A new azorellane diterpenoid from Azorella madreporica

A new azorellane diterpenoid has been isolated and identified from the aerial parts of Azorella madreporica Clos. The structure of 1 was established by one- and two-dimensional NMR techniques.     

Facile syntheses of novel benzo-1,3-dioxolo-, benzothiazolo-, pyrido-, and quinolino-fused 5H-benzo[d]-pyrazolo[5,1-b][1,3]-oxazines and 1H-pyrazoles

A number of novel benzo-1,3-dioxolo-, benzothiazolo-, pyrido-, and quinolino-fused 5H-benzo[d]pyrazolo[5,1-b][1,3]-oxazines and 1H-pyrazoles were synthesized utilizing an easy and effective N,N-bond forming heterocyclization reaction. In so doing, the substrate scope of this heterocyclization reaction, which starts with o-nitroheterocyclic aldehydes, was expanded to provide several unique heterocyclic compounds for biological screening. This work further demonstrates the versatility of this simple, base-mediated, one-pot heterocyclization method in the construction of novel heterocycles.     

Homeomorphisms of the annulus with a transitive lift

Let f be a homeomorphism of the closed annulus A that preserves the orientation, the boundary components and that has a lift ${\tilde{f}}$ to the infinite strip à which is transitive. We show that, if the rotation numbers of both boundary components of A are strictly positive, then there exists a closed nonempty unbounded set ${B^{-} \subset \tilde{A}}$ such that B ^? is bounded to the right, the projection of B ^? to A is dense, ${B^{-}-(1, 0) \subset B^{-}}$ and ${\tilde{f}(B^{-}) \subset B^{-}}$ . Moreover, if p ₁ is the projection on the first coordinate of Ã, then there exists d > 0 such that, for any ${\tilde z \in B^{-}}$ , $$\limsup_{n\to\infty}\frac{p_1(\tilde f^n(\tilde z))-p_1(\tilde z)}{n}<-d.$$ In particular, using a result of Franks, we show that the rotation set of any homeomorphism of the annulus that preserves orientation, boundary components, which has a transitive lift without fixed points in the boundary is an interval with 0 in its interior.     

Alcohol and metal determination in alcoholic beverages through high-temperature liquid-chromatography coupled to an inductively coupled plasma atomic emission spectrometer

In the present work, an inductively coupled plasma atomic emission spectrometry (ICP-AES) system was used as a high temperature liquid chromatography (HTLC) detector for the determination of alcohols and metals in beverages. For the sake of comparison, a refractive index (RI) detector was also employed for the first time to detect alcohols with HTLC. The organic compounds studied were methanol, ethanol, propan-1-ol and butan-1-ol (in the 10-125 mg/L concentration range) and the elements tested were magnesium, aluminum, copper, manganese and barium at concentrations included between roughly 0.01 and 80 mg/L. Column heating temperatures ranged from 80 to 175 °C and the optimum ones in terms of peak resolution, sensitivity and column lifetime were 125 and 100 °C for the HTLC-RI and HTLC-ICP-AES couplings, respectively. The HTLC-ICP-AES interface design (i.e., spray chamber design and nebulizer type used) was studied and it was found that a single pass spray chamber provided about 2 times higher sensitivities than a cyclonic conventional design. Comparatively speaking, limits of detection for alcohols were of the same order for the two evaluated detection systems (from 5 to 25 mg/L). In contrast, unlike RI, ICP-AES provided information about the content of both organic and inorganic species. Furthermore, temperature programming was applied to shorten the analysis time and it was verified that ICP-AES was less sensitive to temperature changes and modifications in the analyte chemical nature than the RI detector. Both detectors were successfully applied to the determination of short chain alcohols in several beverages such as muscatel, pacharan, punch, vermouth and two different brands of whiskeys (from 10 to 40 g of ethanol/100 g of sample). The results of the inorganic elements studied by HTLC-ICP-AES were compared with those obtained using inductively coupled plasma mass spectrometry (ICP-MS) obtaining good agreement between them. Recoveries found for spiked samples were close to 100% for both, inorganic elements (with both HLTC-ICP-AES and ICP-MS) and alcohols (with both HTLC-ICP-AES and HTLC-RI hyphenations).     

