Effect of film thickness on the electro-reduction of molecular oxygen on electropolymerized cobalt tetra-aminophthalocyanine films

We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O₂) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O₂ reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O₂ to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy.     

Heterocyclisation of Unsaturated Phenylsulfides. Synthesis of a Novel Series of 2 Substituted-2,3-dihydrobenzothiazoles

Aminoarylhydroxy thioalkenes react with tosyl derivatives to provide mainly N substituted -2 vinyl -2,3 dihydrobenzothiazoles. A different regiochemistry of cyclization depending on whether a methyl or a phenyl susbtituent was used, was observed Formation of -2H-3,4-dihydrobenzothiazines and dienes was observed.     

Complexes of Tin(IV) Tetrachloride with 3-Formylpyridine Semicarbazone and Thiosemicarbazones

The reaction of tin(IV) tetrachloride with 3-formylpyridine semicarbazone and different 3-formylpyridine thiosemicarbazones produces [Sn(HL)CL 3 ][SnCl 5 ] where HL stands for the neutral ligand. The tin(IV) complexes were characterized using a variety of spectroscopic techniques. Coordination through the pyridine nitrogen occurs in all cases. Solvation studies in DMSO indicated that dissociation of the ligands and their complete replacement by solvent molecules occurs.     

Ring Opening of a Fatty Epoxide by Diethylacetamido Malonate in Basic Medium by Phase Transfer Catalysis or Under Microwave Irradiation

A fatty epoxide (tetradecyl-oxirane) is reacted with diethyl acetamidomalonate in basic medium, with or without solvent under solid-liquid phase transfer catalysis with LiCl, or under microwave irradiation on supported reagents (KF/Al₂O₃/LiCl). The main product is a lactone which is formed after epoxide ring opening and subsequent cyclisation. We put here into evidence, for the first time, the conjugated advantages of “dry media” reactions, lithium salt effects and microwave irradiation.     

First measurements of the HCFC-142b trend from atmospheric chemistry experiment (ACE) solar occultation spectra

The first measurement of the HCFC-142b (CH₃CClF₂) trend near the tropopause has been derived from volume mixing ratio (VMR) measurements at northern and southern hemisphere mid-latitudes for the 2004–2008 time period from spaceborne solar occultation observations recorded at 0.02 cm⁻¹ resolution with the ACE (atmospheric chemistry experiment) Fourier transform spectrometer. The HCFC-142b molecule is currently the third most abundant HCFC (hydrochlorofluorocarbon) in the atmosphere and ACE measurements over this time span show a continuous rise in its volume mixing ratio. Monthly average measurements at northern and southern hemisphere mid-latitudes have similar increase rates that are consistent with surface trend measurements for a similar time span. A mean northern hemisphere profile for the time span shows a near constant VMR at 8–20 km altitude range, consistent on average for the same time span with in situ results. The nearly constant vertical VMR profile also agrees with model predictions of a long lifetime in the lower atmosphere.