Degradable Glycopolyester-like Nanoparticles by Radical Ring-Opening Polymerization

Pesenti, Théo; Domingo‐Lopez, Daniel A.; Gillon, Émilie; Ibrahim, Nada; Messaoudi, Samir; Nicolas, Julien

doi:10.1021/acs.biomac.2c00851

Cited by 7 publications

(26 citation statements)

References 65 publications

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“…22,45 Iodinated and β-galactosylated vinyl ether derivatives were synthesized as previously described. 43 MDO-and BMDO-based copolymers were prepared as previously described. 20,[22][23] Diethylazobisisobutyrate (DEAB) was kindly supplied by Arkema.…”

Section: Methodsmentioning

confidence: 99%

“…To further demonstrate the added value of MTC, we also showed that degradable galactose (Gal)-based P(MTC-co-GalVE) glycopolymer nanoparticles exhibited significantly enhanced interaction with LecA, a tetrameric β-galactosebinding lectin from the Pseudomonas aeruginosa bacterium, [41][42] conversely to P(MDO-co-GalVE) glycopolymer nanoparticles, which gave non-specific interactions. 43 The P(MTC-co-GalVE) nanoparticles also exhibited excellent cytocompatibility on two representative healthy cell lines.…”

Section: Introductionmentioning

confidence: 94%

“…We adapted our previously reported protocol 43 by replacing MDO by MTC with the following amounts: MTC (451 mg, 3.5 mmol), IArVE (60 mg, 0.2 mmol) and DEAB (20 mg, 0.1 mmol). A colorless viscous solid was obtained (144 mg).…”

Section: Synthesis Of Poly(2-methylene-136-trioxocane-co-para-iodoary...mentioning

confidence: 99%

“…) copolymer was synthesized according to our previously reported protocol 43 by replacing MDO by MTC with the following amounts: MTC (1.191 g, 9.2 mmol), (AcO)4GalVE (268 mg, 0.5 mmol) and DEAB (50 mg, 0.2 mmol). Purification of the copolymer was performed by 4 consecutive precipitation in 75 mL of MeOH:H2O (9:1 v/v) previously cooled down by an ice bath of aqueous NaCl.…”

Section: Synthesis Of Poly(2-methylene-136-trioxocane-co-β-thiophenyl...mentioning

confidence: 99%

“…While pendent chlorine atoms can be used for postfunctionalization via nucleophilic substitution or substituted by azide groups to perform click chemistry, 46 IAr groups can serve as a handle to efficiently install thiosugar derivatives by the Buchwald−Hartwig−Migita cross-coupling method. 47 By transposing the polymerization procedures to MTC, the three MTC-based copolymers were successfully obtained (Figure S9-S14). MTC-based copolymers exhibited similar Mns, dispersities and compositions than their MDO-based counterparts.…”

Section: Synthesis Of P(mtc-co-ve) Copolymersmentioning

confidence: 99%

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Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

Pesenti

Gillon

Messaoudi

et al. 2022

Preprint

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Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) with traditional vinyl monomers allows the synthesis of degradable vinyl copolymers. However, since the most commonly used CKAs are hydrophobic, most degradable vinyl copolymers reported so far degrade very slowly by hydrolysis under physiological conditions (phosphate buffer saline, pH 7.4, 37°C) which could be detrimental for biomedical applications. Herein, to design advanced vinyl copolymers by rROP with high CKA content and enhanced degradation profiles, we reported the copolymerization of 2-methylene-1,3,6-trioxocane (MTC) as a CKA with vinyl ether (VE) or maleimide (MI) derivatives. By performing a point-by-point comparison between the MTC/VE and MTC/MI copolymerization systems, and their counterparts based on 2-methylene-1,3-dioxepane (MDO) and 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), we showed negligible impact on the macromolecular characteristics and similar reactivity ratios, suggesting successful substitution of MDO and BMDO by MTC. Interestingly, owing to the hydrophilicity of MTC, the obtained copolymers exhibited a faster hydrolytic degradation under both accelerated and physiological conditions. We then prepared MTC-based glycopolymers which were formulated into surfactant-free nanoparticles, exhibiting excellent colloidal stability up to 4 months and complete degradation under enzymatic conditions. Importantly, MTC-based glyconanoparticles also showed a similar cytocompatibility toward two healthy cell lines and a much stronger lectin affinity than MDO-based glyconanoparticles.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

Section: Synthesis Of Poly(2-methylene-136-trioxocane-co-para-iodoary...mentioning

confidence: 99%

Section: Synthesis Of Poly(2-methylene-136-trioxocane-co-β-thiophenyl...mentioning

confidence: 99%

Section: Synthesis Of P(mtc-co-ve) Copolymersmentioning

confidence: 99%

See 3 more Smart Citations

Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

Pesenti

Gillon

Messaoudi

et al. 2022

Preprint

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Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Sbordone,

Frisch

2024

Chemistry A European J

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Radical polymerization is the most widely applied technique in both industry and fundamental science. However, its major drawback is that it typically yields polymers with non‐functional, non‐degradable all‐carbon backbones—a limitation that radical ring‐opening polymerization (rROP) allows to overcome. The last decade has seen a surge in rROP, primarily focused on creating degradable polymers. This pursuit has resulted in the creation of the first readily degradable materials through radical polymerization. Recent years have witnessed innovations in new monomers that address previous design limitations, such as ring strain and reactivity ratios. Furthermore, advances in integrating rROP with reversible deactivation radical polymerization (RDRP) have facilitated the incorporation of complex, customizable chemical payloads into the main polymer chain. This short review discusses the latest developments in monomer design with a focused analysis of their limitations in a broader historical context. Recently evolving strategies for compatibility of rROP monomers with RDRP are discussed, which are key to precision polymer synthesis. The latest chemistry surveyed expands the horizon beyond mere hydrolytic degradation. Now is the time to explore the chemical potential residing in the previously inaccessible polymer backbone.

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Recyclable/degradable materials via the insertion of labile/cleavable bonds using a comonomer approach

Lefay,

Guillaneuf

2023

Progress in Polymer Science

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Degradable Glycopolyester-like Nanoparticles by Radical Ring-Opening Polymerization

Cited by 7 publications

References 65 publications

Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Recyclable/degradable materials via the insertion of labile/cleavable bonds using a comonomer approach

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