Amphiphilic fluorous random copolymer self‐assembly for encapsulation of a fluorinated agrochemical

Abstract

This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.ABSTRACT: Amphiphilic self-folding random copolymers exhibit different solution behaviors depending on the identity of the hydrophobic/hydrophilic units. Herein, it is demonstrated that changing the hydrophilic unit from poly(ethylene glycol) to the sugar trehalose causes increased discrepancy in the polarity difference with a fluorinated hydrophobic segment and changes the aggregation state of the polymer in water. The PEG-fluorinated and trehalose/PEG-fluorinated amphiphilic random copolymers were the most efficient at encapsulating a fluorinated agrochemical. The small-molecule agrochemical exerts a strong influence on the selfassembly of the polymers, demonstrating that fluorous interactions result in not only intramolecular self-folding behavior but also intermolecular polymer association to form well-defined nanoparticles.

Partially Fluorinated Copolymers as Oxygen Sensitive 19F MRI Agents

“…This is quantitatively supported by as maller solvent-accessible surface area for the fluorine atoms (Figure S6 B), increased positional ordering (Figure S6 C), and a smaller radius of gyration (R g ), hydrodynamic radius (R h ), and (Figure S7 D) for the 40 %N onaFOEAc ase relative to the 10 %N onaFOEAc ase. The culmination of these results are consistent with the single-chain folding of amphiphilic random copolymers in water,w hich ultimately resultsi nt he formation of unimerm icelles [67][68][69][70] and is similar to that characterized by Sawamoto [70][71][72][73] and co-workers. PEGA homopolymers with a perfluoropolyether (PFPE) chain-end also demonstrate analogous behavior.…”

Behavior of Protein-Inspired Synthetic Random Heteropolymers

“…SCNPs are of paramount interest for their potential applications leveraging antibacterial properties, performing chemical encapsulation, as drug delivery vehicles, and as enzyme mimics incorporating catalytic centers. 5,[41][42][43][44][45][46][47] Nevertheless, SCNP research, like many of the theoretical studies preceding it, has delved mostly into twocomponent RHP systems. While theory work often studied systems of hydrophobic and hydrophilic units of uniform size, SCNP experimental work naturally contains a greater variety of chemical and steric heterogeneity, even when limited to only two monomer species.…”

“…Several popular methods in SCNP literature rely on methacrylate-based monomer building blocks due to the variety of available synthesis and functionalization methods, as well as inherent amphiphilicity of these constituents. 5,40,42,[48][49][50][51][52] These methacrylate-based heteropolymers have been used to demonstrate the dramatic effect side chain chemistry can have on polymer collapse and resulting nanoparticle behavior, as revealed through common experimental SCNP analysis techniques. 48,53 Inspired by the recent functionalities observed in RHPs, [6][7][8] here we study the molecular structure and dynamics of complex RHPs containing up to four different monomers using molecular dynamics as well as X-ray scattering.…”

The Effect of Poly(ethylene glycol) (PEG) Length on the Wettability and Surface Chemistry of PEG-Fluoroalkyl-Modified Polystyrene Diblock Copolymers and Their Two-Layer Films with Elastomer Matrix

“…In particular, amphiphilic surface-active additives, composed of polysiloxane and/or fluoropolymer chains as the hydrophobic components, and poly(ethylene glycol) (PEG) chains as the hydrophilic components, have been investigated in different fields of nanotechnology [ 3 , 34 , 36 , 37 , 38 , 39 ]. The self-assembly of such amphiphilic copolymers in fact is also possible in the bulk copolymer itself [ 40 , 41 ], or when dissolved in a selective solvent, determining a variety of nanostructures ranging from single chain nanoparticles to large aggregates [ 42 , 43 , 44 , 45 , 46 ]. A surface reconstruction process of amphiphilic polymers generally involves an increase in hydrophilicity of the film surface after immersion in polar solvents, notably water, and a reversible restoration of the surface hydrophobicity after contact with air [ 4 , 17 ].…”