Switchable pH-Responsive Morphologies of Coassembled Nucleobase Copolymers.

This work presents supramolecular coassembled nucleobase copolymers with transitional morphologies upon pH changes (from 7.4 to 10). Uracil- and adenine-containing copolymers were prepared by RAFT, which allowed us to finely tailor the polymerization degree and the composition.

4-Vinyl Guaiacol: A Key Intermediate for Biobased Polymers.

In order to contribute to the shift from petro-based chemistry to biobased chemistry, necessary to minimize the environmental impacts of the chemical industry, 2-methoxy-4-vinylphenol (4-vinyl guaiacol, 4VG) was used to synthesize a platform of biobased monomers. Thus, nine biobased monomers were successfully prepared. The synthesis procedures were investigated through the green metrics calculations in order to quantify the sustainability of our approaches.

New Insight into Nanoscale Identification of the Polar Axis Direction in Organic Ferroelectric Films.

Ferroelectric poly(vinylidene fluoride--trifluoroethylene) [P(VDF--TrFE)] thin films have been deposited by spin-coating onto the BiNaTiO(BNT)/LNO/SiO/Si heterostructure. The copolymer microstructure investigated by using grazing-incidence wide-angle X-ray diffraction (GIWAXD) and deduced from the (200)/(110) reflections demonstrates that the -axis in the P(VDF--TrFE) orthorhombic unit cell is either in the plane or out of the plane, depending on the face-on or on the two types of edge-on (called and ) lamellar structures locally identified by atomic force microscopy (AFM). For edge-on lamellae regions, the electroactivity ( ∼ -50.

Dynamic PEG-PLA/Hydroxyurethane Networks Based on Imine Bonds as Reprocessable Elastomeric Biomaterials.

The development of dynamic covalent chemistry opens the way to the design of materials able to be reprocessed by an internal exchange reaction under thermal stimulus. Imine exchange differs from other exchange reactions by its relatively low temperature of activation. In this study, amine-functionalized star-shaped PEG-PLA and an aldehyde-functionalized hydroxyurethane modifier were combined to produce PEG-PLA/hydroxyurethane networks incorporating imine bonds.

Dihydroxyacetone: A User Guide for a Challenging Bio-Based Synthon.

1,3-dihydroxyacetone (DHA) is an underrated bio-based synthon, with a broad range of reactivities. It is produced for the revalorization of glycerol, a major side-product of the growing biodiesel industry. The overwhelming majority of DHA produced worldwide is intended for application as a self-tanning agent in cosmetic formulations.

Original Fluorinated Non-Isocyanate Polyhydroxyurethanes.

New fluorinated polyhydroxyurethanes (FPHUs) with various molar weights were synthesized via the polyaddition reaction of a fluorinated telechelic bis(cyclocarbonate) (bis-CC) with a diamine. The fluorinated bis-CC was initially synthesized by carbonylation of a fluorinated diepoxide, 1,4-bis(2',3'-epoxypropyl)perfluorobutane, in the presence of LiBr catalyst, in high yield. Then, several reaction conditions were optimized through the model reactions of the fluorinated bis-CC with hexylamine.

Catalyst-Free Thia-Michael Addition to α-Trifluoromethylacrylates for 3D Network Synthesis.

Thia-Michael additions (1,4-additions of a thiol to a Michael acceptor) are generally catalyzed by an external Brønsted or Lewis base. A spontaneous (uncatalyzed) Michael addition of thiols to α-trifluoromethyl acrylates is described, as well as its application to the very efficient preparation of a thermoset. A thorough mechanistic investigation, based on an experimental kinetic study and on DFT calculations, is presented for the addition of arene- and alkanethiols to tert-butyl trifluoromethyl acrylate in polar aprotic solvents, unveiling a probable solvent-assisted proton transfer in the rate-determining step and a considerable lowering of the energy barrier induced by the CF group.

Coordination Adaptable Networks: Zirconium(IV) Carboxylates.

