Lewis acid promoted aldol additions of α-thiosilylketeneacetals to α-alkoxy aldehydes: diastereoselective synthesis of syn-α-methylene-β-hydroxy-∂-alkoxy esters.

MgBr₂ mediated addition of Methyl α-methylthio propionate silylketene acetal to α and α,β-alkoxy aldehydes is highly 3,4 $\text{syn}$-selective (18:1). $\text{syn}$-α- methylene-β- hydroxy-?-alkoxy esters (6) and (8) are synthesized.     

Solid-phase microextraction gas chromatography/mass spectrometry: a new method for species identification of truffles

This study describes a rapid method to identify different truffle species by analysis of their volatile compound fraction using static headspace solid-phase microextraction gas chromatography/mass spectrometry. The volatile organic compounds (VOCs) were extracted using a new 2-cm 50/30 microm DVB/CAR/PDMS fiber placed for 10 min in the headspace of the truffle sample with the vial maintained at 20 degrees C (in a thermostatically controlled analysis room). The mass spectra of the VOC chromatograms were represented as 'fingerprints' of the analysed samples. Next, stepwise factorial discriminant analysis afforded a limited number of characteristic fragment ions that allowed a classification of the truffle species studied. This new method provides an effective approach to rapid quality control and identification of truffle species by analysis of their volatile fraction. Moreover, this method offers the advantage of minimizing thermal, mechanical, and chemical modifications of the truffles, thereby reducing the risk of analytical artifacts.     

Unprecedented detection of inherent chirality in uranyl-salophen complexes

In complexes with the uranyl dication salophen ligands are highly puckered. This implies that non-symmetrically substituted uranyl-salophen derivatives exist in principle as a pair of enantiomers. However, due to easy disrotations about the bonds connecting the phenoxide units to the imine carbons, the rate of interconversion between enantiomeric forms of simple, sterically unhindered compounds is extremely fast. Bulky substituents in appropriate positions decrease the interconversion rate and make this novel type of inherent chirality detectable by 1H and 13C NMR.     

Mechanistic study of thermal behavior and combustion performance of epoxy resins: I homopolymerized TGDDM

Tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) undergoes homopolymerization on heating. Intramolecular reactions which compete with crosslinking favor the formation of cyclic structures with increasing thermal and fire resistance of the resin, whereas physical mechanical properties tend to decrease. The mechanism of thermal decomposition of TGDDM is studied by thermogravimetry, differential scanning calorimetry and thermal volatilization analysis with characterization of volatiles evolved and residue left. Thermal degradation of poly-(TGDDM) starts at 260°C with elimination of water from secondary alcoholic groups which is a typical pathway for epoxy resin degradation. Resulting unsaturations weaken bonds in the β-position and provoke the first chain breaking at allyl–amine and allyl–either bonds. With increasing temperature, saturated alkyl–ether bonds and alkyl carbon–carbon bonds are broken first, followed by the most stable alkyl–aryl bonds at T>365°C. The combustion performance of TGDDM is discussed on the basis of the thermal degradation behavior.     

Establishing the synthetic origin of amphetamines by 2H NMR spectroscopy

Nine samples of N-acetyl-3,4-methylenedioxyamphetamine (N-acetyl-MDA), prepared according to the most common synthetic procedures, are submitted to (2)H NMR spectroscopy. The relative deuterium content at the various sites of the molecule is shown to depend on its synthetic history. The technique provides a chemical fingerprint of N-acetyl-MDAs and it can be used to trace back the precursor materials and the synthetic pathways employed in the preparation of the samples.     

Unsymmetrically substituted furoxans. Part 16 . Reaction of benzenesulfonyl substituted furoxans with ethanol and ethanethiol in basic medium

The use of benzenesulfonyl substituted furoxans as flexible intermediates for the synthesis of new functionalized furoxans interesting for their potential biological properties is discussed. Reaction of benzenesul-fonylphenylsulfonylfuroxan isomers 7a and 7b with ethanol and ethanethiol in basic medium affords the expected ethers and sulphides respectively. Reaction of bis(benzenesulfonyl)furoxan ( 1 ) with ethanol in basic medium gives 3-benzenesulfonyl-4-ethoxyfuroxan ( 2 ) or diethoxyfuroxan (3), according to the experimental procedure. In contrast the reaction of 1 with ethanethiol gives a mixture of substitution compounds and the 4-benzenesulfonyl-3-ethylthiofurazan ( 11 ). The structure of the compounds has been assigned by nmr spectroscopy and, in the case of 3-benzenesulfonyl-4-ethylthiofuroxan ( 9b ), confirmed by X-ray analysis.     

Analytical assays based on detecting conformational changes of single molecules.

One common strategy for the detection of biomolecules is labeling either the target itself or an antibody that binds to it. Herein, a different approach, based on detecting the conformational change of a probe molecule induced by binding of the target is discussed. That is, what is being detected is not the presence of the target or the probe, but the conformational change of the probe. Recently, a single-molecule sensor has been developed that exploits this mechanism to detect hybridization of a single DNA oligomer to a DNA probe, as well as specific binding of a single protein to a DNA probe. Biomolecular recognition often involves large conformational changes of the molecules involved, and therefore this strategy may be applicable to other assays.     

Fast exopolysaccharide secretion of Pseudomonas aeruginosa on polar polymer surfaces

The influence of the surface chemical structure and related physicochemical properties on the adhesion of P. aeruginosa has been studied for moderately hydrophobic polymers and for hydrophilic surfaces obtained by O2-plasma treatments and 50 keV Ar+ beam irradiation of poly(hydroxymethylsiloxane) and poly(ethyleneterephthalate). The surface chemical structure has been obtained by X-ray photoelectron spectroscopy, the roughness was measured by atomic force microscopy, and the surface free energy was evaluated from contact angle measurements for all the polymer substrates before and after the irradiation treatments. It is shown that a massive and unusually fast secretion of exopolysaccharides onto highly polar surfaces, corresponding to the formation of complex three-dimensional multilayers (i.e., biofilm-like structures), occurs already after 2 h of incubation. It is suggested that such highly polar surfaces can operate either by promoting, by means of a still unknown biomolecular mechanism, an early gene expression process or by mimicking the P. aeruginosa cellular walls.