Publications by authors named "Valerie Heroguez"

In this study, Pickering emulsions of dodecane and medium chain triglyceride (MCT) oils were stabilized by simply alkylated-dextran nanoparticles. Our findings show that very little of these bio-friendly nanoparticles is necessary to stabilize Pickering emulsions while providing a high time stability (more than a year at 37 °C). As dextran is known to be cleavable by dextranase enzyme, hydrolysis of the nanoparticles in the presence of dextranase could be achieved.

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Pickering double oil-in-water-in-oil emulsions O/W/O were stabilized using solely cellulose nanocrystals (CNCs), which were modified by introducing surface brominated functions. The emulsions were formulated using only bio-friendly components, among which isopropyl myristate as oil phase, hydroxyl oligoethylene glycol methacrylate (OEGMA) as macromonomer, tetraethylene glycol diacrylate (TEGDA) as cross-linker, and CNCs as stabilizing particles. Formulation parameters could be tuned easily to modulate the fraction of inner emulsion droplets within the double emulsion drops or change the monomer(s) composition within the aqueous phase.

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The implementation of light-sensitive Pickering emulsions with spatio-temporal responsiveness in advanced applications like drug-delivery, colloidal or reaction engineering would open new avenues. However, curiously, light-sensitive Pickering emulsions are barely studied in the literature and their biocompatibility and/or degradability scarcely addressed. Thus, their development remains a major challenge.

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Pickering inverse emulsions of hydroxyl oligoethylene glycol methacrylate were stabilized in isopropyl myristate, a biofriendly oil, using surface-modified cellulose nanocrystals (CNCs) as stabilizing particles. The emulsions were further polymerized by free or controlled radical polymerization (ATRP), taking advantage of the bromoisobutyrate functions grafted on the CNC surface. Suspension polymerization of the emulsion led to full bead or empty capsule morphologies, depending on the initiation locus.

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Biosourced Pickering emulsion stabilizers with stimuli responsiveness are mostly designed for recycling and do not offer fast degradability as required for drug-delivery applications. Herein, dextran-a hydrophilic and biofriendly polysaccharide obtainable from biomass recovery-was used for the first time as a brick material for the formulation of (bio)degradable pH-sensitive Pickering emulsions. It was first modified with hydrophobic acetal moieties to provide pH-sensitive acetalated dextran.

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Additive manufacturing is a rising field in bone tissue engineering. Additive fabrication offers reproducibility, high precision and rapid manufacture of custom patient-specific scaffolds. The development of appropriate composite materials for biomedical applications is critical to reach clinical application of these novel biomaterials.

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Although metathesis photoinduced catalysis is now well established, there is little development in thin film preparation using photochemically activated ring-opening metathesis polymerization (ROMP). Herein, a N-heterocyclic carbene (NHC) photogenerator (1,3-bis(mesityl)imidazolium tetraphenylborate) is combined with an inactive metathesis catalyst ([RuCl(-cymene)]) to generate under UV irradiation an active catalyst (-cymene)RuCl (NHC), that is capable of producing in a single step cross-linked copolymer films by ROMP of norbornene with dicyclopentadiene. The study shows that the photoinitiated catalytic system can be optimized by increasing the yield of photogenerated NHC through a sensitizer (2-isopropylthioxanthone), and by choosing [RuI(-cymene)] as precatalyst to provide a long-term photolatency.

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Although N-heterocyclic carbenes (NHCs) have brought profound changes in catalytic organic synthesis, their generation generally requires an inert atmosphere and harsh conditions. To overcome these limitations, an air-stable NHC photogenerator has been developed involving two mild components: 1,3-bis(mesityl)imidazolium tetraphenylborate (IMesHBPh) and electronically excited isopropylthioxanthone (ITX). In this study, the photochemical mechanism is investigated via the accurate identification of the transient species and photoproducts.

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In the search of smarter routes to control the conditions of N-heterocyclic carbene (NHCs) formation, a two-component air-stable NHC photogenerating system is reported. It relies on the irradiation at 365 nm of a mixture of 2-isopropylthioxanthone (ITX) with 1,3-bis(mesityl)imidazoli(ni)um tetraphenylborate. The photoinduced liberation of NHC is evidenced by reaction with a mesitoyl radical to form an NHC-radical adduct detectable by electron spin resonance spectroscopy.

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Fast clearance, metabolism, and systemic toxicity are major limits for the clinical use of anti-cancer drugs. Histone deacetylase inhibitors (HDACi) present these defects, despite displaying promising anti-tumor properties on tumor cells in vitro and in in vivo models of cancer. The specific delivery of anti-cancer drugs into the tumor should improve their clinical benefit by limiting systemic toxicity and by increasing the anti-tumor effect.

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We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes and determine the corresponding photochemical mechanism. Then, we describe a protocol to perform ring-opening metathesis polymerization (ROMP) in solution and in miniemulsion using this NHC-photogenerating system. To photogenerate IMes, a system comprising 2-isopropylthioxanthone (ITX) as the sensitizer and 1,3-dimesitylimidazolium tetraphenylborate (IMesHBPh4) as the protected form of NHC is employed.

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We report a novel method to prepare capsules, beads, or open-cell materials from Pickering emulsions of monomers, stabilized by cellulose nanocrystals (CNCs) grafted with reactive isobutyrate bromide moieties (CNC-Br). CNC-Br particles with different hydrophilic/hydrophobic balance at their surface were prepared and subsequently used to stabilize direct (O/W), inverted (W/O), or double emulsions of styrene or n-BuA. The different emulsions obtained were subsequently polymerized, by initiating an AGET-ATRP polymerization from the brominated particles surrounding the stabilized droplets.