Vitrimers are 3D "covalent adaptable networks" (CANs) with flow properties thanks to thermally activated associative exchange reactions. This contribution introduces coordination adaptable networks, or CooANs, that are topologically related to metal-organic frameworks with octahedral Zr clusters as secondary building units in a carboxylic acid-functionalized acrylate-methacrylate copolymer matrix. A series of Zr-CooAN-x materials (x=percent of Zr loading relative to maximum capacity) was synthesized with x=5, 10, 15, 20, 25, 50 and 100.

Stimuli-Responsive Thiomorpholine Oxide-Derived Polymers with Tailored Hydrophilicity and Hemocompatible Properties.

Thermo-responsive hydrophilic polymers, including those showing tuneable lower critical solution temperature (LCST), represent a continuous subject of exploration for a variety of applications, but particularly in nanomedicine. Since biological pH changes can inform the organism about the presence of disequilibrium or diseases, the development of dual LCST/pH-responsive hydrophilic polymers with biological potential is an attractive subject in polymer science. Here, we present a novel polymer featuring LCST/pH double responsiveness.

Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction.

Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction.

Fluorinated nanotubes: synthesis and self-assembly of cyclic peptide-poly(vinylidene fluoride) conjugates.

The synthesis of cyclic peptide-poly(vinylidene fluoride) (CP-PVDF) conjugates comprising (d--l)-cyclopeptides as building blocks and their self-assembly into tube-like structures is described. By growing two PVDF polymeric chains from opposite sides of a preassembled cyclic-peptide macro-chain transfer agent, a PVDF-CP-PVDF conjugate was prepared. This "grafting-from" strategy, allowed the synthesis of the conjugate with high purity and using facile purification steps.

Biobased Composites by Photoinduced Polymerization of Cardanol Methacrylate with Microfibrillated Cellulose.

Biobased monomers and green processes are key to producing sustainable materials. Cardanol, an aromatic compound obtained from cashew nut shells, may be conveniently functionalized, e.g.

Plant-environment microscopy tracks interactions of with plant roots across the entire rhizosphere.

Our understanding of plant-microbe interactions in soil is limited by the difficulty of observing processes at the microscopic scale throughout plants' large volume of influence. Here, we present the development of three-dimensional live microscopy for resolving plant-microbe interactions across the environment of an entire seedling growing in a transparent soil in tailor-made mesocosms, maintaining physical conditions for the culture of both plants and microorganisms. A tailor-made, dual-illumination light sheet system acquired photons scattered from the plant while fluorescence emissions were simultaneously captured from transparent soil particles and labeled microorganisms, allowing the generation of quantitative data on samples ∼3,600 mm in size, with as good as 5 µm resolution at a rate of up to one scan every 30 min.

Semi-Fluorinated Di and Triblock Copolymer Nano-Objects Prepared via RAFT Alcoholic Dispersion Polymerization (PISA).

A set of well-defined amphiphilic, semi-fluorinated di and triblock copolymers were synthesized via polymerization-induced self-assembly (PISA) under alcoholic dispersion polymerization conditions. This study investigates the influence of the length, nature and position of the solvophobic semi-fluorinated block. A poly(,-dimethylaminoethyl methacrylate) was used as the stabilizing block to prepare the di and tri block copolymer nano-objects via reversible addition-fragmentation chain transfer (RAFT) controlled dispersion polymerization at 70 °C in ethanol.

Evaluation of Self-Assembly Pathways to Control Crystallization-Driven Self-Assembly of a Semicrystalline P(VDF--HFP)--PEG--P(VDF--HFP) Triblock Copolymer.

To date, amphiphilic block copolymers (BCPs) containing poly(vinylidene fluoride--hexafluoropropene) (P(VDF--HFP)) copolymers are rare. At moderate content of HFP, this fluorocopolymer remains semicrystalline and is able to crystallize. Amphiphilic BCPs, containing a P(VDF-co-HFP) segment could, thus be appealing for the preparation of self-assembled block copolymer morphologies through crystallization-driven self-assembly (CDSA) in selective solvents.

Photoinduced Polymerization of Eugenol-Derived Methacrylates.

Biobased monomers have been used to replace their petroleum counterparts in the synthesis of polymers that are aimed at different applications. However, environmentally friendly polymerization processes are also essential to guarantee greener materials. Thus, photoinduced polymerization, which is low-energy consuming and solvent-free, rises as a suitable option.

