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

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.

2019 ◽  
Vol 52 (10) ◽  
pp. 3612-3624 ◽  
Author(s):  
Elise Guégain ◽  
Chen Zhu ◽  
Erika Giovanardi ◽  
Julien Nicolas

2021 ◽  
Author(s):  
Chen Zhu ◽  
Stephanie Denis ◽  
Julien Nicolas

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.


2018 ◽  
Author(s):  
Pierre Marcasuzaa ◽  
Samuel Pearson ◽  
Karell Bosson ◽  
Laurence Pessoni ◽  
Jean-Charles Dupin ◽  
...  

A hierarchically structured platform was obtained from spontaneous self-assembly of a poly(styrene)-<i>b</i>-poly(vinylbenzylchloride) (PS-<i>b</i>-PVBC) block copolymer (BCP) during breath figure (BF) templating. The BF process using a water/ethanol atmosphere gave a unique double porosity in which hexagonally arranged micron-sized pores were encircled by a secondary population of smaller, nano-sized pores. A third level of structuration was simultaneously introduced between the pores by directed BCP self-assembly to form out-of-the-plane nano-cylinders, offering very rapid bottom-up access to a film with unprecedented triple structure which could be used as a reactive platform for introducing further surface functionality. The surface nano-domains of VBC were exploited as reactive nano-patterns for site-specific chemical functionalization by firstly substituting the exposed chlorine moiety with azide, then “clicking” an alkyne by copper (I) catalyzed azide-alkyne Huisgen cycloaddition (CuAAC). Successful chemical modification was verified by NMR spectroscopy, FTIR spectroscopy, and XPS, with retention of the micro- and nanostructuration confirmed by SEM and AFM respectively. Protonation of the cyclotriazole surface groups triggered a switch in macroscopic behavior from a Cassie-Baxter state to a Wenzel state, highlighting the possibility of producing responsive surfaces with hierarchical structure.


Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1412
Author(s):  
Eunkyung Ji ◽  
Cian Cummins ◽  
Guillaume Fleury

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.


2021 ◽  
Vol 9 (1) ◽  
pp. 38-50
Author(s):  
Hien Phan ◽  
Vincenzo Taresco ◽  
Jacques Penelle ◽  
Benoit Couturaud

Stimuli-responsive amphiphilic block copolymers obtained by PISA have emerged as promising nanocarriers for enhancing site-specific and on-demand drug release in response to a range of stimuli such as pH, redox agents, light or temperature.


2004 ◽  
Vol 856 ◽  
Author(s):  
Alexandru D. Asandei ◽  
Isaac W. Moran ◽  
Gobinda Saha ◽  
Yanhui Chen

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.


1999 ◽  
Vol 32 (5) ◽  
pp. 1332-1340 ◽  
Author(s):  
G. Evan Roberts ◽  
Michelle L. Coote ◽  
Johan P. A. Heuts ◽  
Leesa M. Morris ◽  
Thomas P. Davis

Sign in / Sign up

Export Citation Format

Share Document