Simultaneous analysis of 13C‐glutathione as its dimeric form GSSG and its precursor [1‐13C]glycine using liquid chromatography/isotope ratio mass spectrometry

Determination of glutathione kinetics using stable isotopes requires accurate measurement of the tracers and tracees. Previously, the precursor and synthesized product were measured with two separate techniques, liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) and gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). In order to reduce sample volume and minimize analytical effort we developed a method to simultaneously determine ¹³C‐glutathione as its dimeric form (GSSG) and its precursor [1‐¹³C]glycine in a small volume of erythrocytes in one single analysis. After having transformed ¹³C‐glutathione into its dimeric form GSSG, we determined both the intra‐erythrocytic concentrations and the ¹³C‐isotopic enrichment of GSSG and glycine in 150 µL of whole blood using liquid chromatography coupled to LC/IRMS. The results show that the concentration (range of µmol/mL) was reliably measured using cycloleucine as internal standard, i.e. with a precision better than 0.1 µmol/mL. The ¹³C‐isotopic enrichment of GSSG and glycine measured in the same run gave reliable values with excellent precision (standard deviation (sd) <0.3‰) and accuracy (measured between 0 and 5 APE). This novel method opens up a variety of kinetic studies with relatively low dose administration of tracers, reducing the total cost of the study design. In addition, only a minimal sample volume is required, enabling studies even in very small subjects, such as preterm infants. Copyright © 2009 John Wiley & Sons, Ltd.     

Free‐radical‐promoted cationic photopolymerization under visible light in aerated media: New and highly efficient silane‐containing initiating systems

New systems for the visible‐light‐induced polymerization of cationic resins working through a free‐radical‐promoted process are presented. They are based on a photoinitiator (camphorquinone, isopropylthioxanthone, Eosin), a silane, and a diphenyl iodonium salt, the new compound being the silane. The overall efficiency is strongly affected by the silane structure. The rates of polymerization and final percent conversion are noticeably higher than those obtained in the presence of already studied reference systems. Moreover, contrary to previously investigated free‐radical‐promoted cationic polymerizations, oxygen does not inhibit the process and an unusual enhancement of the polymerization kinetics is found in aerated conditions: such an observation seems to have never been reported so far. The excited state processes and the role of oxygen as revealed by laser flash photolysis are discussed. The particular behavior of the silyl radicals is outlined. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2008–2014, 2008     

Flat envelopes in commutative rings

We prove that ifR is a commutative ring such that each localization at a prime ideal has finite weak global dimension then everyR-module has a flat envelope if and only ifR is coherent and has weak global dimension less than or equal to two. The authors have been partially supported by the C.A.I.C.Y.T.     

Équations hyperboliques non-strictes: contre-exemples,du type De Giorgi,aux théorèmes d'existence et d'unicité

Sans résuméDédié àM. Gottfried Köthe à l'occasion de son anniversaire 60-ième     

New families of hypohamiltonian graphs

We construct three new infinite families of hypohamiltonian graphs having respectively 3k+1 vertices (k?3), 3k vertices (k?5) and 5k vertices (k?4); in particular, we exhibit a hypohamiltonian graph of order 19 and a cubic hypohamiltonian graph of order 20, the existence of which was still in doubt. Using these families, we get a lower bound for the number of non-isomorphic hypohamiltonian graphs of order 3k and 5k. We also give an example of an infinite graph G having no two-way infinite hamiltonian path, but in which every vertex-deleted subgraph G - x has such a path.