Dual functionalization of carboxymethyl cellulose and alginate via Passerini three-component reaction to graft two hydrophobic moieties: Toward modular thin films.

Passerini reaction was advantageously exploited to hydrophobize carboxymethyl cellulose (CMC) and alginates (ALG) by employing various hydrophobic aldehydes and isocyanides. The Passerini reaction, carried out in ecofriendly conditions, allowed to design never described twofold hydrophobized polysaccharide derivatives via the covalent grafting of two hydrophobic moieties. The modified CMC and ALG products were in-depth characterized to guaranty the success of the modification and to calculate the degrees of substitution (DS).

Nanoassemblies of Chitosan-Based Polyelectrolyte Complexes as Nucleic Acid Delivery Systems.

Nucleic acid delivery requires vectorization for protection from nucleases, preventing clearance by the reticuloendothelial system, and targeting to allow cellular uptake. Nanovectors meeting the above specifications should be safe for the patient, simple to manufacture, and display long-term stability. Our nanovectors were obtained via the green process of polyelectrolyte complexation, carried out at 25 °C in water at a low shear rate using chitosan (a polycationic biocompatible polysaccharide of specific molar mass and acetylation degree) and dextran sulfate as a polyanionic biocompatible polysaccharide.

Poly(vinyl alcohol)s and Their Glycoderivatives as Efficient Shell-Builders of Nanocapsules by Nanoprecipitation.

Poly(vinyl alcohol)s (PVAs) are very popular dispersants for the construction of colloids and common shell-constituents of microcapsules but remain mostly unexplored as building blocks for the design of nanocapsules through nanoprecipitation or other processes. Herein, we first show that model commercial PVAs and oils can be concomitantly engaged in solvent-shifting procedures to give rise to oil-filled nanocapsules in one step. Next, we report the synthesis of precisely defined water-soluble glyco-PVAs by reversible addition-fragmentation chain transfer (RAFT) copolymerization of 6--vinyladipoyl-d-glucopyranose and vinyl chloroacetate and selective alcoholysis reactions.

Wet-Spun Chitosan-Sodium Caseinate Fibers for Biomedicine: From Spinning Process to Physical Properties.

We designed and characterized chitosan-caseinate fibers processed through wet spinning for biomedical applications such as drug delivery from knitted medical devices. Sodium caseinate was either incorporated directly into the chitosan dope or allowed to diffuse into the chitosan hydrogel from a coagulation bath containing sodium caseinate and sodium hydroxide (NaOH). The latter route, where caseinate was incorporated in the neutralization bath, produced fibers with better mechanical properties for textile applications than those formed by the chitosan-caseinate mixed collodion route.

LipoParticles: a lipid membrane coating onto polymer particles to enhance the internalization in osteoblast cells.

LipoParticles, core-shell assemblies consisting of a polymer core coated by a lipid membrane, are promising carriers for drug delivery applications with intracellular targets. This is of great interest since it is actually challenging to treat infections involving intracellular bacteria such as bone and joint infections where the bacteria are hidden in osteoblast cells. The present work reports for the first time to the best of our knowledge the proof of enhanced internalization of particles in osteoblast cells thanks to a lipid coating of particles (= LipoParticles).

Mixed-Matrix Membranes Based on Polyetherimide, Metal-Organic Framework and Ionic Liquid: Influence of the Composition and Morphology on Gas Transport Properties.

In this work, membranes based on polyetherimide (PEI), a ZIF-8 metal-organic framework and 1-ethyl-methylimidazolium tetrafluoroborate ionic liquid (IL) were prepared. IL and ZIF-8 contents amounting to 7 wt% and 25 wt%, respectively, were investigated. CO, He and H transport properties of PEI/IL/ZIF-8 membranes were compared to those obtained for the respective PEI/ZIF-8 and PEI/IL systems.

Cytocompatibility / Antibacterial Activity Trade-off for Knittable Wet-Spun Chitosan Monofilaments Functionalized by the In Situ Incorporation of Cu and Zn.

The wet spinning of cytocompatible, bioresorbable, and knittable chitosan (CTS) monofilaments would be advantageous for a variety of surgical applications. The complexation capacity of chitosan with Cu or Zn can be leveraged to enhance its antibacterial activity, but not at the expense of cytocompatibility. In this work, a wet-spinning process was adapted for the in situ incorporation of Cu or Zn with chitosan dopes to produce monofilaments at different drawing ratios (τ) with various cation/glucosamine molar ratios, evaluated in the fibers ( and ).

Functional Hybrid Glyconanocapsules by a One-Pot Nanoprecipitation Process.

Herein, we report on one-pot fabrication of oil-filled nanocapsules wrapped with both RAFT-made glycopolymers and neutral polysaccharides (dextran and pullulan). We have made use of the nanoprecipitation technique, relying on coprecipitation of both oil and polymers in conditions thoroughly established from phase diagrams' interpretation. Mixed mono- or multilayered nanocapsules were obtained through simultaneous or sequential nanoprecipitations, respectively.

