakes. In the UVR treatments filamentation was induced after the first 24 h and the proportion continued to increase for the next 48–72 h. A comparison of the gross composition and diversity of the entire community (cells >0.2 μm) with bacterial filaments alone (>5.0 μm) showed that UVR-induced filamentation is not a feature of any particular cluster. By sequencing part of the 16S rRNA gene of the taxonomic units obtained using denaturing gels, we observed that strains in the β-Proteobacteria group were of relatively high importance in filament formation, followed by Cytophaga–Flavobacterium–Bacteroides, γ-Proteobacteria and α-Proteobacteria, whereas Actinobacteria were almost nonexistent in the filaments. We propose that UVR doses equivalent to those of Andean lakes produce bacterial morphological changes, and that all bacterial groups except Actinobacteria can potentially form filaments.     

Effect of diphenyldiethoxysilane on the self-organized formation of nanocrystalline layered organosilicates in organic–inorganic hybrid films

Hybrid organic–inorganic films containing layered organosilicate nanocrystals have been obtained through self-organization from aqueous precursor sols containing 3-glycidoxypropyltrimethoxysilane. Diethoxydiphenylsilane has been added, in different amounts, to the precursor sol containing 3-glycidoxypropyltrimethoxysilane to prepare hybrid films with the ordered nanostructures. The effect of aging time of the precursor sol has been studied preparing different samples from sols aged up to 8 days; the formation of crystalline layered films has been observed in the samples obtained from sols of higher aging time. The hybrid films have been characterized by gracing incidence X-ray diffraction, Raman and Fourier transform infrared spectroscopy, transmission electron microscopy and UV–Vis spectroscopy. The change of the surface contact angle as a function of sol aging time and composition has been also measured. The capability of the films to be used in devices through lithographic techniques has been tested by writing the films with direct exposition to deep X-ray lithography and soft lithography with micromolds; patterns of different geometries with a thickness up to 100 μm have been obtained.     

Vinyl ester resin modified with silicone-based additives: III. Curing kinetics

Silicone-based additives have been used as fire retardants for thermoplastics with the advantageous of improving the processing and the impact resistance of the polymers. In this work the influence of these additives on the curing kinetics of a vinyl ester resin was studied. Three silicone-based additives were used to modify the properties of the vinyl ester resin. The principal differences between them are the functional groups inserted in the polydimethylsiloxane chains. The additives were dispersed in the resin containing a commonly used mixture of initiator and catalyst methylethylKetone peroxide and cobalt-II octanoate, respectively. For some reactional mixtures N,N-dimethylaniline (DMA) was used as promoter. Differential scanning calorimetry (DSC) was used to perform the non-isothermal cure of the non-modified resin and of the resins modified with the additives. Ozawa´s, Kissinger´s and Ozawa´s isoconversional methods were used to determine the kinetic parameters. For resin cured in absence of DMA the silicone-based additives act as retardants for the curing reaction, a typical diluent effect, while in presence of this promoter the reaction enthalpy as well as the reaction rate were improved. This effect was attributed to specific interactions and reactions between DMA and the silicone-based additives that changed the curing mechanism as well as controlled the phase segregation.     

Density-functional model cluster studies of EPR g tensors of Fs+ centers on the surface of MgO

We report g tensors of surface color centers, so-called F(s) (+) centers, of MgO calculated with two density-functional approaches using accurately embedded cluster models. In line with recent UHV measurements on single-crystalline MgO film, we determined only small g-tensor anisotropies and negative shifts Deltag identical with g-g(e) for all F(s) (+) sites considered, namely, (001)-terrace, step, edge, and corner sites. The g values are very sensitive to the local structure of the defect: relaxation reverses the sign of Deltag. However, accounting for the spin-orbit interaction either self-consistently or perturbatively yields very similar results. In addition to the values of the tensor components, their direction with respect to the surface was determined. In contrast to edges, significant deviations from ideal C(2v) symmetry were found for F(s) (+) centers at steps. Recent data on single-crystalline thin films are reevaluated in the light of these results.     

Kinetic resolution of racemic allylic alcohols via iridium-catalyzed asymmetric hydrogenation: scope,synthetic applications and insight into the origin of selectivity

Asymmetric hydrogenation is one of the most commonly used tools in organic synthesis, whereas, kinetic resolution via asymmetric hydrogenation is less developed. Herein, we describe the first iridium catalyzed kinetic resolution of a wide range of trisubstituted secondary and tertiary allylic alcohols. Large selectivity factors were observed in most cases (s up to 211), providing the unreacted starting materials in good yield with high levels of enantiopurity (ee up to >99%). The utility of this method is highlighted in the enantioselective formal synthesis of some bioactive natural products including pumiliotoxin A, inthomycin A and B. DFT studies and a selectivity model concerning the origin of selectivity are presented.

Asymmetric hydrogenation is one of the most commonly used tools in organic synthesis, whereas, kinetic resolution via asymmetric hydrogenation was less developed.     

Red-shifted luminescence from naphthalene-containing ligands due to pi-stacking in self-assembled coordination cages

Incorporation of ligands containing substituted naphthalene cores into coordination cages results in extensive aromatic pi-stacking between ligands; this results in a red-shifted 'excimer-like' luminescence component from the naphthyl groups compared to the free ligands, which is diagnostic of, and can be used to monitor, cage assembly.