Éditeur(s) : HAL CCSD
Résumé : International audience
The Glaser-Eglinton reaction between either two C or N propargylglycine (Pra or NPra) amino acids, in the presence of copper(II), led to cyclic hexa- and octapeptides constrained by a butadiyne bridge. The on-resin cyclization conditions were analyzed and optimized. The consequences of this type of constraint on the three dimensional structure of these hexapeptides and octapeptides were analyzed in details by NMR and molecular dynamics. We show that stabilized short cyclic peptides could be readily prepared via the Glaser oxidative coupling either with a chiral (Pra), or achiral (NPra) residue. The 1,3-butadiyne cyclization, along with disulfide bridged and lactam cyclized hexapeptides expands the range of constrained peptides that will allow exploring the breathing of amino acids around a β-turn structure.
Bioorganic and Medicinal Chemistry

hal-01091920
https://hal.archives-ouvertes.fr/hal-01091920
PUBMED : 25456082
DOI : 10.1016/j.bmc.2014.10.026

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A new method was proposed to determine the nitrogen content of nitrocelluloses (NCs). It is based on the finding of a linear relationship between the nitrogen content and the molar ratio of nitrite-to-nitrate ions released after alkaline hydrolysis. Capillary electrophoresis was used to monitor the concentration of nitrite and nitrate ions. The influences of hydrolysis time and molar mass of NC on the molar ratio of nitrite-to-nitrate ions were investigated, and new insights into the understanding of the alkaline denitration mechanism of NCs, underlying this analytical strategy is provided. The method was then tested successfully with various explosive and non-explosive NC-containing samples such as various daily products and smokeless gunpowders. Inherently to its principle exploiting a concentration ratio, this method shows very good repeatability in the determination of nitrogen content in real samples with relative standard deviation (n=3) inferior to 1.5%, and also provides very significant advantages with respect to sample extraction, analysis time (1h for alkaline hydrolysis, 3min for electrophoretic separation), which was about 5 times shorter than for the classical Devarda's method, currently used in industry, and safety conditions (no need for preliminary drying NC samples, mild hydrolysis conditions with 1M sodium hydroxide for 1h at 60°C).
Journal of Hazardous Materials

hal-01103120
https://hal.archives-ouvertes.fr/hal-01103120
PUBMED : 25562808

Éditeur(s) : HAL CCSD The Royal Society of Chemistry
Résumé : International audience
This review is devoted to the description of synthetic strategies for glycodendrimers synthesis. Dendrimers can be classified into three categories: carbohydrate-coated, carbohydrate-centered and carbohydrate-based dendrimer. In this paper we will focus on the third one, in which the core unit is originated from a monosaccharide. Compare to classical Pamam, Boltorn cores, carbohydrate units add much more three dimension information, coded in the chirality in almost each carbon. Various coupling chemistry have been developed and are presented here: glycosylation, amide bound formation, and click chemistry (thiol-ene reaction, epoxide - thiol reaction).
Carbohydrate Chemistry: Volume 40

ISBN : 978-1-84973-965-8
hal-01362709
https://hal.archives-ouvertes.fr/hal-01362709
DOI : 10.1039/9781849739986-00257