Linear and three-arm star hydroxytelechelic poly(benzyl β-malolactonate)s: a straightforward one-step synthesis through ring-opening polymerization

International audienceRing-opening polymn. (ROP) of racemic-benzyl β-malolactonate (MLABe) initiated by an alc. such as 1,3-propanediol (PPD) or 2-hydroxymethyl-1,3-propanediol (TMM), and catalyzed by a metal triflate M(OTf)3 with M = Nd, Bi, proceeded under mild operating conditions (in bulk at 60 °C). The functionality of the alc. dictates the topol. of the resulting hydroxy telechelic PMLABe. The ROP promoted by the neodymium-based catalytic system afforded a satisfactory activity and control in terms of molar mass and dispersity values (Mn,NMR up to 7000 g mol-1, DM \textless 1.35). Mechanistic insights revealed that ring-opening of MLABe took place through the selective oxygen-acyl bond cleavage without undesirable side reactions such as transesterification or crotonisation, as evidenced by NMR and mass spectrometry analyses of the recovered polyesters. The structure of the corresponding α,ω-hydroxy telechelic PMLABes was ascertained by 1H and 13C\1H\ NMR, SEC, and MALDI-ToF mass spectrometry analyses. In comparison, methane and trifluoromethane sulfonic acids did not allow the formation of well-defined PMLABe diols. Differences in the behavior of MLABe and the related β-butyrolactone are highlighted. The present Nd(OTf)3/PPD or TMM catalytic ROP of MLABe thus represents a valuable direct synthesis of PMLABe diols and triols, resp., without requiring chem. modification of a preformed PMLABe precursor

Synthetic and natural speech intelligibility in individuals with visual impairments: Effects of experience and presentation rate

The present study aims to compare the intelligibility of words produced in natural and synthetic speech both with normal and fast speaking rate. The effect of several individual parameters on the intelligibility of synthetic speech was also investigated. Thirty adults with visual impairment took part in the research. The experimental design consisted of two parts: a structured interview and a psychoacoustic test. The interviews were focused on the participants' demographic data experience in using synthetic speech. The results indicated that participants performed more accurately in recognizing words presented in normal speaking rate than in a fast rate. Moreover, the results indicated that the differences between synthetic and natural speech were statistically significant. © 2013 The authors and IOS Press. All rights reserved

Opsonisation of nanoparticles prepared from poly(β-hydroxybutyrate) and poly(trimethylene carbonate)-b-poly(malic acid) amphiphilic diblock copolymers: Impact on the in vitro cell uptake by primary human macrophages and HepaRG hepatoma cells

International audienceThe present work reports the investigation of the biocompatibility, opsonisation and cell uptake by human primary macrophages and HepaRG cells of nanoparticles (NPs) formulated from poly(β-malic acid)-b-poly(β-hydroxybutyrate) (PMLA-b-PHB) and poly(β-malic acid)-b-poly(trimethylene carbonate) (PMLA-b-PTMC) diblock copolymers, namely PMLA800-b-PHB7300, PMLA4500-b-PHB4400, PMLA2500-b-PTMC2800 and PMLA4300-b-PTMC1400. NPs derived from PMLA-b-PHB and PMLA-b-PTMC do not trigger lactate dehydrogenase release and do not activate the secretion of pro-inflammatory cytokines demonstrating the excellent biocompatibility of these copolymers derived nano-objects. Using a protein adsorption assay, we demonstrate that the binding of plasma proteins is very low for PMLA-b-PHB-based nano-objects, and higher for those prepared from PMLA-b-PTMC copolymers. Moreover, a more efficient uptake by macrophages and HepaRG cells is observed for NPs formulated from PMLA-b-PHB copolymers compared to that of PMLA-b-PTMC-based NPs. Interestingly, the uptake in HepaRG cells of NPs formulated from PMLA800-b-PHB7300 is much higher than that of NPs based on PMLA4500-b-PHB4400. In addition, the cell internalization of PMLA800-b-PHB7300 based-NPs, probably through endocytosis, is strongly increased by serum pre-coating in HepaRG cells but not in macrophages. Together, these data strongly suggest that the binding of a specific subset of plasmatic proteins onto the PMLA800-b-PHB7300-based NPs favors the HepaRG cell uptake while reducing that of macrophages

Studies on the alcoholysis of poly(3-hydroxybutyrate) and the synthesis of PHB-b-PLA block copolymer for the preparation of PLA/PHB-b-PLA blends

[[abstract]]Molecular interactions, rheological behaviors and microstructures of 1,3:2,4-dibenzylidene-d-sorbitol (DBS)/poly(ethylene glycol) (PEG) organogel-inorganic silica hybrid materials are discussed in this study. DBS can dissolve in low-molecular-weight PEG to form organogels. The self-assembly behavior of these organogels was significantly influenced by the addition of the inorganic silica. The π interactions between the phenyl rings of DBS were not influenced by silica addition; however, the addition of silica affected the intermolecular hydrogen bonding of DBS, which interacts with PEG. The silica more likely interacted with PEG and decreased the intermolecular interactions between DBS and PEG, which resulted in an increase in the self-assembly of DBS. Therefore, the gel formation time and gel dissolution temperature increased as the amount of silica increased, as determined by dynamic rheological instruments. In addition, these organogel systems were all found to exhibit spherulite-like textures under polarized optical microscopy. The addition of silica and the increased DBS self-assembly in PEG resulted in a higher self-assembly temperature of the organogels. The higher temperature resulted in the presence of fewer nucleation sites and larger spherulite sizes in these systems. Small-angle X-ray scattering results demonstrated lamellar packing in these spherulite-like morphologies. Furthermore, the organogels with silica affected the intermolecular hydrogen bonding between DBS and PEG to facilitate the self-assembly of DBS, which resulted in increased diameter sizes of the DBS nanofibrils, as observed using scanning electron microscopy. It was observed that the silica was entrapped within these nanofibrillar networks.[[notice]]補正完