Adsorption of phenol on supercritically activated carbon fibres: effect of texture and surface chemistry

The influence of texture and surface chemistry on the phenol adsorption capacity of activated carbon fibres (ACFs) was studied. ACFs were prepared by carbonization of a phenolic textile fibre under nitrogen flow, followed by activation with H(2)O and CO(2) (under atmospheric pressure and supercritical state). The materials were characterised by N(2) and CO(2) adsorption, and by temperature programmed desorption studies. A strong correlation between the amount of adsorbed phenol and the micropore volume has been observed. The relationship between surface oxygen concentration and amount of physisorbed and chemisorbed phenol was assessed, and it was shown that higher amounts of surface oxygen groups decreased the phenol chemisorption capacity of ACFs.     

Highly selective and sensitive chromo-fluorogenic detection of the Tetryl explosive using functional silica nanoparticles

Silica nanoparticles containing polyamines and thiol groups have been used as probes for the selective detection of Tetryl.     

Divalent cations reduce the pH sensitivity of OmpF channel inducing the pK(a) shift of key acidic residues

In contrast to the highly-selective channels of neurophysiology employing mostly the exclusion mechanism, different factors account for the selectivity of large channels. Elucidation of these factors is essential for understanding the permeation mechanisms in ion channels and their regulation in vivo. The interaction between divalent cations and a protein channel, the bacterial porin OmpF, has been investigated paying attention to the channel selectivity and its dependence on the solution pH. Unlike the experiments performed in salts of monovalent cations, the channel is now practically insensitive to pH, being anion selective all over the pH range considered. Electrostatic calculations based on the available structural data suggest that the binding of divalent cations has two main effects: (i) the pK(a) values of key ionizable groups differ significantly from those of the isolated groups in solution and (ii) the cation binding has a decisive impact on the effective electric charge regulating the channel selectivity. A simple molecular model based on statistical thermodynamics provides additional qualitative explanations to the experimental findings that could also be useful for other related systems like synthetic nanopores, ion exchange membranes, and polyelectrolyte multilayers.     

Shades of green in 15th century paintings: combined microanalysis of the materials using synchrotron radiation XRD, FTIR and XRF

A representative selection of green paintings from fifteenth century Catalonia and the Crown of Aragon are analyzed by a combination of synchrotron radiation microanalytical techniques including FTIR, XRD, and XRF. The green pigments themselves are found to be a mixture of copper acetates/basic copper acetates and basic copper chlorides. Nevertheless, a broader range of green shades were obtained by mixing the green pigment with yellow, white, and blue pigments and applied forming a sequence of micrometric layers. Besides the nature of the pigments themselves, degradation and reaction products, such as carboxylates, formates and oxalates were also identified. Some of the copper based compounds, such as the basic copper chloride, may be either part of the original pigment or a weathering product. The high resolution, high brilliance, and small footprint of synchrotron radiation proved to be essential for the analysis of those submillimetric paint layers made of a large variety of compounds heterogeneous in nature and distribution and present in extremely low concentrations.     

Simultaneous determination of benzodiazepines by ultraviolet--visible spectrophotometry in micellar media

A method for the simultaneous determination of benzodiazepines in binary mixtures is proposed, based on the acid hydrolysis of benzodiazepines to benzophenones and the spectrophotometric determination of the latter in the presence of Nemol K 1030, a non-ionic surfactant condensate of ethylene oxide with nonylphenol. The experimental conditions for the hydrolysis of several benzodiazepines in sealed Pyrex tubes were determined. The addition of Nemol K 1030 to acidic solutions of benzophenones modified the positions of the absorption bands and made possible the simultaneous analysis of binary mixtures of benzodiazepines.