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The goal of this investigation was the development of smart plurifunctional polymeric particles able to deliver a biocide following an acidic trigger due to the presence of microorganisms. Such particles were synthesized by Ring-Opening Metathesis Polymerization of an α-norbornenyl polyglycidol macromonomer functionalized with biocide through a pH-sensitive imine bond. H.

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1,3-Bis(mesityl)imidazolium tetraphenylborate (IMesH BPh ) can be synthesized in one step by anion metathesis between the corresponding imidazolium chloride and sodium tetraphenylborate. In the presence of 2-isopropylthioxanthone (sensitizer), an IMes N-heterocyclic carbene (NHC) ligand can be photogenerated under irradiation at 365 nm through coupled electron/proton transfer reactions. By combining this tandem NHC photogenerator system with metathesis inactive [RuCl (p-cymene)] precatalyst, the highly active RuCl (p-cymene)(IMes) complex can be formed in situ, enabling a complete ring-opening metathesis polymerization (ROMP) of norbornene in the matter of minutes at room temperature.

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Autografts remain the gold standard for orthopedic transplantations. However, to overcome its limitations, bone tissue engineering proposes new strategies. This includes the development of new biomaterials such as synthetic polymers, to serve as scaffold for tissue production.

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Fast clearance, metabolism and systemic toxicity are major limits for the clinical use of anti-cancer drugs. Histone deacetylase inhibitors (HDACi) present these defects despite displaying promising anti-tumor properties on tumor cells in vitro and in in vivo model of cancers. Specific delivery of anti-cancer drugs into the tumor should improve their clinical benefit by limiting systemic toxicity and by increasing the anti-tumor effect.

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In this paper, we describe a simple and powerful way to synthesize antibacterial biomaterials with applications as implants in orthopedic surgery. Such implants are obtained by covalently grafting onto the Ti90A16 V4 alloy surface with vancomycin-functionalized nanoparticles. Nanoparticles were produced by ring-opening metathesis polymerization of α-norbornenyl-ω-vancomycin poly(ethylene oxide) macromonomers.

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We report the synthesis of acid-responsive polymeric nanoparticles (NPs) consisting of a polymer-histone deacetylase inhibitor conjugate. An innovative aspect of this drug delivery particle lies in the NP conjugation of a histone deacetylase (HDAC) inhibitor, CI-994 (Tacedinaline), introduced with a clickable acid-responsive prodrug during monomer synthesis, prior to polymerization. Another novelty lies in the selected norbornene (NB)-polyethylene oxide (PEO) macromonomer allowing standardization of the polymerization process by Ring-Opening Metathesis Polymerization (ROMP) and functionalization through azide-alkyne click chemistry.

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In vivo histone deacetylase (HDAC) inhibition by vorinostat under clinically acceptable dosing is limited by its poor pharmacokinetics properties. A new type of nontoxic pH-responsive delivery system has been synthesized by ring-opening metathesis polymerization, allowing for the selective distribution of vorinostat in mesothelioma tumors in vivo and subsequent histone reacetylation. The delivery system is synthesized by generic click chemistry, possesses native stealth properties for passive tumor targeting, and does not need additional chemistry for cellular internalization.

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We synthesized surface-active lipophilic core-hydrophilic shell latex particles, and we probed their efficiency as emulsion stabilizers. The relative weight percentage of the shell, RS/P, was varied to trigger the balance between lipophilicity and hydrophilicity of the particles. Particle wettability could concomitantly be tuned by the pH of the aqueous phase determining the surface charge.

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We described a norbornenyl-poly(ethylene oxide) nanoparticles ligand-free generic platform, made fluorescent with straightforward preparation by ring-opening metathesis polymerization (ROMP). Our method allowed to easily obtain a drug delivery system (DDS) with facilitated functionalization by means of azide-alkyne click chemistry and with a high selectivity for the tumor in vivo, while cellular internalization is obtained without cell targeting strategy. We demonstrated that our nanoparticles are internalized by endocytosis and colocalized with acidic intracellular compartments in two models of aggressive tumoral cell lines with low prognostic and limited therapeutic treatments.

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The aim of this study was to develop clickable prodrugs bearing a tunable pH responsive linker designed for acidic pH-mediated release of histone deacetylase inhibitors. HDACi are an important class of molecules belonging to the epigenetic modulators used for innovative cancer strategies. The behavior of these prodrugs was determined by a bioluminescence resonance energy transfer assay in living tumor cells.

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Twelve new glucosidic and galactosidic derivatives of N-alkylaminosugars with different alkylamines from 6 to 18 carbons were synthesized and characterized by (1)H and (13)C NMR. Their antifungal activity against the food fungal pathogen Aspergillus niger was evaluated using the radial growth assay. The influence of the variation of the alkyl chain length of N-alkylaminosugars on the mycelium growth was then discussed.

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Since the beginning of the 1970s, controlled release technology has witnessed great advancement, and motivated numerous researchers in materials science. These systems overcome the drawbacks of traditional drug dosage form, and offer more effective and favorable methods to optimize drug delivery in optimum dose to specific sites or to prolong delivery duration. This paper deals with the synthesis of pH-controlled drug delivery systems for bone implant, allowing the local release of gentamicin sulfate (GS), an antibiotic commonly used to prevent infections during orthopedic surgeries.

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This work reports on the synthesis of titanium bone implants functionalized with nanoparticles (NPs) containing Arg-Gly-Asp-Cys peptide (RGDC) and shows the adhesion behavior of cells seeded on these materials. RGDC peptides were first conjugated to a norbornenyl-poly(ethylene oxide) macromonomer (Nb-PEO). Then, functional NPs with a size of ∼300 nm and constituted of polynorbornene core surrounded by poly(ethylene oxide) shell were prepared by ring-opening metathesis polymerization in dispersed medium.

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