scholarly journals A Simple Route to Aqueous Suspensions of Degradable Copolymer Nanoparticles from Radical Ring-Opening Polymerization-Induced Self-Assembly (rROPISA)

2021 ◽  
Author(s):  
Chen Zhu ◽  
Stephanie Denis ◽  
Julien Nicolas
Keyword(s):  
Self Assembly ◽  
Ring Opening ◽  
Hydrolytic Degradation ◽  
Structural Diversity ◽  
Radical Ring ◽  
Aliphatic Polyesters ◽  
Degradable Polymer ◽  
Aqueous Suspensions ◽  
Research Fields ◽  
Synthetic Strategy

Degradable polymer nanoparticles are almost exclusively obtained by formulation of preformed degradable polymers, such as aliphatic polyesters, thus resulting is very low nanoparticle concentrations and limited structural diversity. On the other hand, many different vinyl polymers can be obtained by polymerization in aqueous dispersed media, but their non-degradability limits their use especially in the biomedical field. Herein, we combined the best of both worlds by developing a two-step radical ring-opening copolymerization-induced self-assembly (rROPISA) process, allowing to generate aqueous suspensions of narrowly dispersed, degradable vinyl copolymer nanoparticles at 15 wt.% solid contents, containing cyclic ketene acetal (CKA) units in the nanoparticle core. This strategy relied on rROPISA in DMF, followed by a simple transfer step to water. It was successfully applied to the three main CKAs used in rROP and yielded nanoparticles of ~80–215 nm in diameter with tunable amount of CKA up to 21 mol.%. Successful incorporation of ester groups in the copolymers was demonstrated by hydrolytic degradation of both the copolymers and the nanoparticles. The nanoparticles’ cytocompatibility was then established by cell viability assays and cell morphology observation with three representative healthy cell lines. Not only this synthetic strategy could be of great potential for drug delivery applications, but it can also be beneficial to other research fields to yield more environmentally friendly materials involving the use of latexes, such as paints or coatings.

scholarly journals Degradable polymer prodrugs with adjustable activity from drug-initiated radical ring-opening copolymerization

2018 ◽  
Vol 9 (43) ◽  
pp. 8291-8306 ◽  
Author(s):  
Elise Guégain ◽  
Johanna Tran ◽  
Quentin Deguettes ◽  
Julien Nicolas
Keyword(s):  
Cell Lines ◽  
Cancer Cell ◽  
Ring Opening ◽  
Cancer Cell Lines ◽  
Radical Ring ◽  
Degradable Polymer

Degradable polymer prodrugs were synthesized by ‘drug-initiated’ nitroxide-mediated radical ring-opening copolymerization and led to either nanoparticles or soluble prodrugs with adjustable cytotoxicity on two different cancer cell lines.

scholarly journals Radical Ring-Opening Copolymerization-Induced Self-Assembly (rROPISA)

2019 ◽  
Vol 52 (10) ◽  
pp. 3612-3624 ◽  
Author(s):  
Elise Guégain ◽  
Chen Zhu ◽  
Erika Giovanardi ◽  
Julien Nicolas
Keyword(s):  
Self Assembly ◽  
Ring Opening ◽  
Radical Ring

scholarly journals Progress in the Preparation of Functional and (Bio)Degradable Polymers via Living Polymerizations

2020 ◽  
Vol 21 (24) ◽  
pp. 9581
Author(s):  
Si-Ting Lin ◽  
Chung-Chi Wang ◽  
Chi-Jung Chang ◽  
Yasuyuki Nakamura ◽  
Kun-Yi Andrew Lin ◽  
...  
Keyword(s):  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Synthetic Methods ◽  
Degradable Polymers ◽  
Radical Ring ◽  
Aliphatic Polyesters ◽  
Innovative Methods ◽  
Living Polymerizations ◽  
Step Growth ◽  
Synthetic Methodologies

This review presents the latest developments in (bio)degradable approaches and functional aliphatic polyesters and polycarbonates prepared by typical ring-opening polymerization (ROP) of lactones and trimethylene carbonates. It also considers several recent innovative synthetic methods including radical ring-opening polymerization (RROP), atom transfer radical polyaddition (ATRPA), and simultaneous chain- and step-growth radical polymerization (SCSRP) that produce aliphatic polyesters. With regard to (bio)degradable approaches, we have summarized several representative cleavable linkages that make it possible to obtain cleavable polymers. In the section on functional aliphatic polyesters, we explore the syntheses of specific functional lactones, which can be performed by ring-opening copolymerization of typical lactone/lactide monomers. Last but not the least, in the recent innovative methods section, three interesting synthetic methodologies, RROP, ATRPA, and SCSRP are discussed in detail with regard to their reaction mechanisms and polymer functionalities.

