Homoconjugated ketones with extended unsaturation: Wavelength-selective,regioselective, diastereoselective,and enantiospecific photochemical transformations of methyl 7-oxospiro[5.5]undeca-1,3-and -2,4,-diene-2-carboxylate

The title molecules were shown to photorearrange with remarkable selectivity. Wavelength variation steers the rearrangement modes, of which the [1,2]-acyl shift was found to be largely regioselective, diastereoselective, and enantiospecific. Chemical intercorrelation of products and mechanistic studies were carried out all along. The potential significance of these photochemical processes in selective synthetic schemes is discussed.     

10.1007/s10955-006-9040-z

We derive hydrodynamic equations describing the evolution of a binary fluid segregated into two regions, each rich in one species,which are separated (on the macroscopic scale) by a sharp interface. Our starting point is a Vlasov-Boltzmann (VB) equation describing the evolution of the one particle position and velocity distributions, f_i (x, v, t), i = 1, 2. The solution of the VB equation is developed in a Hilbert expansion appropriate for this system. This yields incompressible Navier-Stokes equations for the velocity field u and a jump boundary condition for the pressure across the interface. The interface, in turn, moves with a velocity given by the normal component of u.     

On the dehydration enthalpies of some beta-aluminas

The energetics of the dehydration reaction of single crystal (Na, Na 50%-Li, Li) and ceramic Na beta-aluminas have been studied.From the dependence of the dehydration enthalpy values on the water content it has been deduced that lattice water can be bound in two different ways i.e. by ion-dipole interactions with conducting cations and by hydrogen bonds with spinel block oxygens. As expected, the first one gives binding energies depending on the nature of the monovalent cation (H=84.5 and 59.4 kJ/mol H₂O for Li and Na beta-alumina respectively). In contrast, the enthalpy change associated with the second one is identical for the three beta-aluminas (H=15.1 kJ/mol H₂O). The ceramic Na beta-alumina undergoes a surface reaction too (with CO₂) leading to the formation of carbonates and bicarbonates.

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Zusammenfassung Die Energetik der Dehydratisierungsreaktion von Einkristallen von Na-, Na (50%)/Li- und Li- sowie von Na--Aluminiumoxid wurde untersucht. Aus der Abhängigkeit der Dehydratisierungsenthalpie vom Wassergehalt ergibt sich, daß Wasser auf zwei verschiedene Weisen gebunden ist, nämlich durch Ion-Dipol-Wechselwirkung mit leitenden Kationen und durch Wasserstoffbrückenbindungen mit Sauerstoffatomen. Wie zu erwarten war werden für die ersteren von der Natur der einwertigen Kationen abhängige Bindungsenergien (H=84.1 kJ/Mol H₂O bzw. 59.4 kJ/Mol H₂O für Li- bzw. Na--Alumina) erhalten. Die auf die zweite Wechselwirkung zurückzuführenden Enthalpieänderung ist dagegen für die drei-Aluminiumoxide identisch (H=15.1 kJ/Mol H₂O). Das keramische Na--Aluminiumoxid zeigt auch eine Oberflächenreaktion mit CO₂, die zur Bildung von Carbonaten und Bicarbonaten führt.

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(Na, Na 50%-Li, Li)- -- . , - . , Li — Na-- , , 84.5 59.4 / ₂. , - 15.1 / ₂. Na- , .

     

Preliminary characterization of anhydrous ethanol used in Brazil as automotive fuel

This work reports preliminary studies on the characterisation of anhydrous ethanol (AEA) used as an automotive fuel mixed with gasoline in Porto Alegre (South Brazil). Pre-concentration of the impurities contained in 1000 ml of AEA was carried on through solid-phase extraction using XAD4 resin. The main compounds in the extract were identified by means of spectral data from the library of the equipment. The concentrate was then fractionated using a preparative liquid chromatographic column filled with activated silica gel and the elution procedure was carried out with, n-hexane, n-hexane-benzene (1:1, v/v) and dichloromethane. Prior to analysis by GC-MS, each fraction was reduced to 1 ml with a gentle stream of nitrogen. Saturated linear hydrocarbons and aromatic hydrocarbons eluted in the first fraction and oxygenated compounds such as aldehydes. ketones and alcohols, eluted in the second one. were the main compounds detected in the sample.     

Importance of van der Waals Interactions in QM/MM Simulations

The importance of accurately treating van der Waals interactions between the quantum mechanical (QM) and molecular mechanical (MM) atoms in hybrid QM/MM simulations has been investigated systematically. First, a set of van der Waals (vdW) parameters was optimized for an approximate density functional method, the self-consistent charge-tight binding density functional (SCC-DFTB) approach, based on small hydrogen-bonding clusters. The sensitivity of condensed phase observables to the SCC-DFTB vdW parameters was then quantitatively investigated by SCC-DFTB/MM simulations of several model systems using the optimized set and two sets of extreme vdW parameters selected from the CHARMM22 forcefield. The model systems include a model FAD molecule in solution and a solvated enediolate, and the properties studied include the radial distribution functions of water molecules around the solute (model FAD and enediolate), the reduction potential of the model FAD and the potential of mean force for an intramolecular proton transfer in the enediolate. Although there are noticeable differences between parameter sets for gas-phase clusters and solvent structures around the solute, thermodynamic quantities in the condensed phase (e.g., reduction potential and potential of mean force) were found to be less sensitive to the numerical values of vdW parameters. The differences between SCC-DFTB/MM results with the three vdW parameter sets for SCC-DFTB atoms were explained in terms of the effects of the parameter set on solvation. The current study has made it clear that efforts in improving the reliability of QM/MM methods for energetical properties in the condensed phase should focus on components other than van der Waals interactions between QM and MM atoms.     

