Decarbonylation of complex iridium carbonyls in solution: A problem in chemical dynamics

The kinetics of decarbonylation of [Ir(CO)(dp)₂]Cl and [IrCl(CO)₂(Ph₃P)₂] has been studied in different solvents, at temperatures between ?25° and +70°C, by means of reactors of defined fluid dynamics which allow a separation to be made between “physical” and “chemical” rate constants. Chemical rate constants have been found to depend markedly on the diffusion coefficients of carbon monoxide in the various solvents. The process of decarbonylation has been described, for both reactions, by the sequence: structural isomerization, characterized by a very low preexponential factor, decomposition of the less stable isomer against the solvent's barrier, and diffusion of carbon monoxide to the gas–liquid interface. The kinetic problems involved in the determination of rate constants and their implications have been emphasized.     

Bile enterogastric reflux sensor using plastic optical fibers

A portable optical-fiber sensor for ambulatory assessment of the enterogastric reflux, based on the optical properties of the bile, was developed. It makes use of two light-emitting diodes and of an appropriate electronic circuit that processes the signals and provides the readout on a display. A suitable probe for in vivo measurements was designed. Plastic fiber bundles are used in order to obtain probe flexibility and low price. In vivo measurements performed on different patients show the superiority of this technique over existing methods.     

Bounding the number of connected components of a real algebraic set

For every polynomial mapf=(f ₁,…,f _k): ℝ ⁿ →ℝ ^k , we consider the number of connected components of its zero set,B(Z _f) and two natural “measures of the complexity off,” that is the triple(n, k, d), d being equal to max(degree off _i), and thek-tuple (Δ₁,...,Δ₄), Δ _k being the Newton polyhedron off _i respectively. Our aim is to boundB(Z _f) by recursive functions of these measures of complexity. In particular, with respect to (n, k, d) we shall improve the well-known Milnor-Thom’s bound μ _d (n)=d(2d−1) ⁿ⁻¹. Considered as a polynomial ind, μ _d (n) has leading coefficient equal to 2 ⁿ⁻¹. We obtain a bound depending onn, d, andk such that ifn is sufficiently larger thank, then it improves μ _d (n) for everyd. In particular, it is asymptotically equal to 1/2(k+1)n ^k−1 dⁿ, ifk is fixed andn tends to infinity. The two bounds are obtained by a similar technique involving a slight modification of Milnor-Thom's argument, Smith's theory, and information about the sum of Betti numbers of complex complete intersections.     

v-Triazolines—IV: NMR configuration assignment of 5-dialkylamino-v-triazolines

A series of 1-aryl-5-amino-4,5-dihydro-v-triazoles bearing at least one hydrogen atom at the C-4 position has been prepared. The NMR features of the above compounds have been studied with the purpose of differentiating the triazolines with a trans configuration from those with a cis configuration. It has been shown that the hydrogen atom at C-4 lying on the same side of the amine group at C-5 always resonates at lower field than the hydrogen atom on the opposite side. This rule can be applied for identifying the configuration of the 5-amino-v-triazolines.     

Monitoring of the principal carbonyl compounds involved in malolactic fermentation of wine by solid-phase microextraction and positive ion chemical ionization GC/MS analysis

A new method has been developed to determine acetaldehyde, 2,3-butanedione (diacetyl) and 3-hydroxy-2-butanone (acetoin) in wine by solid-phase microextraction (SPME) and positive ion chemical ionization GC/MS analysis of O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBOA) derivatives. For SPME, a 65-microm PEG/DVB fibre was used; chemical ionization was performed with methane as reagent gas. The best analysis-time/sensitivity compromise was to perform the PFBOA reaction at 50 degrees C for 20 min, followed by 5-min SPME at the same temperature. Quantitative analysis was performed in SCAN mode using o-chlorobenzaldehyde as internal standard (IS), on the signal of the [M + H](+) ion at m/z 240 for acetaldehyde, 266 for acetoin (corresponding to the [M + H - 18](+) ion), 282 for diacetyl (protonated mono-derivatized compound), and 336 for IS. The accuracy and repeatability of the method were suitable for the study aims, and linearity was good in the range of concentration studied, with correlation coefficients of calibration curves 0.997, 0.998 and 0.988 for acetaldehyde, diacetyl and acetoin respectively. Due to the higher polarity of acetoin with respect to other two compounds, lower sensitivity in the detection of this compound was observed. By following the variation of the three carbonyl compounds, malolactic fermentations (MLF) were monitored in Merlot wines and this was carried out in the laboratory by two different bacteria strains.     

