Highly selective silylformylation of internal and functionalised alkynes with a cationic dirhodium(II) complex catalyst

The tetracationic complex [Rh₂(MeCN)₂(Naft)₄](BF₄)₄ (Naft = μ-1,8-naphthyridine) was found to be an efficient catalyst for the silylformylation of internal and functionalised alkynes to yield useful synthetic intermediates. The complex exhibits an unprecedented chemoselectivity towards alkyne silylformylation instead of simple hydrosilylation, as well as a good stereoselectivity. The catalytic efficiency of the complex is markedly superior compared to that of previously reported catalysts such as [] or Rh₄(CO)₁₂; incidentally, the performance of the latter catalyst was found to vary dramatically with its shelf-life, which indicates that the catalyst evolves with ageing towards other species, most notably higher nuclearity rhodium carbonyl clusters, which are more chemoselective towards silylformylation. Preliminary results on the determination of the catalytically active species in the case of complex [Rh₂(MeCN)₂(Naft)₄](BF₄)₄ indicate that the complex is reduced in situ to a dirhodium(I) species which maintains the dimeric, lantern-shaped structure.     

On the Cosmological Implications of Irreversible Thermodynamics

The usual arguments related to the validity ofa thermostatical approach to several cosmologicalproblems are reviewed. It is seen that a nonequilibriumformalism is needed to solve conceptual problems in cosmology, such as the the generalization ofthe second law of thermodynamics. A cosmologicalnon-equilibrium formalism with a positive-semidefiniteentropy production is derived. The main features of a universe formulated under such a basis arestudied.     

Monte Carlo simulation of mini TEPC microdosimetric spectra: Influence of low energy electrons

In the past few years, miniaturized tissue-equivalent gas detectors (mini TEPCs) have been developed for application of microdosimetry in radiotherapy. These mini-TEPCs are characterised by millimetric dimensions. They are equipped neither with an internal calibration source nor with electric field tubes, which would properly define the sensitive volume hence the simulated site size. In spite of these lacks, mini TEPCs working in gas flow conditions have proven to be precise and reliable detectors. However, for future therapeutic plans including microdosimetric data, consistency between experimental and calculated data is important. Existing general-purpose Monte Carlo codes have proven to be very useful to calculate the energy deposition due to ionization in macroscopic targets, even in various complex radiation fields. However, theoretical models implemented in these codes for simulating electron transport and straggling are valid only for energies above a few keV. This restricts their applicability for simulating radiation transport at a micrometric level, where low-energy electrons play a dominant role. In this work, we calculate frequency distributions of deposited energy in a mini TEPC (with sizes equivalent to 1 and 2 μm) due to photons using the Monte Carlo code FLUKA. Comparisons between simulated and experimental data show a rather good agreement. Differences due to different FLUKA settings are discussed.     

Fast survey analysis of biomass by-product samples based on ICP optical emission spectra

Prehydrolysate samples from the acidic prehydrolysis of Eucalyptus wood residues were submitted to survey analysis by inductively coupled plasma (ICP) optical emission spectrometry (OES) based on the multicomponent and multiline techniques. The survey analysis software is designed to determine 64 elements. The semiquantitative data obtained for the unknown prehydrolysate samples provided fast and valuable information for the determination of important inorganic constituents (Al, B, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, S, Si, Sr, Zn, Co, Pb, Sn) for further utilisation of the prehydrolysate in the production of fertilisers, animal feed and furfural. To validate the survey analysis approach, the prehydrolysate samples were quantitatively analysed by the standard additions method. For the prehydrolysate samples the relative difference between the results obtained by both techniques was generally ± 25% for the majority of the elements, a typical value for the survey approach. Analyte recoveries in the spiked prehydrolysate samples analysed by the survey approach ranged from 95 to 125%. Independent replicates of prehydrolysate samples were measured over a 15-day period showing relative standard deviations of ≤ 4% for all elements, except for Zn (10%) and S (16%). Received: 1 February 1999 / Revised: 15 April 1999 / Accepted: 20 April 1999     

Two natural products from the algae Laurencia scoparia

The structures and absolute stereochemistries of two chamigrene-type metabolites (spiro­[5.5]­un­decane derivatives) isolated from the red algae Laurencia scoparia are described. One, a non-sesquiterpene named ma?lione (8-bromo-9-hydroxy-7,7-di­methyl-11-methyl­ene­spiro­[5.5]­undec-1-en-3-one), C₁₄H₁₉BrO₂, was detected previously in Laurencia cartilaginea, while the other, the sesquiterpene isorigidol (8-bromo-3,7,7-tri­methyl-11-methyl­ene­spiro­[5.5]-undec-1-ene-3,9-diol), C₁₅H₂₃BrO₂, is a new isomer of rigidol, first isolated from Laurencia rigida. The A rings of these spiro­cyclic compounds show the same carbon skeleton. However, the relative stereochemistry of the 8-Br and 9-OH substituents is different. While ma?lione displays the usual syn (or cis) relative stereochemistry of the bromo­hydroxy vicinal group, isorigidol shows an anti (or trans) arrangement. The 8-Br and 9-OH groups are both in equatorial positions in isorigidol, while the 9-OH group is axial in ma?lione, as in most chamigrenes. The absolute configurations of the chiral centers were determined as 6S, 8S and 9R in ma?lione, and 3R, 6S, 8S and 9S in isorigidol.     

