scholarly journals Synthesis of Non-Uniform Functionalized Amphiphilic Block Copolymers and Giant Vesicles in the Presence of the Belousov–Zhabotinsky Reaction

Biomolecules ◽  
2019 ◽  
Vol 9 (8) ◽  
pp. 352 ◽  
Author(s):  
Isadora Berlanga

Giant vesicles with several-micrometer diameters were prepared by the self-assembly of an amphiphilic block copolymer in the presence of the Belousov–Zhabotinsky (BZ) reaction. The vesicle is composed of a non-uniform triblock copolymer synthesized by multi-step reactions in the presence of air at room temperature. The triblock copolymer contains poly(glycerol monomethacrylate) (PGMA) as the hydrophilic block copolymerized with tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)3), which catalyzes the BZ reaction, and 2-hydroxypropyl methacrylate (HPMA) as the hydrophobic block. In this new approach, the radicals generated in the BZ reaction can activate a reversible addition-fragmentation chain transfer (RAFT) polymerization to self-assemble the polymer into vesicles with diameters of approximately 3 µm. X-ray photoelectron spectroscopy (XPS) measurements demonstrated that the PGMA-b-Ru(bpy)3-b-PHPMA triblock copolymer is brominated and increases the osmotic pressure inside the vesicle, leading to micrometer-sized features. The effect of solvent on the morphological transitions are also discussed briefly. This BZ strategy, offers a new perspective to prepare giant vesicles as a platform for promising applications in the areas of microencapsulation and catalyst support, due to their significant sizes and large microcavities.

2019 ◽  
Vol 10 (19) ◽  
pp. 2424-2435 ◽  
Author(s):  
Bingjie Zhao ◽  
Sen Xu ◽  
Sixun Zheng

A novel organic–inorganic ABA triblock copolymer with a poly(acrylate amide) (PAA) midblock and poly(POSS acrylate) [P(POSS)] endblocks was synthesized via sequential reversible addition–fragmentation chain transfer (RAFT) polymerization.


Polymers ◽  
2021 ◽  
Vol 13 (15) ◽  
pp. 2502
Author(s):  
Gregoire Desnos ◽  
Adrien Rubio ◽  
Chaimaa Gomri ◽  
Mathias Gravelle ◽  
Vincent Ladmiral ◽  
...  

A set of well-defined amphiphilic, semi-fluorinated di and triblock copolymers were synthesized via polymerization-induced self-assembly (PISA) under alcoholic dispersion polymerization conditions. This study investigates the influence of the length, nature and position of the solvophobic semi-fluorinated block. A poly(N,N-dimethylaminoethyl methacrylate) was used as the stabilizing block to prepare the di and tri block copolymer nano-objects via reversible addition-fragmentation chain transfer (RAFT) controlled dispersion polymerization at 70 °C in ethanol. Benzylmethacrylate (BzMA) and semi-fluorinated methacrylates and acrylates with 7 (heptafluorobutyl methacrylate (HFBMA)), 13 (heneicosafluorododecyl methacrylate (HCFDDMA)) and 21 (tridecafluorooctyl acrylate (TDFOA)) fluorine atoms were used as monomers for the core-forming blocks. The RAFT polymerization of these semi-fluorinated monomers was monitored by SEC and 1H NMR. The evolution of the self-assembled morphologies was investigated by transmission electron microscopy (TEM). The results demonstrate that the order of the blocks and the number of fluorine atoms influence the microphase segregation of the core-forming blocks and the final morphology of the nano-objects.


RSC Advances ◽  
2015 ◽  
Vol 5 (119) ◽  
pp. 98559-98565 ◽  
Author(s):  
Muhammad Mumtaz ◽  
Karim Aissou ◽  
Dimitrios Katsigiannopoulos ◽  
Cyril Brochon ◽  
Eric Cloutet ◽  
...  

Controlled polymerization and self-assembly of novel block copolymer electrolytes.


Materials ◽  
2019 ◽  
Vol 12 (19) ◽  
pp. 3145 ◽  
Author(s):  
Katharina Nieswandt ◽  
Prokopios Georgopanos ◽  
Clarissa Abetz ◽  
Volkan Filiz ◽  
Volker Abetz

In this work, we present a novel synthetic route to diblock copolymers based on styrene and 3-vinylpyridine monomers. Surfactant-free water-based reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene in the presence of the macroRAFT agent poly(3-vinylpyridine) (P3VP) is used to synthesize diblock copolymers with molecular weights of around 60 kDa. The proposed mechanism for the poly(3-vinylpyridine)-block-poly(styrene) (P3VP-b-PS) synthesis is the polymerization-induced self-assembly (PISA) which involves the in situ formation of well-defined micellar nanoscale objects consisting of a PS core and a stabilizing P3VP macroRAFT agent corona. The presented approach shows a well-controlled RAFT polymerization, allowing for the synthesis of diblock copolymers with high monomer conversion. The obtained diblock copolymers display microphase-separated structures according to their composition.


2021 ◽  
Author(s):  
bingbing zhao ◽  
Yuting Yan ◽  
Junmei Zhang ◽  
Enping Chen ◽  
Ke Wang ◽  
...  

A novel zwitterionic triblock copolymer of poly(dimethylamino carbonate)-polycaprolactone-poly((2-(methacryloyloxy)ethyl)dimethyl-(3-sulfopropyl)ammonium) [PAC(DMA)-PCL-PMDMSA] was designed and synthesized via sequential ring-opening polymerization (ROP) and reversible addition-fragmentation chain transfer (RAFT) polymerization successively. The 1H NMR and...


2018 ◽  
Vol 9 (39) ◽  
pp. 4908-4916 ◽  
Author(s):  
Qin Xu ◽  
Yuxuan Zhang ◽  
Xueliang Li ◽  
Jun He ◽  
Jianbo Tan ◽  
...  

Enzyme catalysis-induced aqueous reversible addition–fragmentation chain transfer (RAFT) polymerization was conducted at room temperature for the preparation of epoxy-functionalized triblock copolymer vesicles.


2020 ◽  
Vol 11 (21) ◽  
pp. 3564-3572
Author(s):  
Jing Wan ◽  
Bo Fan ◽  
Yiyi Liu ◽  
Tina Hsia ◽  
Kaiyuan Qin ◽  
...  

The first room temperature synthesis of diblock copolymer nano-objects with different morphologies using ultrasound (990 kHz) initiated reversible addition-fragmentation chain transfer PISA (sono-RAFT-PISA) in aqueous system.


2015 ◽  
Vol 6 (34) ◽  
pp. 6129-6132 ◽  
Author(s):  
Zhenzhong Liu ◽  
Gongjun Zhang ◽  
Wei Lu ◽  
Youju Huang ◽  
Jiawei Zhang ◽  
...  

Reversible addition–fragmentation chain transfer (RAFT) polymerization induced self-assembly (PISA) initiated by UV light is exploited as a new strategy to prepare polymeric nanomicelles at room temperature.


2021 ◽  
Author(s):  
Panagiotis G. Falireas ◽  
Vincent Ladmiral ◽  
Bruno Ameduri

The synthesis of fluorinated dual-responsive block terpolymers via sequential reversible addition–fragmentation chain transfer (RAFT) polymerization is presented.


Polymers ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 1107 ◽  
Author(s):  
Ahmad Joumaa ◽  
Florence Gayet ◽  
Eduardo J. Garcia-Suarez ◽  
Jonas Himmelstrup ◽  
Anders Riisager ◽  
...  

A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 °C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO)2] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.


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