Thin film deposition from hexamethyldisiloxane fed glow discharges

Hexamethildisiloxane-oxygen fed radiofrequency discharges have been studied under high power density and 0.05÷0.1 torr pressure, i.e., experimental conditions of high monomer fragmentation. Actinometric Optical Emission Spectroscopy of plasma phase, X-Ray Photoelectron Spectroscopy and Infrared Spectroscopy analyses of the deposited films allowed to set the basis of the first “semi-quantitative” mechanism of deposition of siloxane films which can reasonably account for both deposition rates and film compositions. A by-product of the research is the use of CH-to-Ar emission ratio as a probe of carbon content in the film, an important practical parameter for process control.     

Global optimization of bimetallic cluster structures. II. Size-matched Ag-Pd, Ag-Au, and Pd-Pt systems

Genetic algorithm global optimization of Ag-Pd, Ag-Au, and Pd-Pt clusters is performed. The 34- and 38-atom clusters are optimized for all compositions. The atom-atom interactions are modeled by a semiempirical potential. All three systems are characterized by a small size mismatch and a weak tendency of the larger atoms to segregate at the surface of the smaller ones. As a result, the global minimum structures exhibit a larger mixing than in Ag-Cu and Ag-Ni clusters. Polyicosahedral structures present generally favorable energetic configurations, even though they are less favorable than in the case of the size-mismatched systems. A comparison between all the systems studied here and in the previous paper (on size-mismatched systems) is presented.     

A heterostructure composed of conjugated polymer and copper sulfide nanoparticles

A heterostructure formed by a conjugated polymer and semiconducting nanoparticles was produced. The conjugated polymer was synthesized by oxidative copolymerization of 3-thiopheneacetic acid and 3-hexylthiophene, thus obtaining an amphiphilic polythiophene that allows the formation of a stable polymer layer at the air-water interface. Different numbers of monolayers were deposited on solid substrates. CuS nanoparticles were grown directly in the polymeric matrix using the carboxylic groups as nucleation centers. The reactions were monitored by quartz crystal microbalance, Brewster angle, and fluorescence microscopy. The heterostructure showed increased conductivity as compared to the pristine polymer.     

QUANTUM YIELDS FOR LASER PHOTOCYCLIZATION OF BILIRUBIN IN THE PRESENCE OF HUMAN SERUM ALBUMIN. DEPENDENCE OF QUANTUM YIELD ON EXCITATION WAVELENGTH

The quantum yield for laser photocyclization of bilirubin to lumirubin in the presence of human serum albumin (phi LR) was measured at five monochromatic excitation wavelengths in the range 450-530 nm. Solutions used were optically thin throughout the wavelength range and precautions were taken to exclude contributions from photocyclization of bilirubin XIII alpha impurities. The values obtained (7.2-18 x 10(-4] were lower than those previously reported and showed the following wavelength dependence: 457.9 less than 488.0 less than 501.7 less than 514.5 approximately equal to 528.7. However, the rate of lumirubin formation, normalized to constant fluence, decreased with wavelength over the same wavelength range and no evidence was found that photoisomerization of bilirubin to lumirubin is faster with green (514.5 or 528.7 nm) than with blue (457.9 or 488.0 nm) light. The stereoselectivity of the configurational isomerization of bilirubin to 4Z,15E and 4E,15Z isomers also was studied. This reaction became less regioselective for the 4Z,15E isomer with increasing wavelength. The observed wavelength dependence of phi LR and of the [4E,15Z]: [4Z,15E] ratio at photoequilibrium are consistent with an exciton coupling model in which intramolecular energy transfer can occur between the two pyrromethenone chromophores of the bilirubin molecule in the excited state. Relative rates of lumirubin formation in vivo at different excitation wavelengths and constant fluence were estimated for different optical thicknesses and for different skin thicknesses. These estimates suggest that the recently reported clinical equivalence of blue and green phototherapy lights probably reflects the marked variation of skin transmittance with wavelength more than wavelength-dependent photochemistry. The calculations also indicated that the optimal wavelength for phototherapy is probably on the long wavelength side of the bilirubin absorption maximum.