Polyhydroxybutyrate (PHB)-based triblock copolymers: synthesis of hydrophobic PHB/poly(benzyl beta-malolactonate) and amphiphilic PHB/poly(malic acid) analogues by ring-opening polymerization

International audiencePolyhydroxyalkanoates (PHAs) are biocompatible and biodegradable polyesters widely used for biomedical applications. Amphiphilic triblock copolymers with a PHB hydrophobic segment recently demonstrated attractive advantages such as high colloidal stability and low critical micellar concentration (CMC) values for the elaboration of drug delivery systems. Our approach aims at associating PHB with a fully biodegradable hydrophilic block to access new self-assembled systems with unique potential. Well-defined alpha,omega-dihydroxy telechelic PHA-based hydrophobic triblock copolymers with tunable segments length were synthesized by the controlled ring-opening polymerization (ROP) of benzyl beta-malolactonate, using polyhydroxybutyrate (PHB) diol/Nd(OTf)(3) as the catalytic system. Remarkably, the reaction proceeds with the selective oxygen-acyl bond cleavage of the beta-lactone. The corresponding amphiphilic copolymers were then obtained by hydrogenolysis. These copolymers are the only examples of fully biodegradable PHA-PHB-PHA triblock copolymers. The hydrophilic weight fraction of the copolymers was tuned from 7 to 83% upon modulating the monomer loading thus affording the ability to next access different self-assembling architectures

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

alpha,omega-Bis(trialkoxysilyl) difunctionalized polycyclooctenes from ruthenium-catalyzed chain-transfer ring-opening metathesis polymerization

International audienceThe ring-opening metathesis polymerization/cross-metathesis (ROMP/CM) of cyclooctene (COE) using bis(trialkoxysilyl)alkenes as chain-transfer agents (CTAs) and Ru catalysts to afford difunctionalized polyolefins is reported. The formation of alpha,omega-bis(trialkoxysilyl) telechelic polycycloolefins (DF) with controlled molar mass values takes place quite selectively (>90 wt%), along with minor amounts of cyclic non-functionalized polymers (CNF), as evidenced by NMR, MALDI-ToF MS, SEC analyses and fractionation experiments. The nature of the CTA and catalyst influenced much the efficiency and selectivity of the reaction. (MeO)(3)SiCH2CH=CHCH2Si(OMe)(3) (2) and (MeO)(3)Si(CH2)(3)NHC(O)OCH2CH=CHCH2OC(O)NH (CH2)(3)Si(OMe)(3) (5) proved to be the most efficient CTAs in terms of reactivity, catalyst productivity and selectivity towards DF. Diurethane CTA 5 is easily prepared, and can also be conveniently generated in situ during the ROMP/CM. Grubbs' 2nd-generation catalyst (G2) and Hoveyda-Grubbs's catalyst (HG2) afforded the best compromise in terms of selectivity and productivity, with turnover numbers of up to 95 000 mol(COE) mol(Ru)(-1) and 5000 mol(CTA) mol(Ru)(-1)

Factors affecting feelings of justice in biodiversity conflicts : towards fairer jaguar management in Calakmul, Mexico

Funding was provided by Mitacs through a Globalink Research Award to MLL, BS and SC, a José-Sarukhan Excellence Award given by the Centro del Cambio Global y Sustentabilidad del Sureste to MLL, an Excellence Award from the Quebec Center for Biodiversity Science to MLL, and a grant from the Université de Sherbrooke to SC.Conservation focuses on environmental objectives, but neglecting social concerns can lead to feelings of injustice among some actors and thus jeopardise conservation aims. Through a case study on a biodiversity conflict around jaguar management in Southern Mexico, we explored actors' feelings of injustice and their associated determinants. We employed a framework distinguishing four dimensions of justice: recognition, ecological, distributive and procedural. By conducting and analysing 235 interviews with farmers and ranchers, we investigated what drive their feeling of injustice, namely their perceptions of the injustice itself, individual characteristics and interactions with their environment. The participants selected 10 statements representing criteria characterizing their feeling of justice toward jaguar management, which they compared using pair-wise comparisons. A pioneering statistical analysis, BTLLasso, revealed that self-interest assumptions were not upheld; feelings of injustice were only weakly influenced by experience of depredation. Feelings of injustice were influenced mainly by factors related to actors' intra-and inter-group relationships (e.g. perception of collective responsibility, perceived coherence in the group to which they identified). This nuanced understanding of how people build their perception of justice can inform fairer and more effective conservation approaches. Whilst details will be context specific, it emerged that building relationships and enabling debate over ecological responsibilities are important and conservation efforts should go beyond merely offering financial compensation. We conclude that perception of justice is a neglected but important aspect to include in integrative approaches to managing biodiversity conflicts, and that novel mixed methods can advance both conceptual and applied understanding in this area.PostprintPeer reviewe

Ring-opening metathesis polymerization of cyclooctene derivatives with chain transfer agents derived from glycerol carbonate

