In recent years,
the self-assembly of copolymer micelles has become
an appealing frontier of supramolecular chemistry as a strategy to
construct superstructures with multiple levels of complexity. The
assembly of copolymer micelles is a form of higher-level self-assembly
occurring at the nanoscale level where the building blocks are preassembled
micelles. Compared to one-step hierarchical self-assembly, this assembly
strategy is superior for manipulating multilevel architectures because
the structures of the building blocks and higher-order hierarchies
can be regulated separately in the first and higher-level assembly,
respectively. However, despite the substantial advances in the self-assembly
of copolymer micelles in recent years, universal laws have not been
comprehensively summarized. This review article aims to provide an
overview of the current progress and developing prospects of the self-assembly
of copolymer micelles. In particular, the significant role of theoretical
simulations in revealing the mechanism of copolymer micelle self-assembly
is discussed.
A theoretical approach combining self-consistent-field theory (SCFT) for fluids and density
functional theory (DFT) for particles was applied to investigate the self-assembly behavior of amphiphilic diblock
copolymer/nanoparticle mixture in dilute solution. Two kinds of hydrophobic nanoparticles are studied: one is
that the particles are selective to hydrophobic blocks but are incompatible with hydrophilic blocks, and the other
is that the particles are nonselective to hydrophobic and hydrophilic blocks. For both cases, the self-association
of amphiphilic block copolymer/nanoparticle mixture is observed, and the nanoparticles are spatially organized
in the clusters. The aggregate morphologies can be tuned by the particle radius and particle volume fraction. For
the selective particles, the aggregate morphologies of amphiphilic block copolymer/nanoparticle mixture can
experience a transition from vesicles to mixture of circlelike and rod micelles as the particle radius and/or particle
volume fraction increase. For the nonselective nanoparticles, the large compound micelles are produced instead
of the vesicles. The large compound micelles transform to the mixture of large compound micelles and circlelike
micelles with an increase in particle volume fraction and/or radius. The distribution of nanoparticles in the clusters
is also affected by the particle radius and volume fraction. For both cases, when the values of nanoparticle radius
and/or volume fraction are small, the nanoparticles are almost uniformly distributed in the cores of micelles.
However, the particles tend to localize near the interfaces between the core and shell with increasing particle
volume fraction and/or radius.
The effect of chain conformation change on the self-assembly behavior of poly(gamma-benzyl- l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) was studied both experimentally by transmission electron microscopy, laser light scattering, and circular dichroism and computationally using molecular dynamics (MD) simulation. It was found that, by introducing trifluoroacetic acid to the PBLG-b-PEG solution, the conformation of the PBLG chain transforms from alpha-helix to random coil, which results in a change of the micelle structures formed by PBLG-b-PEG from rod to sphere. Meanwhile, the MD simulations were performed by using Brownian dynamics on the self-assembly behavior of model AB-type diblock copolymers with various chain rigidities of the A-block. The results show that, by decreasing the fraction of rigid chain conformation of the A-block, which corresponds to the helix-coil transition in the PBLG-b-PEG sample, the aggregate structure transforms from rod to sphere. The MD simulations also provide chain packing information in the micelles. On the basis of both experimental and MD simulation results, the mechanism regarding the effect of the conformation change of the polypeptide block copolymer on its self-association behavior is suggested.
Using real-space self-consistent field theory, we explored hierarchical microstructures self-assembled from A(BC)
n
multiblock copolymers. The multiblock copolymers were classified into two types in terms of relative magnitude of A/B and A/C interaction strengths: one is that χAB
N is less than or equal to χAC
N, and the other is that χAB
N is greater than χAC
N. For both cases, the multiblock copolymers can self-assemble into hierarchically ordered microstructures with two different length scales. For χAB
N ≤ χAC
N, various hierarchical microstructures, such as cylinders-in-lamellae∥, lamellae-in-lamella∥, cylinders-in-cylinder∥, and spheres-in-sphere∥, were observed. In these microphases, the small-length-scale structures and the large-length-scale structures are packed in the doubly parallel forms. It was found the number of internal small-length-scale structures can be tailored by tuning the number of BC block and the interaction strength between A and BC blocks. For χAB
N > χAC
N, in addition to the parallel packed hierarchical structures, the multiblock copolymers can self-organize into perpendicular packed hierarchical structures, in which the structures with small periods are arranged perpendicular to structures with large periods. These perpendicular packed hierarchical structures were found to be only stable at higher value of χBC
N.
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