Communication Macromolecular Rapid Communications wileyonlinelibrary.com 813 DOI: 10.1002/marc.201300889 1. Introduction The self-directed assembly of amphiphilic surfactants and copolymers in a selective solvent at, or above, a crit- ical temperature and concentration is well documented and results in the formation of nanosized particles with an impressive range of solution morphologies including micelles, cylinders, and vesicles. [1] In the case of polymers, this has involved, by necessity, the synthesis of suitable amphiphilic block copolymers that may have AB-, ABA-, or ABC-type topologies with suitable molar compositions. As a consequence of the required block architecture, an appro- priate polymerization technique must be employed that allows for the control of copolymer molecular weight, composition (hydrophilic–hydrophobic balance), and dis- persity, since each of these features is known to play a role in the self-assembly process and on the final solu- tion morphology formed. [2] Fortunately, the discovery and development of the suite of reversible deactivation radical polymerizations (RDRPs) now allows for the direct syn- thesis of almost any conceivable type of block copolymer with respect to functionality, composition, topology, and overall architecture. In homopolymers, or copolymers, of sufficiently low molecular weight, the nature of the end groups becomes an important consideration with respect to the bulk and solution properties since these groups can repre- sent an overall significant weight/molar fraction of the polymeric material. [3] For example, Furyk et al. [4] have evaluated the effect of end groups on the lower critical Well-defined poly[pentafluorophenyl (meth)acrylate] (PPFP(M)A) homopolymers are pre- pared by RAFT radical polymerization mediated by a novel chain transfer agent containing two cholesteryl groups in the R-group fragment. Subsequent reaction with a series of small-molecule amines in the presence of an appropriate Michael acceptor for ω-group end-capping yields a library of novel bischolesteryl functional hydrophilic homopolymers. Two examples of statistical copolymers are also prepared including a biologically relevant sugar derivative. Specific examples of these homopolymers are examined with respect to their ability to self assemble in aqueous media—a process driven entirely by the cholesteryl end groups. In all instances evaluated, and under the preparation conditions examined, the homopolymers aggregate clearly forming polymersomes spanning an impressive size range. Novel α, α-Bischolesteryl Functional (Co)Polymers: RAFT Radical Polymerization Synthesis and Preliminary Solution Characterization Peter J. Roth, Thomas P. Davis, Andrew B. Lowe* Dr. P. J. Roth, Prof. A. B. Lowe Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, University of New South Wales, Kensington, Sydney, NSW 2052, Australia E-mail: a.lowe@unsw.edu.au Prof. T. P. Davis Monash Institute of Pharmaceutical Sciences, Monash University, Parkville, VIC 3052, Australia Prof. T. P. Davis Department of Chemistry, University of Warwick, Gibbet Hill, Coventry, CV4 7AL, UK Macromol. Rapid Commun. 2014, 35, 813−820 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim