Flow Chemistry Controls Both Self-Assembly and the Entrapped Oscillatory Cargo in Belousov-Zhabotinsky Driven Polymerization-Induced Self-Assembly

2019 ◽  
Author(s):  
Liman Hou ◽  
Marta Dueñas-Diez ◽  
Rohit Srivastava ◽  
Juan Perez-Mercader

<p></p><p>Belousov-Zhabotinsky (B-Z) reaction driven polymerization-induced self-assembly (PISA), or B-Z PISA, is a novel method for the autonomous one-pot synthesis of polymer vesicles from a macroCTA (macro chain transfer agent) and monomer solution (“soup”) containing the above and the BZ reaction components. In it, the polymerization is driven (and controlled) by periodically generated radicals generated in the oscillations of the B-Z reaction. These are inhibitor/activator radicals for the polymerization. Until now B-Z PISA has only been carried out in batch reactors. In this manuscript we present the results of running the system using a continuously stirred tank reactor (CSTR) configuration which offers some interesting advantages.Indeed, by controlling the CSTR parameters we achieve reproducible and simultaneous control of the PISA process and of the properties of the oscillatory cargo encapsulated in the resulting vesicles. Furthermore, the use of flow chemistry enables a more precise morphology control and chemical cargo tuning. Finally, in the context of biomimetic applications a CSTR operation mimics more closely the open non-equilibrium conditions of living systems and their surrounding environments.</p><p></p>

2019 ◽  
Author(s):  
Liman Hou ◽  
Marta Dueñas-Diez ◽  
Rohit Srivastava ◽  
Juan Perez-Mercader

<p></p><p>Belousov-Zhabotinsky (B-Z) reaction driven polymerization-induced self-assembly (PISA), or B-Z PISA, is a novel method for the autonomous one-pot synthesis of polymer vesicles from a macroCTA (macro chain transfer agent) and monomer solution (“soup”) containing the above and the BZ reaction components. In it, the polymerization is driven (and controlled) by periodically generated radicals generated in the oscillations of the B-Z reaction. These are inhibitor/activator radicals for the polymerization. Until now B-Z PISA has only been carried out in batch reactors. In this manuscript we present the results of running the system using a continuously stirred tank reactor (CSTR) configuration which offers some interesting advantages.Indeed, by controlling the CSTR parameters we achieve reproducible and simultaneous control of the PISA process and of the properties of the oscillatory cargo encapsulated in the resulting vesicles. Furthermore, the use of flow chemistry enables a more precise morphology control and chemical cargo tuning. Finally, in the context of biomimetic applications a CSTR operation mimics more closely the open non-equilibrium conditions of living systems and their surrounding environments.</p><p></p>


2019 ◽  
Vol 2 (1) ◽  
Author(s):  
Liman Hou ◽  
Marta Dueñas-Díez ◽  
Rohit Srivastava ◽  
Juan Pérez-Mercader

AbstractAmphiphilic block-copolymer vesicles are increasingly used for medical and chemical applications, and a novel method for their transient self-assembly orchestrated by periodically generated radicals during the oscillatory Belousov-Zhabotinsky (BZ) reaction was recently developed. Here we report how combining this one pot polymerization-induced self-assembly (PISA) method with a continuously stirred tank reactor (CSTR) strategy allows for continuous and reproducible control of both the PISA process and the chemical features (e.g. the radical generation and oscillation) of the entrapped cargo. By appropriately tuning the residence time (τ), target degree of polymerization (DP) and the BZ reactants, intermediate self-assembly structures are also obtained (micelles, worms and nano-sized vesicles). Simultaneously, the chemical properties of the cargo at encapsulation are known and tunable, a key advantage over batch operation. Finally, we also show that BZ-driven polymerization in CSTR additionally supports more non-periodic dynamics such as bursting.


Soft Matter ◽  
2021 ◽  
Vol 17 (15) ◽  
pp. 4011-4018
Author(s):  
E. Poros-Tarcali ◽  
J. Perez-Mercader

pH oscillatory chemistry-driven generation of polymer vesicles from homogenous medium and their pH-responsive self-assembly in a one-pot reaction network.


2019 ◽  
Vol 64 (1) ◽  
pp. 1-8
Author(s):  
Balázs Szabó ◽  
Kiara Szakter ◽  
Angelika Thurner ◽  
Ferenc Faigl ◽  
János Éles ◽  
...  

A novel method for synthesis of tricyclic benzimidazole derivatives by using continuous flow reactor is reported. Disadvantages of the well-known batch methods have been avoided utilizing the flow chemistry technology. Beside the one pot reductive cyclization using H-Cube Pro®, the dehydration step was also optimized producing the desired lactam compounds. Then the acylation was optimized under microwave conditions and that reaction was also integrated into the flow system using an Asia heater module. This acylation dramatically reduced the reaction time under continuous-flow conditions, with a residence time of 30 min.


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.


ChemInform ◽  
2005 ◽  
Vol 36 (41) ◽  
Author(s):  
Peyman Salehi ◽  
Minoo Dabiri ◽  
Mohammad Ali Zolfigol ◽  
Mostafa Baghbanzadeh
Keyword(s):  
One Pot ◽  

2015 ◽  
Vol 22 (2) ◽  
pp. 486-490 ◽  
Author(s):  
Joseph P. Byrne ◽  
Miguel Martínez-Calvo ◽  
Robert D. Peacock ◽  
Thorfinnur Gunnlaugsson

2016 ◽  
Vol 8 (43) ◽  
pp. 7774-7779 ◽  
Author(s):  
Hee-Jin Jeong ◽  
Tomoki Kojima ◽  
Jinhua Dong ◽  
Hiroyuki Ohashi ◽  
Hiroshi Ueda

A novel method to construct a fluorescent biosensor Quenchbody in one pot is devised using an optimized fluorescence-labeled antibody binding protein and human/mouse antibody Fab fragment.


RSC Advances ◽  
2015 ◽  
Vol 5 (44) ◽  
pp. 34942-34948 ◽  
Author(s):  
Sayantan Mazumdar ◽  
Aninda J. Bhattacharyya

An unprecedented morphology of a titanium dioxide (TiO2) and cadmium sulfide (CdS) self-assembly obtained using a ‘truly’ one-pot and highly cost effective method with a multi-gram scale yield is reported here.


2021 ◽  
Author(s):  
Valene Wang ◽  
Jiwon Kim ◽  
Junyoung Kim ◽  
Seul Woo Lee ◽  
Kyoung Taek Kim

The shape control of nanostructures formed by the solution self-assembly of block copolymers is of significance for drug delivery. In particular, site-specific perturbation resulting in the conformational change of the...


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