Visible Light-Mediated Polymerization-Induced Self-Assembly Using Continuous Flow Reactors

Abstract

We present the synthesis of polymeric nanoparticles of targeted morphology in a continuous process via visible light-mediated aqueous RAFT polymerization-induced self-assembly (PISA). A trithiocarbonate-derived poly­(ethylene glycol) (PEG) macroRAFT was activated in the presence of hydroxypropyl methacrylate (HPMA) at 37 °C under blue light irradiation (460 nm), leading to the formation of PEG-b-P­(HPMA) nanoparticles. The method is attractive in its simplicityspheres, worms, and vesicles can easily be obtained in a continuous fashion with higher control in comparison to conventional batch procedures. This allows for more accurate production of particle morphologies and scalable synthesis of these nano-objects. The versatility of this process was demonstrated by the in situ encapsulation of an active compound.

Flow chemistry controls self-assembly and cargo in Belousov-Zhabotinsky driven polymerization-induced self-assembly

“…2 in the Supporting Information. Conversion dynamic trends for three different residence times (40,90, and 120 min), BZ 0.2 mM Ru-catalyst recipe, and monomer/RAFT ratio of concentration of 400 are shown in Fig. 3c.…”

“…Thus, coupling BZ-PISA with the CSTR operation of BZ holds great potential for achieving better control and consistency of both the self-assembled vesicles and their encapsulated cargo. Interest in running PISA in continuous reactors is growing rapidly [38][39][40][41][42][43][44][45] with the focus placed on plug-flow reactors and their variants such as slug flow 45 , since such mode of operation leads to the narrowest residence time distributions, and with it to the tightest control of the final polymer length distribution and self-assembled objects. However, a plug-flow reactor is not adequate for our purpose because when BZ is run in plug flow, it results in stationary space-periodic structures ("waves") 46 with constant forcing at the inflow and to traveling space-periodic waves with periodic forcing at the inflow 47 , and our focus is on encapsulating temporal-periodic oscillations and not spaceperiodic oscillations.…”

Tailoring polymer dispersity and shape of molecular weight distributions: methods and applications

“…), the possibility of block formation where the dispersity of both blocks can be controlled and the broader scope of monomers compared to anionic polymerisation. 50 There are challenges however, as the ow process cannot easily be adapted to the synthesis of polymer brushes (material whereby polymer chains are tethered to a surface) or other complex polymer architectures and the MWDs produced are typically bimodal or multimodal as they are in all polymer blending approaches. It should also be noted that by tuning the residence time, an increase of the dispersity values can be achieved although the breadth of the MWDs is more limited when compared to mixing.…”

Interpolymer association of amphiphilic diblock copolymers bearing pendant siloxane and phosphorylcholine groups

“…The spherical objects with R TEM = about 36 nm were also observed in PMPC 120 -PTSM 68 , which may be small vesicles. 33 We observed spherical objects with various sizes for PMPC 20 -PTSM 76 (m/n = 0.3) during the TEM observation. The average R TEM value for the spherical objects was approximately 95 nm.…”