Potassium trimethylsilanolate induced cleavage of 1,3-oxazolidin-2- and 5-ones,and application to the synthesis of (R)-salmeterol

A convenient and efficient method for the cleavage of 1,3-oxazolidin-5-ones and 1,3-oxazolidin-2-ones utilising potassium trimethylsilanolate in tetrahydrofuran is described. The benzyloxycarbonyl-protecting group is readily removed under the reaction conditions, whereas the N-benzoyl group is stable. A synthesis of (R)-salmeterol exploiting the 2-oxazolidinone ring as a protecting group for the ethanolamine moiety is also described.     

pKa calculations in solution and proteins with QM/MM free energy perturbation simulations: a quantitative test of QM/MM protocols

The accuracy of biological simulations depends, in large part, on the treatment of electrostatics. Due to the availability of accurate experimental values, calculation of pKa provides stringent evaluation of computational methods. The generalized solvent boundary potential (GSBP) and Ewald summation electrostatic treatments were recently implemented for combined quantum mechanical and molecular mechanics (QM/MM) simulations by our group. These approaches were tested by calculating pKa shifts due to differences in electronic structure and electrostatic environment; the shifts were determined for a series of small molecules in solution, using various electrostatic treatments, and two residues (His 31, Lys 102) in the M102K T4-lysozyme mutant with large pKa shifts, using the GSBP approach. The calculations utilized a free energy perturbation scheme with the QM/MM potential function involving the self-consistent charge density functional tight binding (SCC-DFTB) and CHARMM as the QM and MM methods, respectively. The study of small molecules demonstrated that inconsistent electrostatic models produced results that were difficult to correct in a robust manner; by contrast, extended electrostatics, GSBP, and Ewald simulations produced consistent results once a bulk solvation contribution was carefully chosen. In addition to the electrostatic treatment, the pKa shifts were also sensitive to the level of the QM method and the scheme of treating QM/MM Coulombic interactions; however, simple perturbative corrections based on SCC-DFTB/CHARMM trajectories and higher level single point energy calculations were found to give satisfactory results. Combining all factors gave a root-mean-square difference of 0.7 pKa units for the relative pKa values of the small molecules compared to experiment. For the residues in the lysozyme, an accurate pKa shift was obtained for His 31 with multiple nanosecond simulations. For Lys 102, however, the pKa shift was estimated to be too large, even after more than 10 nanosecond simulations for each lambda window; the difficulty was due to the significant, but slow, reorganization of the protein and water structure when Lys 102 was protonated. The simulations support that Lys 102 is deprotonated in the X-ray structure and the protein is highly destabilized when this residue is protonated.     

Model for the study of the impact of atmospheric heavy metals on soil microbial biomass

In the Castelporziano (Rome) protected area the inputs of atmospheric heavy metals on the soil-plant system were evaluated by the analysis of stem-flowing water from Quercus ilex L. The heavy metals detected in the soil under the canopies exhibited higher concentrations near to the tree trunks, highlighting the tree's capacity to concentrate such polluting substances. Microbial biomass, its specific respiration and the biomass calculated as a percentage of total soil organic matter, were utilised as indicators of the state of the soil and consequently also its quality with respect to heavy metal contamination.     

Synthesis of (R)-alpha-benzylmethionine: a novel rearrangement during alkylation of the Seebach (R)-methionine oxazolidinone

Alkylation of the enolate of the Seebach (R)-methionine oxazolidinone with benzyl bromide gave the expected benzylated product in low yield. The major product was a novel amine arising from oxazolidinone cleavage, decarboxylation, alkylation and finally hydrolysis. The rearrangement could be suppressed by using a more reactive electrophile or by using the N-Cbz instead of the N-benzoyl protecting group, and the required (R)-alpha-benzyl-methionine was obtained in 78% yield and in an enantiomeric ratio of 90:10.     

Isotope dilution determination of polycyclic aromatic hydrocarbons in olive pomace oil by gas chromatography-mass spectrometry

A gas chromatographic (GC) method with mass spectrometry detection (MS) for the determination of eight polycyclic aromatic hydrocarbons (PAHs) in olive pomace oil has been developed. The oil was diluted with n-pentane and extracted by liquid-liquid partition with dimethyl sulphoxide (DMSO). After water addition and back-extraction with cyclohexane, a thin-layer chromatography on silica gel was performed as a further purification step. The PAHs spot was scraped off from the plate and the final extract was concentrated and analysed by GC-MS in full scan mode. The eight PAHs under investigation were determined in the presence of the corresponding labelled compounds added as internal standards to the sample at the beginning of the analytical process. The identified PAHs were then quantified by the isotope dilution methodology assuring the compensation of the concentration of each analyte for any variation in the sample preparation. The method precision was satisfactory with relative standard deviation (R.S.D.) values in the range 3.6-12.7% for all PAHs. The average recovery rates ranged from 69.0 to 97.5%. Accuracy was also calculated for benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene by analysing a certified reference material (CRM 458, coconut oil) with adequate results. All response curves exhibited a linear fit from 0.1 to 10 microg ml(-1) and the determination coefficients R2 were better than 0.9942. The limits of detection (0.1-0.4 microg kg(-1)) were acceptable when compared with the maximum permitted limit of 2 microg kg(-1) for each of the eight considered PAHs and 5 microg kg(-1) for the sum of the eight PAHs established by the Italian legislation. Measurement uncertainty was finally calculated identifying and quantifying the uncertainty components of the analytical process. The relative expanded uncertainties (Uc), expressed as percent values were in the range 8.5-11.4% thus appropriate for residues quantification in the range of concentrations considered in the present study.