scholarly journals Towards nanoparticles with site-specific degradability by ring-opening copolymerization induced self-assembly in organic medium

2021 ◽  
Author(s):  
Chen Zhu ◽  
Julien Nicolas
Keyword(s):  
Self Assembly ◽  
Ring Opening ◽  
Organic Medium ◽  
Radical Ring ◽  
Site Specific ◽  
Core Surface

Radical ring-opening copolymerization-induced self-assembly (rROPISA) was successfully applied to the synthesis of core-, surface- or surface plus core-degradable nanoparticles in heptane, leading to site-specific degradability by rROPISA.

scholarly journals Unraveling the History and Revisiting the Synthesis of Degradable Polystyrene Analogues via Radical Ring-Opening Copolymerization with Cyclic Ketene Acetals

Materials ◽  
2020 ◽  
Vol 13 (10) ◽  
pp. 2325
Author(s):  
Alexander W. Jackson ◽  
Srinivasa Reddy Mothe ◽  
Lohitha Rao Chennamaneni ◽  
Alexander van Herk ◽  
Praveen Thoniyot
Keyword(s):  
Ring Opening ◽  
Hydrolytic Degradation ◽  
Degradation Pathway ◽  
Historical Record ◽  
Radical Ring ◽  
Nmr Characterization ◽  
Cyclic Ketene Acetals ◽  
Ketene Acetals ◽  
First Time

Degradable analogues of polystyrene are synthesized via radical ring-opening (co)polymerization (rROP) between styrene and two cyclic ketene acetals, namely 2-methylene-1,3-dioxepane (MDO) and 5,6-benzo-2-methylene-1,3-dioxepane (BMDO). This approach periodically inserts ester bonds throughout the main chain of polystyrene, imparting a degradation pathway via ester hydrolysis. We discuss the historical record of this approach, with careful attention paid to the conflicting findings previously reported. We have found a common 1H NMR characterization error, repeated throughout the existing body of work. This misinterpretation is responsible for the discrepancies within the cyclic ketene acetal (CKA)-based degradable polystyrene literature. These inconsistencies, for the first time, are now understood and resolved through optimization of the polymerization conditions, and detailed characterization of the degradable copolymers and their corresponding oligomers after hydrolytic degradation.

scholarly journals Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1412
Author(s):  
Eunkyung Ji ◽  
Cian Cummins ◽  
Guillaume Fleury
Keyword(s):  
Thin Film ◽  
Block Copolymers ◽  
Self Assembly ◽  
Ring Opening ◽  
Periodic Structures ◽  
One Pot ◽  
Ordered Structures ◽  
Carbonyl Chloride ◽  
Thin Film Patterning ◽  
Nanoporous Templates

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.

TiCp2Cl-Catalyzed Living Radical and Ring Opening Polymerizations Initiated from Epoxides and Aldehydes in the Synthesis of Linear, Graft and Branched Polymers

2004 ◽  
Vol 856 ◽  
Author(s):  
Alexandru D. Asandei ◽  
Isaac W. Moran ◽  
Gobinda Saha ◽  
Yanhui Chen
Keyword(s):  
Electron Transfer ◽  
Ring Opening ◽  
Glycidyl Methacrylate ◽  
Ring Opening Polymerization ◽  
Branched Polymers ◽  
Single Electron Transfer ◽  
Radical Ring ◽  
Polymer Architectures ◽  
Complex Polymer

ABSTRACTTi(III)Cp2Cl-catalyzed radical ring opening (RRO) of epoxides or single electron transfer (SET) reduction of aldehydes generates Ti alkoxides and carbon centered radicals which add to styrene, initiating a radical polymerization. This polymerization is mediate in a living fashion by the reversible termination of growing chains with the TiCp2Cl metalloradical. In addition, polymers or monomers containing pendant epoxide groups (glycidyl methacrylate) can be used as substrates for radical grafting or branching reactions by self condensing vinyl polymerization. In addition, Ti alkoxides generated in situ by both epoxide RRO and aldehyde SET initiate the living ring opening polymerization of ε-caprolactone. Thus, new initiators and catalysts are introduced for the synthesis of complex polymer architectures.

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