An Orthogonal Modular Approach to Macromonomers Using Clickable Cyclobutenyl Derivatives and RAFT Polymerization

A series of cyclobutene-based macromonomers derived from monomethyl ether poly(ethylene oxide) (PEO), poly(ethyl acrylate) (PEA), poly(N-isopropylacrylamide) (PNIPAM), and PEO-b-PNIPAM were synthesized by “click” copper-catalyzed azide−alkyne cycloaddition (CuAAC) and reversible addition−fragmentation chain transfer (RAFT) polymerization. First, original di- and trifunctional cyclobutene precursors with azido, alkyne and/or chain transfer agent were successfully obtained and fully characterized. Azido- and alkyne-functionalized cyclobutenes were then conjugated with modified PEO bearing azido or alkyne groups, resulting in cyclobutene-based PEOs in quantitative conversions as ascertained by NMR spectroscopy and MALDI−TOF mass spectrometry. The new chain transfer agent-terminated cyclobutene was used to mediate the RAFT polymerization of ethyl acrylate and N-isopropylacrylamide. Well-defined polymers with controlled molecular weights (Mn = 3700−11 500 g·mol−1) and narrow molecular weight distributions (PDI = 1.06−1.14) were thus obtained that retain the cyclobutene functionality, demonstrating the orthogonality of the RAFT process toward the cyclobutenyl insaturation. Combination of CuACC and RAFT polymerization was used to afford PEO-b-PNIPAM block copolymer functionalized by a cyclobutene end-group

Cyclobutenyl macromonomers: Synthetic strategies and ring-opening metathesis polymerization

AbstractIn contrast to their (oxa)norbornenyl counterparts, cyclobutenyl derivatives have remained relatively unexplored in ring-opening metathesis polymerization (ROMP), despite ROMP of cyclobutene derivatives yields unsaturated polymers based on a strictly 1,4-polybutadiene backbone that is not easily attainable by other routes. This article summarizes work done in our group in the field of cyclobutenyl-capped macromonomers that are convenient building blocks for the synthesis of graft (bottle-brush) copolymers by ROMP via the so-called macromonomer (or grafting-through) route. Synthetic strategies employing orthogonal chemistries such as reversible deactivation radical polymerization techniques (atom transfer radical polymerization – ATRP, and reversible addition-fragmentation chain transfert (RAFT) polymerization) and recent developments using copper-catalyzed azide–alkyne cycloaddition click chemistry are highlighted. Furthermore, ROMP of the so-obtained macromonomers, including preliminary novel results regarding ROMP of cyclobutenyl-capped macromonomers prepared through RAFT polymerization and click chemistry are reported and discussed

L’Aubance et le Layon, évolutions paysagères de deux vallées en contexte viticole

Cet ouvrage propose une analyse approfondie de la controverse environnementale portant sur le démantèlement des seuils et barrages en vue de restaurer la qualité de l’eau et des milieux aquatiques. Le sujet est traité sous l’angle des sciences humaines et sociales et plus précisément celui de la géographie environnemental

Novel hydrogel obtained by chitosan and dextrin-VA co-polymerization

A novel hydrogel was obtained by reticulation of chitosan with dextrin enzymatically linked to vinyl acrylate (dextrin-VA), without cross-linking agents. The hydrogel had a solid-like behaviour with G′ (storage modulus) >> G″ (loss modulus). Glucose diffusion coefficients of 3.9 × 10−6 ± 1.3 × 10−6 cm2/s and 2.9 × 10−6 ± 0.5 × 10−6 cm2/s were obtained for different substitution degrees of the dextrin-VA (20% and 70% respectively). SEM observation revealed a porous structure, with pores ranging from 50 µm to 150 µm

Synthesis and characterization of polymers for nonlinear optical applications

International audienceA difunctional NLO Azo-Dye chromophore has been synthesized and polymerization has been performed with a comonomer bearing a side-chain epoxy group. Deposition of the polymer on glass substrates was performed by spin-coating, resulting in uniform films up to 2 µm thickness. The orientation of the chromophore was performed under a " pin-to-plane " positive corona discharge followed by a heat-treatment in order to obtain reticulation of the films. Molecular orientation has been investigated using UV-Vis. and Raman spectroscopy. Poling of the films results in a decay of absorbency as well as in a blue shift of the spectrum. At the same time, the 1600 cm-1 band disappears from the Raman spectra, indicating orientation of the chromophores. Cross-linking has been studied by FTIR and all-optical poling and showed an improved stability of the electro-optic thin films

Interplay between Structure and Dynamics in Chitosan Films Investigated with Solid-State NMR, Dynamic Mechanical Analysis, and X-ray Diffraction

Modern solid-state NMR techniques, combined with X-ray diffraction, revealed the molecular origin of the difference in mechanical properties of self-associated chitosan films. Films cast from acidic aqueous solutions were compared before and after neutralization, and the role of the counterion (acetate vs Cl⁻) was investigated. There is a competition between local structure and long-range order. Hydrogen bonding gives good mechanical strength to neutralized films, which lack long-range organization. The long-range structure is better defined in films cast from acidic solutions in which strong electrostatic interactions cause rotational distortion around the chitosan chains. Plasticization by acetate counterions enhances long-range molecular organization and film flexibility. In contrast, Cl⁻ counterions act as a defect and impair the long-range organization by immobilizing hydration water. Molecular motion and proton exchange are restricted, resulting in brittle films despite the high moisture content

Chitosan hydrogels for sustained drug delivery

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Chitosan Hydrogels Incorporating Colloids For Sustained Drug Delivery

International audienceIn today's biomedical research, a huge effort is being made towards the development of efficient drug delivery systems, achieving sustainable and controlled delivery of drugs. Chitosan (CS) hydrogels are high water content materials with very relevant biological properties to that purpose. Their use for a local and delayed delivery has already been demonstrated for a wide variety of therapeutic agents. One relatively recent strategy to improve these CS-based systems consists in the insertion of colloids, embedding drugs, within their three-dimensional matrix. This provides a second barrier to the diffusion of drugs through the system, and allows to better control their release. The main objective of this review is to report the many existing complex systems composed of CS hydrogels embedding different types of colloids used as drug delivery devices to delay the release of drugs. The various biomedical applications of such final systems are also detailed in this review

Cell elongation is an adaptative response for clearing long chromatid arms from the cleavage plane.

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