Amphiphilic linear ternary block copolymers (ABC) were synthesized in three consecutive steps by the reversible additionfragmentation chain transfer (RAFT) method. Using oligo(ethylene oxide) monomethyl ether acrylate, benzyl acrylate, and 1H,1H-perfluorobutyl acrylate monomers, the triblock copolymers consist of a hydrophilic (A), a lipophilic (B), and a fluorophilic (C) block. The block sequence of the triphilic copolymers was varied systematically to provide all possible variations: ABC, ACB, and BAC. All blocks have glass transition temperatures below 0 °C. Self-assembly into spherical micellar aggregates was observed in aqueous solution, where hydrophobic cores undergo local phase separation into various ultrastructures as shown by cryogenic transmission electron microscopy (cryo-TEM). Selective solubilization of substantial quantities of hydrocarbon and fluorocarbon low molar mass compounds by the lipophilic and fluorophilic block, respectively, is demonstrated.

In order to mimic a key functional feature of the transport protein serum albumin that disposes of several different simultaneous binding sites, new ternary linear block copolymers were synthesized. The block copolymers are made of one non‐ionic hydrophilic block based on derivatives of poly(oligoethyleneglycol), and of two mutually immiscible hydrophobic poly(acrylate) blocks, based on hydrocarbon and fluorocarbon esters of acrylic acid, respectively. The polymers self‐organize in aqueous solution to micellar aggregates, which undergo microphase separation within the hydrophobic micellar core. The different aggregate structures were imaged by transmission electron cryo‐microscopy (cryo‐TEM). Depending on the detailed polymer architecture, either core‐shell‐corona micelles, or micelles with a true multicompartment structure were formed, that are capable of selective solubilization.magnified image

An amphiphilic linear ternary block copolymer was synthesised in three consecutive steps via reversible addition-fragmentation chain transfer polymerisation. Oligo(ethylene glycol) monomethyl ether acrylate was engaged as a hydrophilic building block, while benzyl acrylate and 3-tris(trimethylsiloxy)silyl propyl acrylate served as hydrophobic building blocks. The resulting "triphilic" copolymer consists thus of a hydrophilic (A) and two mutually incompatible "soft" hydrophobic blocks, namely, a lipophilic (B) and a silicone-based (C) block, with all blocks having glass transition temperatures well below 0 °C. The triphilic copolymer self-assembles into spherical multicompartment micellar aggregates in aqueous solution, where the two hydrophobic blocks undergo local phase separation into various ultrastructures as evidenced by cryogenic transmission electron microscopy. Thus, a silicone-based polymer block can replace the hitherto typically employed fluorocarbon-based hydrophobic blocks in triphilic block copolymers for inducing multicompartmentalisation

Polymer-peptide conjugates are a promising class of compounds, where polymers can be used to overcome some of the limitations associated with peptides intended for therapeutic and/or diagnostic applications. Linear polymers such as poly(ethylene glycol) can be conjugated through terminal moieties and have therefore limited loading capacities. In this research, functionalised linear poly(ethylene glycol)s are utilised for peptide conjugation, to increase their potential loading capacities. These poly(ethylene glycol) derivatives are conjugated to peptide sequences containing representative side-chain functionalised amino acids, using different conjugation chemistries, including copper-catalysed azide-alkyne cycloaddition, amide coupling and thiol-ene reactions. Conjugation of a sequence containing the RGD motif to poly(allyl glycidyl ether) by the thiol-ene reaction, provided a conjugate which could be used in platelet adhesion studies.