Capillary gas chromatography combined with high performance liquid chromatography for the structural analysis of olive oil triacylglycerols

The triacylglycerol composition of olive oil samples has been determined by stereospecific analysis after partial hydrolysis with ethyl magnesium bromide, derivatization, preparative chiral HPLC, transesterification, and GC quantitation of fatty acid methyl esters. The data obtained for position sn-2 were compared with those from capillary GC analysis of monoacyl sn-2-glycerols after enzymatic lipolysis of triacylglycerols. The determination of triacylglycerols collected by silver ion HPLC and quantified (as fatty acid methyl esters) by GC, together with direct GC analysis on a polar column, have then furnished a comprehensive picture of the triacylglycerol content of olive oil.     

Electrochemical fluorination of the n-methylmorpholine

The results of some researches as regards the possibility to carry out selective electrochemical fluorinations of organic compounds by use of organic solvents are reported.Various organic solvents (acetonitrile, 1,4-dioxane, N,N-dimethylformamide) have been employed in the electrochemical fluorination of the N-methylmorpholine (NMM), but the results have not been those expected. Because of strong interactions taken place within certain ratios solvent/HF, many difficulties have been got into as regards the conductivity.Better results were obtained working without the solvent and with a great concentration (40 %) of the NMM in hydrogen fluoride. In the experiments carried out, the electrochemical fluorination of the NMM appeared highly selective: at first it took place on the positions beside the oxygen atom, then on those beside the nitrogen atom and at last on the methylic group. A mechanism of the reaction is proposed.     

A high-pressure liquid chromatographic-tandem mass spectrometric method for the determination of ethambutol in human plasma, bronchoalveolar lavage fluid, and alveolar cells

A technique is presented for the specific and sensitive determination of ethambutol concentrations in plasma, bronchoalveolar lavage (BAL), and alveolar cells (AC) using a high-pressure liquid chromatographic (HPLC)-tandem mass spectrometric (MS-MS) method. The preparation of samples requires a deproteinization step with acetonitrile. The retention times for ethambutol, neostigmine bromide, and propranolol are 2.0, 1.4, and 1.1 min, respectively, with a total run time of 2.8 min. The detection limits for ethambutol are 0.05 microg/mL for plasma and 0.005 microg/mL for the BAL supernatants and AC suspensions. The assay has excellent performance characteristics and has been used to support a study of the intrapulmonary pharmacokinetics of ethambutol in human subjects.     

Simultaneous determination of volatile and semi-volatile aromatic hydrocarbons in virgin olive oil by headspace solid-phase microextraction coupled to gas chromatography/mass spectrometry

A reliable, simple and relatively fast method for the simultaneous determination of volatile and semi-volatile aromatic hydrocarbons in virgin olive oil was developed, based on headspace solid-phase microextraction (HS-SPME). The investigation regarded eco-contaminants such as alkylated monoaromatic hydrocarbons from C1- to C4-benzenes and light polyaromatic hydrocarbons up to four aromatic rings. Sampling and chromatographic conditions were optimized by using standard solutions in deodorized olive oil and the analytical performances of the method were determined. The proposed method was then applied to real samples of virgin olive oil were the target hydrocarbons could be identified and quantified. Several of them had not been previously quantified in virgin olive oil. Moreover, by the analysis of olive oil samples an additional number of C4-benzenes could be tentatively identified.     

A systematic investigation of the role of material parameters in metastability of hydrogenated amorphous silicon

In this work, the role of structural, electronic and optical parameters of as-deposited amorphous silicon films in photoconductivity decay during light soaking was systematically investigated. Deposition temperature was varied in the range 130–270°C, in order to obtain samples with different structural, optical and electronic properties. As a result, two degradation regimes were identified. At short illumination times (within a few days in typical samples, and within a few hours in the low quality samples), the material showed different tendency to degradation depending on the content of the SiH bond clusters. At long illumination times, in all the light soaked samples the photoconductivity decay followed the t^−1/3 law. The measured photoconductivity degradation was simulated starting from the bond-breaking model. The observed correlation between the material structural parameters and the different tendencies to degradation is explained in terms of variations of the Staebler-Wronski susceptibility.