Porous surfaces

In fractal modeling, porous surfaces in the plane are usually described as the residual setE of a packing by connected open domains \(C_n\) . In the case whereE is nonempty, we investigate the relationships between the dimensionality ofE and the geometry of the complementary sets \(C_n\) . If they satisfy suitable regularity conditions, then the Bouligand dimension ofE is equal to the exponent of convergence of the series ∑(diam \(C_n\) ) ^α . We give here general conditions to obtain this equality, together with numerous examples and possible ways of developing this theory.     

Study of the spectrum of CH335C1 between 4250 and 4600 CM?1: thev2+v4 andv4+v5 rovibrational bands

About 2500 lines of CH₃ ³⁵Cl have been assigned. The strong xy Coriolis resonance between thev ₂ andv ₅ modes is quite visible between thev ₄+v ₄ ^±1 perpendicular band, centered around 4383 cm^–1, and thev ₄ ^±1 +v ₅ ^±1 perpendicular component, centered around 4475 cm^–1, with a crossing of upper energy levels allowing the observation of lines which are normally forbidden. Although not yet observed with certainty, because of the great density of lines of the spectrum, thev ₄ ¹ +v ₅ ^±1 parallel component is nevertheless detectable by its effects onv ₂+v ₄ ^±1 which is linked by Coriolis resonance to both components ofv ₄+v ₅. Moreover the spectrum is much complicated by many other resonances with weak bands which occur at level crossings: it is the case ofv ₂+3v ₆ ^±1 , connected tov ₂+v ₄ ^±1 by the well known Darling Dennison resonance which couplesv ₄ ^±1 and 3v ₆ ^±1 , and also ofv ₅ ^±1 +3v ₆ ^±1 connected tov ₄ ^±1 +v ₅ ^±1 by the same resonance; but this last case is complicated by an anharmonic resonance betweenv ₅ ^±1 +3v ₆ ^±1 and 2v ₃+3v ₆ ¹ . Two more perturbations occur on the K=–1 side ofv ₂+v ₄: a weak Coriolis resonance gives rise to one subband ofv ₁+v ₂ at a level crossing withv ₂+v ₄, and thev ₁+v ₅ band (linked of course tov ₁+v ₂ by the Coriolis resonance between thev ₂ andv ₅ modes) is quite visible and perturbs several subbands ofv ₂+v ₄ of high values of K through an anharmonic resonance. Moreover, the complex (3v ₅ ^±1 ,v+2v ₅ ⁰ , 2v ₂+v ₅ ^±1 , 3v ₂,v ₂+2v ₅ ^±2 , 3v ₅ ^±3 ) system of Coriolis-connected bands is linked to the bands studied in the present work by two Fermi resonances: one betweenv ₂+2v ₅ ⁰ andv ₁+v ₂, and the other one betweenv ₁+v ₅ and 3v ₅ ^±1 , whose several subbands have been observed on the low part of the spectrum. The values of all the band centres and of the different coupling constants have been estimated, but all these interactions make the line assignments and the interpretation of the spectrum very difficult.     

Oriented immobilization of Desulfovibrio gigas hydrogenase onto carbon electrodes by covalent bonds for nonmediated oxidation of H2

The orientation of hydrogenase bound covalently to a pyrolytic graphite edge electrode modified with a 4-aminophenyl monolayer can be modulated via electrostatic interactions during the immobilization step. At low ionic strength and when the amino groups of the electrode surface are mostly protonated, the hydrogenase is immobilized with the negatively charged region that surrounds its 4Fe4S cluster nearer to the protein surface facing the electrode. This allows direct electron transfer between the immobilized hydrogenase and the electrode, which is observed by the strong catalytic currents measured in the presence of the H2 substrate. Therefore, a very stable enzymatic electrode is produced that catalyzes nonmediated H2 oxidation.     

A novel stereocontrolled synthesis of enantiopure bicyclic lactams

A study on the reactivity of 3,4-dihydro-2-pyridones 9, derived from (S)-phenylglycinol, toward different bases is presented. Using a catalytic amount of bases, the cis bicyclic lactams were obtained with excellent diastereoselectivities.     

Synthesis of pyridone and pyridine rings by [4+2] hetero-cyclocondensation

Substituted pyridones and pyridines have been synthesised efficiently by employing iminium salt as a key precursor. These compounds were prepared using tandem [4+2] cycloaddition/deamination between azabutadiene and dienophiles.     

Rapid analysis of triterpenic acids by liquid chromatography using porous graphitic carbon and evaporative light scattering detection

An original system which uses Porous Graphitic Carbon as support and a mixture of organic solvents as mobile phase is proposed for the analysis of triterpenic acids by liquid chromatography. The separation of betulinic acid, ursolic acid, oleanolic acid, and 18alpha- and 18beta-glycyrrhetinic acids was carried out within a short time and monitored by evaporative light scattering detection as universal detection method. Molecular modelling studies show that the main contribution to the selectivity comes from the electrostatic interaction characterised by the dipole moment of the products.     

The standard redox potential of the phenyl radical/anion couple

The voltammogram of aryldiazonium tetrafluoroborates in acetonitrile (ACN), at low concentration, shows a first one-electron wave followed at a more negative potential by a small second wave; this last one corresponds to the reduction of the radical formed at the level of the first wave. Simulation of the voltammogram permits one to determine the standard redox potential of the radical/anion couple Eo(Ph./Ph-) = 0.05 V/SCE and the reduction mechanism of the diazonium cation. An electron transfer concerted with the cleavage of the C-N bond furnishes the aryl radical; this radical undergoes two competitive reactions: reduction at the electrode and H-atom transfer.     

Intensités des transitions optiques de [PtCl4]2−

The oscillator strengths of the “d-d” transitions of the ion [PtCl₄]^2? were calculated. The method, based on the evaluation of the MO of the distorted ion, gives results in good accordance with the experimental data. The transition to ¹ B _1g (a _1g →b _1g ^* ), as a consequence of the participation of the orbital 6s, mixed with \(5d_{z^2 } \) in \(a_{1_g } ,a_{1_g } \) is characterized by a very low intensity in the case of thex,y polarization.