Radical Aqueous Emulsion Copolymerization of Eugenol-Derived Monomers for Adhesive Applications.

Biobased monomers derived from eugenol were copolymerized by emulsion polymerization to produce latexes for adhesive applications. Stable latexes containing ethoxy dihydroeugenyl methacrylate and ethoxy eugenyl methacrylate with high total solids content of 50 wt % were obtained and characterized. Latexes synthesis was carried out using a semibatch process, and latexes with particle diameters in the range of 159-178 nm were successfully obtained.

Fluoroalkyl Pentacarbonylmanganese(I) Complexes as Initiators for the Radical (co)Polymerization of Fluoromonomers.

The use of [Mn(R)(CO)] (R = CF, CHF, CHCF COCFCH) to initiate the radical polymerization of vinylidene fluoride (FC=CH, VDF) and the radical alternating copolymerization of vinyl acetate (CH=CHOOCCH, VAc) with -butyl 2-(trifluoromethyl)acrylate (MAF-TBE) by generating primary R radicals is presented. Three different initiating methods with [Mn(CF)(CO)] (thermal at ca. 100 °C, visible light and UV irradiations) are described and compared.

π-Stacking Interactions of Graphene-Coated Cobalt Magnetic Nanoparticles with Pyrene-Tagged Dendritic Poly(Vinylidene Fluoride).

This study investigates the non-covalent coating of cobalt magnetic nanoparticles (MNPs) involving a graphene surface with pyrene-tagged dendritic poly(vinylidene fluoride) (PVDF). Dendrimers bearing a pyrene moiety were selected to play the role of spacers between the graphene surface of the MNPs and the PVDF chains, the pyrene unit being expected to interact with the surface of the MNPs. The pyrene-tagged dendritic spacer 11 decorated with ten acetylenic units was prepared and fully characterized.

Crystal structure of penta-carbon-yl(2,2-di-fluoro-propane-thio-ato-κ)manganese(I).

The title compound, [Mn{SC(O)CFCH}(CO)], has been isolated as a by-product during the reaction of K[Mn(CO)] with CHCFCOCl. It is built up from a di-fluoro-methyl-propane-thio-ate bonded to an Mn(CO) moiety through the S atom. The Mn atom has an almost perfect octa-hedral coordination sphere.

Critical Dependence of Molecular Weight on Thermoresponsive Behavior of Diblock Copolymer Worm Gels in Aqueous Solution.

Reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate was used to prepare three poly(glycerol monomethacrylate) -poly(2-hydroxypropyl methacrylate) (denoted G -H  or PGMA-PHPMA) diblock copolymers, namely G-H, G-H, and G-H. A master phase diagram was used to select each copolymer composition to ensure that a pure worm phase was obtained in each case, as confirmed by transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS) studies. The latter technique indicated a mean worm cross-sectional diameter (or worm width) ranging from 11 to 20 nm as the mean degree of polymerization (DP) of the hydrophobic PHPMA block was increased from 80 to 200.

Grafting of Polymer Brushes from Xanthate-Functionalized Silica Particles.

Monodisperse silica particles (SiPs) were surface-modified with a newly designed silane coupling agent comprising a triethoxysilane and an alkyl halide, namely, 6-(triethoxysilyl)hexyl 2-bromopropionate, which was further treated with potassium O-ethyl dithiocarbonate (PEX) to immobilize xanthate molecules on the particle surfaces. Surface-initiated macromolecular design via interchange of xanthates (MADIX) polymerization of vinyl acetate (VAc) was conducted with the xanthate-functionalized SiPs. The polymerization was well controlled and produced SiPs coated with poly(vinyl acetate) (PVAc) with a well-defined target molar mass and a graft density of about 0.

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives.

Thermal decarbonylation of the acyl compounds [Mn(CO) (COR )] (R =CF , CHF , CH CF , CF CH ) yielded the corresponding alkyl derivatives [Mn(CO) (R )], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn( CO) (eq- CO)(R )] and [Mn( CO) (ax- CO)(R )] isotopomers and a ranking of the R donor power in the order CF View Article and Find Full Text PDF