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Homopolymer self-assembly has attracted much attention in polymer science and soft nanomaterials due to the fuzzy boundary between hydrophilic and hydrophobic moieties of homopolymers, which brings new insights into understanding the self-assembly behaviors of amphiphilic polymers and the structural features of their corresponding assemblies. The coexisting hydrophilic and hydrophobic segments in homopolymer assemblies can promote their applications in drug delivery, cancer therapy, protein detection, catalysis, water remediation, etc. This review seeks to provide a comprehensive view on the homopolymer self-assembly from the aspects of design principles, driving forces, morphology control, and potential applications. First, various driving forces of homopolymer self-assembly are summarized, including the hydrophobic effect, electrostatic interactions, hydrogen bonding, π–π stacking and crystallization. Subsequently, two different strategies for designing homopolymer assemblies are introduced: the amphiphilic repeating unit strategy and the terminal group strategy. Furthermore, we demonstrate the structural features and morphology control of homopolymer assemblies on the basis of the fuzzy boundary between the hydrophilic and the hydrophobic moieties of amphiphilic homopolymers. Finally, the potential applications of homopolymer self-assembly in biological, environmental, and energy fields, as well as the future perspectives, are discussed.
Li et al. (Fri,) studied this question.