A DFT study of several L→Al(OR ) (L=Lewis bases) adducts allowed the identification of ( Pr S)→Al(OR ) 1-S Pr as a "stable yet reactive" adduct. 1-S Pr was shown to act as a masked Lewis superacid able to release Al(OR ) under mild conditions. It could be used to abstract a OR ligand from (bipyMe )Ni(OR ) (bipyMe : 6,6'-dimethyl-2,2'-dipyridyl) and generate the nickel alkoxide complex [(bipyMe )Ni(OR )( Pr S)] [(R O) Al-F-Al(OR ) ] 5.
View Article and Find Full Text PDFChelating P^P and hemilabile P^N ligands were found to trigger the oxidation of Au(i) complexes by -benzoquinones. The ensuing Au(iii) catecholate complexes have been characterized by NMR spectroscopy, single crystal X-ray diffraction and X-ray absorption spectroscopy. They adopt tetracoordinate square-planar structures.
View Article and Find Full Text PDFNosocomial infections are often induced by the presence of pathogenic organisms on the surface of medical devices or hospital equipment. Chemical or topographical modifications of the surface are recognized as efficient strategies to prevent bacteria adhesion but they may have negative impact on the material interaction with living tissues. Here we have developed a photoactivated method for the modification of a biocompatible polymer, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) under aqueous conditions.
View Article and Find Full Text PDFA straightforward and versatile method for immobilizing polysaccharides on the surface of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) electrospun fibers is developed with the objective of designing a new functional biomaterial having a significant effect on cell proliferation. The approach relies on a one-step procedure: UV grafting of a photosensitive dextran (AQ-Dext) on the surface of PHBHV fibers according to a "grafting onto" method, with the use of an anthraquinone derivative. The photografting is conducted through a photoinduced free radical process employing an anthraquinone-based photosensitizer in aqueous medium.
View Article and Find Full Text PDFIn this paper, a straightforward method to produce poly(3-hydroxyalkanoate)-based multicompartment micelles (MCMs) is presented. Thiol-ene addition is used to graft sequentially perfluorooctyl chains and poly(ethylene glycol) oligomers onto poly(3-hydroxyoctanoate-co-hydroxyundecenoate) oligomers backbone. Well-defined copolymers are obtained as shown by ¹H NMR and size-exclusion chromatography.
View Article and Find Full Text PDFWe present a straightforward method to prepare amphiphilic graft copolymers consisting of hydrophobic poly(3-hydroxyalkanoates) (PHAs) backbone and hydrophilic α-amino-ω-methoxy poly(oxyethylene-co-oxypropylene) (Jeffamine®) units. Poly(3-hydroxyoctanoate)-co-(3-hydroxyundecenoate) (PHOU) was first methanolyzed to obtain the desired molar mass. The amino end groups of Jeffamine were converted into thiol by a reaction with N-acetylhomocysteine thiolactone and subsequently photografted.
View Article and Find Full Text PDFAmphiphilic graft copolymers composed of biocompatible bacterial poly(3-hydroxyalkanoate) and poly(ethylene glycol) have been synthesized by thiol-ene addition. They were demonstrated to form well-defined nanoscale vesicles in water by cryo-transmission electron microscopy.
View Article and Find Full Text PDFIn this article, we report the first micellization study of amphiphilic copolymers composed of bacterial medium chain length poly(3-hydroxyalkanoates) (mcl-PHAs). A series of diblock copolymers based on fixed poly(ethylene glycol) (PEG) block (5000 g mol(-1)) and a varying poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate) (PHOHHx) segment (1500-7700 g mol(-1)) have been synthesized using "click" chemistry. These copolymers self-assembled to form micelles in aqueous media.
View Article and Find Full Text PDFA new synthesis of amphiphilic biodegradable copolymers consisting of hydrophobic poly(3-hydroxyalkanoate) (PHA) backbone and hydrophilic poly(ethylene glycol) (PEG) units as side chains is described. Poly[(3-hydroxyoctanoate)-co-(3-hydroxyundecenoate)] (PHOU) was first methanolyzed and its unsaturated side chains were quantitatively oxidized to carboxylic acid. Esterification with propargyl alcohol led to an alkyne-containing "clickable" PHA in 71% conversion.
View Article and Find Full Text PDF