Amphiphilic monomer units contain both hydrophobic and hydrophilic groups. They are characterized by affinity and antagonism simultaneously to both polar and nonpolar solvents, tend to settle themselves at solvent interfaces rather than in the bulk of the solvent and, thus, possess effective surface activity. For this reason, in selective solvents the macromolecules with amphiphilic monomer units self-assemble to complex morphologies with enlarged surface which could be similar to those formed by low-molecular surfactants, lipids and amphiphilic diblock-copolymers. In literature, macromolecules with amphiphilic monomer units are also referred to as polymer amphiphiles. When they consist of identical amphiphilic monomer units, they are called amphiphilic homopolymers. The article aims to review the macromolecular self-assembly driven by amphiphilicity of monomer units containing both solvophobic and solvophilic (hydrophobic and hydrophilic) groups. The particular attention is paid to the situation when such macromolecules assemble into the hollow and vesicle-like particles being especially prospective for different applications. We present the current state of experimental, computational and analytical research in this field and reveal the conditions favoring the formation of vesicles with thin (mono-, bi- or multilayer) membranes.
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