In situ synthesis of FeO nanoparticles coated by chito-oligosaccharides: physico-chemical characterizations and cytotoxicity evaluation for biomedical applications.

FeO nanoparticles coated with chito-oligosaccharides (COS) were prepared in situ by a simple co-precipitation method through a mixing of iron ions (Fe and Fe) and COS aqueous solutions followed by precipitation with ammonia. The impact of COS with different degree of polymerization (DP 10, 24 and 45) and degree of N-acetylation (DA) ∼ 24% and 50% (exhibiting high solubility) on the synthesis and physical properties of the coated magnetic nanoparticles was evaluated. Several advantages were found when the magnetic nanoparticles were prepared in the presence of the studied COS, such as: preparation of functionalized magnetic nanoparticles with narrower size distributions and, consequently, higher saturation magnetization (an increase of up to 22%); and an expressive increasing in the concentration of COS-coated magnetic nanoparticles (up to twice) in the cell viability test in comparison with pure FeO nanoparticles.

Embedment of liposomes into chitosan physical hydrogel for the delayed release of antibiotics or anaesthetics, and its first ESEM characterization.

This work describes the characterization of an original liposomes/hydrogel assembly, and its application as a delayed-release system of antibiotics and anaesthetics. This system corresponds to drug-loaded liposomes entrapped within a chitosan (CS) physical hydrogel. To this end, a suspension of pre-formed 1,2-dipalmitoyl-sn-glycero-3-phosphocoline liposomes loaded with an antibiotic (rifampicin, RIF), an anaesthetic (lidocaine, LID), or a model fluorescent molecule (carboxyfluorescein, CF), was added to a CS solution.

Programmable Hierarchical Construction of Mixed/Multilayered Polysaccharide Nanocapsules through Simultaneous/Sequential Nanoprecipitation Steps.

We report here on a one-pot construction of oil-filled hierarchical capsular assemblies using the nanoprecipitation technique. Relying on multicomponent phase diagrams, we show that simultaneous and/or sequential nanoprecipitations involving polymer combinations can be precisely programmed to design a new class of mixed/multilayered multicomponent nanocapsules, with a precise control of the dimensions, shell thickness/composition, and spatial distribution of the building blocks. The simplicity and tunability of this approach are exemplified here with a library of neutral and ionic polysaccharides giving access to a range of functional multilayered nanocarriers of interest for biomedical applications.

The morphology of rigid polyurethane foam matrix and its evolution with time during foaming - New insight by cryogenic scanning electron microscopy.

This paper presents an investigation of the morphology of growing polyurethane (PU) rigid foams during the very first seconds of the process by cryogenic scanning electron microscopy (cryo-SEM) performed at -150 °C. The heterogeneous nature of the initial mixture has been revealed with the presence of sub-micron size physical blowing agent droplets (isopentane), µm size dispersed phase nodules, and large air bubbles dispersed in a continuous matrix. Following the evolution of the microstructure during foaming by cryo-SEM suggested that the isopentane liquid droplets (undissolved part of the physical blowing agent) did not vaporize to create their own bubbles.

Self-crosslinked fibrous collagen/chitosan blends: Processing, properties evaluation and monitoring of degradation by bi-fluorescence imaging.

Porous collagen/chitosan scaffolds with different Collagen:Chitosan (Coll:Ch) ratios were prepared by freeze-drying followed by self-crosslinking via dehydrothermal treatment (DHT) and characterized as biomaterials for tissue engineering. Cy7 and Cy5.5 fluorochromes were covalently grafted to collagen and chitosan, respectively.

Polyether Sulfone-Based Epoxy Toughening: From Micro- to Nano-Phase Separation via PES End-Chain Modification and Process Engineering.

The toughness of a high-performance thermosetting epoxy network can be greatly improved by generating polyether sulfone-based macro- to nano-scale morphologies. Two polyethersulfones (PES) which only differ by their chain-end nature have been successively investigated as potential tougheners of a high-T thermoset matrix based on a mixture of trifunctional and difunctional aromatic epoxies and an aromatic diamine. For a given PES content, morphologies and toughness of the resulting matrices have been tuned by changing curing conditions and put into perspective with PES chain-end nature.

Tuning relaxation dynamics and mechanical properties of polymer films of identical thickness.

Using dewetting as a characterization tool, we demonstrate that physical properties of thin polymer films can be regulated and tuned by employing variable processing conditions. For different molecular weights, the variable behavior of polystyrene films of identical thickness, prepared along systematically altered pathways, became predictable through a single parameter P, defined as the ratio of time required over time available for the equilibration of polymers. In particular, preparation-induced residual stresses, the corresponding relaxation times as well as the rupture probability of such films (of identical thickness) varied by orders of magnitude following scaling relations with P.

