Oxygen reduction in acid media: influence of the heat treatment on the FeNPc(1–20 isomer mixture impregnated on carbon blacks and active charcoals
Oxygen reduction with the aid of a number of FeNPc(1–2) impregnated carbon supports in sulphuric acid solutions has been investigated. 
 
Loading of the carbon samples amounted to about 10 wt.%. After a 10 day stay in the aerated solutions the samples were investigated with rotating disk electrode and X-ray photoelectron spectroscopy techniques. The most active and stable samples correspond to mono- or submonolayers of FeNPc deposited on high dibutylphthalate adsorption carbon blacks. Comparison with data obtained previously on Norit BrX impregnations emphasizes the role of the electron density on the inner nitrogen atoms rather than that on the iron centres.
Oxygen reduction in an acid medium: electrocatalysis by CoNPc(1,2) impregnated on a carbon black support; effect of loading and heat treatment
O2 reduction in an acid medium has been investigated on a transition metal macrocycle, CoNPc(1,2), impregnated on a carbon black support with a high dibutylphthalate adsorption value, using a rotating disk electrode and voltammetry techniques described previously, combined with X-ray photoelectron spectroscopy measurements. Optimal activity was found for a bilayer coverage (n = 2) at 17%-18% w/w loading. Heat treatment seems to be beneficial for n 3: it increases the overall number N of exchanged electrons and improves the electrode wetting. For the most active samples, mixed Co(II)/Co(III) valencies were displayed.
Collagen dynamics in articular cartilage under osmotic pressure
Cartilage is a complex biological tissue consisting of collagen, proteoglycans and water. The structure and molecular mobility of the collagen component of cartilage were studied by 13C solid‐state NMR spectroscopy as a function of hydration. The hydration level of cartilage was adjusted between fully hydrated (∼80 wt% H2O) and highly dehydrated (∼30 wt% H2O) using the osmotic stress technique. Thus, the conditions of mechanical load could be simulated and the response of the tissue macromolecules to mechanical stress is reported. From the NMR measurements, the following results were obtained. (i) Measurements of motionally averaged dipolar 1H–13C couplings were carried out to study the segmental mobility in cartilage collagen at full hydration. Backbone segments undergo fast motions with amplitudes of ∼35° whereas the collagen side‐chains are somewhat more mobile with amplitudes between 40 and 50°. In spite of the high water content of cartilage, collagen remains essentially rigid. (ii) No chemical shift changes were observed in 13C cross‐polarization magic angle spinning spectra of cartilage tissue at varying hydration indicating that the collagen structure was not altered by application of high osmotic stress. (iii) The 1H–13C dipolar coupling values detected for collagen signals respond to dehydration. The dipolar coupling values gradually increase upon cartilage dehydration, reaching rigid limit values at ∼30 wt% H2O. This indicates that collagen is essentially dehydrated in cartilage tissue under very high mechanical load, which provides insights into the elastic properties of cartilage collagen, although the mechanical pressures applied here exceed the physiological limit. Copyright © 2006 John Wiley & Sons, Ltd.