Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Summary Dependences of rate constants on pressure (up to 1 kbar) and on added salt concentration (up to 6.0 mol dm^–3 LiNO₃, NaNO₃, NaCl, Na₂SO₄ or KNO₃) have been established for dissociative substitution of pentacyanoferrates(II), [Fe(CN)₅L]^3– with L = 4-cyanopyridine, 4,4-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine. Activation volumes derived directly from pressure effects, and indirectly from salt effects via surface tension dependences and derived surfaces of activation, are reported, compared and discussed.     

Giant vesicles formed by gentle hydration and electroformation: a comparison by fluorescence microscopy

Giant unilamellar vesicles (diameter of a few tens of micrometers) are commonly produced by hydration of a dried lipidic film. After addition of the aqueous solution, two major protocols are used: (i) the gentle hydration method where the vesicles spontaneously form and (ii) the electroformation method where an ac electric field is applied. Electroformation is known to improve the rate of unilamellarity of the vesicles though it imposes more restricting conditions for the lipidic composition of the vesicles. Here we further characterize these methods by using fluorescence microscopy. It enables not only a sensitive detection of the defects but also an evaluation of the quantity of lipids in these defects. A classification of the defects is proposed and statistics of their relative importance in regard to both methods and lipid composition are presented: it shows for example that 80% of the vesicles obtained by electroformation from 98% 1,2-dioleoyl-sn-glycero-3-phosphocholine are devoid of significant defects against only 40% of the vesicles with the gentle hydration method. It is also shown that the presence of too many negatively charged lipids does not favor the formation of unilamellar vesicles with both methods. For the gentle hydration, we checked if the negatively charged lipids were inserted in the vesicles membrane in the same proportion as that of the lipid mixture from which they are formed. The constant incorporation of a negatively charged labeled lipid despite an increasing presence of negatively charged 1,2-dioleoyl-sn-glycero-3-[phospho-l-serine] tends to confirm that the composition of vesicles is indeed close to that of the initial mixture.     

From galactose to highly functionalized seven- and eight-membered carbocyclic rings by ring-closing metathesis

[reaction: see text]A short synthesis of highly functionalized seven- and eight-membered carbocyclic rings from galactose derivatives has been achieved. The key steps are a zinc-mediated reductive ring opening of 6-iodogalactopyranoses and a subsequent ring-closing olefin metathesis using Grubbs' ruthenium catalyst.     

Analysis of sterol oxidation products in foods

The main aspects related to the analysis of sterol oxidation products (SOP) in foods are comprehensively reviewed. Special emphasis is placed on the critical and controversial points of this analysis because these points affect crucial analytical parameters such as precision, accuracy, selectivity, and sensitivity. The effect of sample preparation and the conditions of quantification by gas chromatography and liquid chromatography on these parameters are also reviewed. The results show that, in order to choose an adequate method to analyze SOP in a certain food, the analyst must consider its SOP concentration and matrix complexity. The term SOP includes both cholesterol oxidation products (COP) and phytosterol oxidation products (POP). The state of the art of COP and POP analysis is quite different; many more studies have dealt with the analysis of COP than of POP. However, most of the results presented here about COP analysis may be extrapolated to POP analysis because both groups of compounds show similar structures and characteristics.