International audienceThe synthesis of a variety of mono- and di-(glycerol carbonate) telechelic polyolefins has been achieved upon ruthenium-catalyzed ring-opening metathesis polymerization (ROMP) of cyclooctene (COE) derivatives in the presence of a vinyl or acryloyl derivative of glycerol carbonate (GC) acting as a chain-transfer agent (CTA). Reaction monitoring based on SEC and 1H NMR analyses suggested that the ROMP proceeds through the formation of first the α-GC,ω-vinyl-poly(cyclooctene) (PCOE) intermediate, which eventually evolves over time into the α,ω-di(GC)-PCOE. The nature of the solvent was shown to have a significant impact on both the reaction rates and the eventual selectivity for the mono-/di-telechelic PCOE. ROMP of 3-alkyl (methyl, ethyl, n-hexyl)-substituted COEs (3-R-COEs) afforded only the α-GC,ω-vinyl-poly(3-R-COE)s, as a result of the steric hindrance around the active intermediate, while a 5-ethyl substituted COE (5-Et-COE) enabled access to the corresponding α,ω-di(GC)-poly(5-Et-COE). The ROMP of 5,6-epoxy-, 5-hydroxy- and 5-oxo-functionalized COEs in the presence of acryloyl-GC as the CTA has also been achieved, affording from the first two monomers polymers with GC end-groups at both extremities, while a 60 : 40 mixture of mono- and di-GC terminated P(5-O[double bond, length as m-dash]COE) was observed in the latter case

α,ω-Di(glycerol carbonate) telechelic polyesters and polyolefins as precursors to polyhydroxyurethanes: an isocyanate-free approach

International audienceα,ω-Di(glycerol carbonate) telechelic poly(propylene glycol) (PPG), poly(ethylene glycol) (PEG), poly(ester ether) (PEE), and poly(butadiene) (PBD) have been synthesized through chemical modification of the corresponding α,ω-dihydroxy telechelic polymers (PPG-OH2, PEG-OH2, PEE-OH2 and PBD-OH2, respectively). Tosylation of the polymer diols with 4-tosylmethyl-1,3-dioxolan-2-one (GC-OTs) afforded, in high yields, the desired PPG, PEG, PEE and PBD end-capped at both termini with a five-membered ring cyclic glycerol carbonate (4-hydroxymethyl-1,3-dioxolan-2-one, GC). The GC-functionalization of the polymers at both chain-ends has been confirmed by NMR (1H, 13C, 1D and 2D) and FTIR spectroscopies. Using PPG-GC2 to demonstrate the concept, the corresponding polyhydroxyurethanes (PHUs/non-isocyanate polyurethanes (NIPUs)) have been subsequently prepared following a non-isocyanate method upon ring-opening catalyst-free polyaddition of the PPG-GC2 with JEFFAMINEs (Mn = 230-2000 g mol−1). The effect of various additives introduced during the polyaddition reaction has been studied at different temperatures. In particular, addition of LiBr (5 mol%) to the reaction medium was found to slightly promote the cyclocarbonate/amine reaction. The polymerization process was supported by FTIR and SEC analyses

Synthesis and polymerization of cyclobutenyl-functionalized polylactide and polycaprolactone: a consecutive ROP/ROMP route towards poly(1,4-butadiene)-g-polyesters

International audienceEfficient preparation of cyclobutenyl end-functionalized polyester macromonomers bearing polylactide (PLA) or poly(ε-caprolactone) (PCL) arms was achieved by organocatalyzed ring-opening polymerization (ROP) of L-lactide or ε-caprolactone in the presence of cis-3,4-bis(hydroxymethyl)cyclobutene or cis-4-benzyloxymethyl-3-hydroxymethylcyclobutene acting as an initiator. Cyclobutenyl end-functionalized PLA and PCL macromonomers having one or two arms were obtained in high yields with excellent control over molecular weights (up to 11 000 g mol−1) and dispersity (PDI < 1.25) by organocatalyzed ROP using 4-(N,N-dimethylamino)pyridine (DMAP) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), respectively. Ring-opening metathesis polymerization (ROMP) of the macromonomers using ruthenium-based Grubbs' second generation catalyst afforded well-defined polybutadiene-g-polyester copolymers having an exclusively linear polybutadiene backbone with a strictly 1,4-type microstructure, with molecular weights ranging from 20 000 to 170 000 g mol−1 and low dispersities (PDI ≤ 1.30). The products resulting from this consecutive ROP/ROMP route represent the first examples of poly(1,4-butadiene)-g-polyesters through the macromonomer route

Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts

International audienceThe ring-opening polymerization (ROP) of trans-1,4-cyclohexadiene carbonate (CHDC) has been investigated computationally and experimentally. DFT computations indicate that ring-opening of CHDC is thermodynamically possible, yet to a lesser extent than that of trans-cyclohexene carbonate (CHC). Effective homopolymerizations of rac-CHDC and simultaneous or sequential copolymerizations of rac-CHDC with rac-CHC and L-LA were achieved with a diaminophenolate zinc-based complex ([(NNO)ZnEt]) or a guanidine (TBD) associated with an alcohol. These ROP reactions, which confirmed the lower reactivity of rac-CHDC vs. rac-CHC, especially in homopolymerization, proceeded without any decarboxylation. Quite uniquely, highly syndiotactic PCHDC was obtained from ROP of rac-CHDC with both the zinc- and TBD-based catalysts, as revealed by 13C{1H} NMR studies. The prepared homopolymers and block or random copolymers were characterized by 1H, 13C{1H} NMR, MALDI-ToF MS, SEC and DSC techniques

Viability and Resilience of Languages in Competition

We study the viability and resilience of languages, using a simple dynamical model of two languages in competition. Assuming that public action can modify the prestige of a language in order to avoid language extinction, we analyze two cases: (i) the prestige can only take two values, (ii) it can take any value but its change at each time step is bounded. In both cases, we determine the viability kernel, that is, the set of states for which there exists an action policy maintaining the coexistence of the two languages, and we define such policies. We also study the resilience of the languages and identify configurations from where the system can return to the viability kernel (finite resilience), or where one of the languages is lead to disappear (zero resilience). Within our current framework, the maintenance of a bilingual society is shown to be possible by introducing the prestige of a language as a control variable