Multicompartment micelles are an intriguing class of self-assembled aggregates with subdivided solvophobic cores. They have been subject to extensive research in part due to their unique morphological and sequestration properties as a result of multiple distinct chemical environments being in close proximity within one nanostructure. Multicompartment micelles hold potential for use in various applications that include the therapeutic delivery of multiple incompatible drug payloads. The present Perspective reviews recent achievements in strategies for the synthesis, self-assembly, and morphological control of multicompartment micelles and highlights future challenges and potential applications.
A quaternary amine end functionalised diblock copolymer (PtBuA-b-PNIPAM) has been synthesised using RAFT polymerisation and shown to undergo a thermally induced morphology transition from micelles to vesicles, as evidenced by TEM, AFM, SLS and DLS analyses.
An SCS "pincer"-based nitroxide-mediated polymerization (NMP) initiator has been synthesized and utilized to polymerize tert-butyl acrylate ( ( t )BuA), affording polymers with control over molecular weight and polydispersity. (1)H NMR spectroscopy indicates that the sulfur end group remains intact after deprotection of the P ( t )BuA segment to yield a poly(acrylic acid) segment. The hydrophilic polymer-tethered SCS ligand has been demonstrated to bind to palladium(II), as characterized by a distinctive Pd-C shift in the (13)C NMR spectrum and a diagnostic metal-to-ligand charge-transfer band in the UV-vis spectrum. A pyridine-functionalized NMP initiator has also been synthesized and used to initiate the NMP of styrene with good control and end group fidelity. The binding of these two chain end ligand-functionalized polymers to form an amphiphilic metallosupramolecular diblock copolymer is facile, as indicated through extended (1)H and (13)C NMR studies. The self-assembly of this diblock into well-defined, monodisperse, noncovalently connected micelles (NCCMs) is reported and has been characterized by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. The NCCMs were selectively stabilized throughout the shell layer to produce stable noncovalently connected nanoparticles, resulting in a distinctive reduction in the solution hydrodynamic radius and zeta potential compared to those of the precursor micelle. The hydrophobic core domain was then readily removed via dialysis at low pH to afford a hollow polymeric nanocage with well-defined interior functionality. A significant increase in the solution hydrodynamic radius and shape by AFM analysis was observed upon removal of the core, and the hydrophilic nanocages were shown to be ineffective in the sequestration of hydrophobic dye molecules relative to the parent nanoparticle.
The design and synthesis of a tuneable and reversible morphology switching copolymer system is reported. The kinetics of the transition under a range of conditions has been explored, as has the stabilization of the resultant structures.
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