Biohybrid cellulose fibers: Toward paper materials with wet strength properties.

Herein, we report on the preparation of novel cellulose-PEG biohybrid papers with wet strength properties. The biohybrid paper sheets are obtained using a two-step procedure where ω- or α, ω-azide functionalized PEG chains are anchored onto alkyne-functionalized wood fibers through CuAAC ligation in mild and aqueous conditions. The incorporation of the PEG grafts mostly occurs at the periphery of the cellulose fibers and degrees of substitution up to 0.

Processing and antibacterial properties of chitosan-coated alginate fibers.

The preparation of chitosan-coated alginate fibers by a wet spin process is presented and the characterization of the antibacterial activities of these fibers is discussed. Preformed calcium alginate fibers were passed in chitosan acetate solutions. The coagulation method of the coating consisted in the immersion of fibers in a bath of calcium dihydroxide solution (0.

Nanoprecipitation of PHPMA (Co)Polymers into Nanocapsules Displaying Tunable Compositions, Dimensions, and Surface Properties.

A series of PHPMA homopolymers and of mannose- and dimethylamino-functionalized copolymers, were prepared by RAFT polymerization and engaged in the preparation of oil-loaded nanocapsules using the "Shift'N'Go" process. Playing with the phase diagrams of both oil and homo- or copolymers afforded the preparation of functional camptothecin-loaded nanocapsules displaying tunable dimensions (90-350 nm), compositions and surface properties.

Modular construction of single-component polymer nanocapsules through a one-step surfactant-free microemulsion templated synthesis.

Formation of O/W surfactant-free microemulsions from water/oil/acetone ternary systems is exploited to construct precisely-defined shell-functionalized core-loaded nanocapsules with tunable diameters (ranging from 50 to 190 nm) in one step.

Macro-hydrogels versus nanoparticles by the controlled assembly of polysaccharides.

The controlled assembly of oppositely charged chitosan (CS, Mw ∼ 33 × 10(3) to 600 × 10(3)g mol(-1)) and dextran sulfate (DS, Mw = 1.3 × 10(6)g mol(-1)) or heparin (HP, Mw = 1.8 × 10(4)g mol(-1)) led either to nanoparticles or macro-hydrogels, at room temperature.

Aqueous RAFT Polymerization of Imidazolium-Type Ionic Liquid Monomers: En Route to Poly(ionic liquid)-Based Nanoparticles through RAFT Polymerization-Induced Self-Assembly.

The synthesis by aqueous RAFT polymerization of hydrophilic narrowly dispersed imidazolium-based poly(ionic liquid)s ( typically below 1.20) is reported. Full monomer conversion is achieved within hours and high end-group fidelity of the living end groups affords the preparation of well-defined block copolymers.

Fine microstructure of processed chitosan nanofibril networks preserving directional packing and high molecular weight.

Crystalline chitosan nanofibril networks were prepared, preserving the native structural packing and the polymer high molecular weight. The fine microstructure of the nanomaterial, obtained by mild hydrolysis of chitosan (CHI), was characterized by using synchrotron small- and wide-angle X-ray scattering (SAXS and WAXS), transmission electron microscopy (TEM) and electron diffraction. Hydrolysis of chitosan yielded a network of crystalline nanofibrils, containing both allomorphs of chitosan: hydrated and anhydrous.

Brilliant glyconanocapsules for trapping of bacteria.

Nanoprecipitation of miglyol into droplets surrounded by a functional glycopolymer generates nanocapsules of biointerest. Fluorophores are trapped in situ or post-grafted onto the crosslinked polymer shell for efficient imaging. The resulting colloids induce aggregation of bacteria through strong specific interactions and promote their facile removal.

Nanofluidics Approach to Separate between Static and Kinetic Nanoconfinement Effects on the Crystallization of Polymers.

Here we report a nanofluidics approach that allows one to discriminate, for the first time, between static and kinetic effects on the crystallization of polymers in 2-dimensional nanoconfinement. Nanofluidics cells designed to monitor in real time, via permittivity measurements, the flow process of polymers into cylindrical nanopores were employed to investigate the crystallization of poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE) under static and under kinetic confinement conditions. A significant separation between static confinement effects and flow effects in confinement is reported.

Liposome-loaded chitosan physical hydrogel: toward a promising delayed-release biosystem.

This work deals with the elaboration of an original biosystem in view of its application as drug delayed-release device in biomedical area. This innovative "hybrid" system is composed of phosphatidylcholine liposomes entrapped within a chitosan physical hydrogel (only constituted of polymer and water). To this end, pre-formed liposomes were suspended into chitosan solutions, and the polymer gelation process was subsequently carried out following particular experimental conditions.