We report how to control the self-assembly of magnetic nanoparticles and a prototypical amphiphilic block-copolymer composed of poly(acrylic acid) and polystyrene (PAA-b-PS). Three distinct structures were obtained by controlling the solvent-nanoparticle and polymer-nanoparticle interactions: (1) polymersomes densely packed with nanoparticles (magneto-polymersomes), (2) core-shell type polymer assemblies where nanoparticles are radially arranged at the interface between the polymer core and the shell (magneto-core shell), and (3) polymer micelles where nanoparticles are homogeneously incorporated (magneto-micelles). Importantly, we show that the incorporation of nanoparticles drastically affects the self-assembly structure of block-copolymers by modifying the relative volume ratio between the hydrophobic block and the hydrophilic block. As a consequence, the self-assembly of micelle-forming block-copolymers typically produces magneto-polymersomes instead of magneto-micelles. On the other hand, vesicle-forming polymers tend to form magneto-micelles due to the solubilization of nanoparticles in polymer assemblies. The nanoparticle-polymer interaction also controls the nanoparticle arrangement in the polymer matrix. In N,N-dimethylformamide (DMF) where PS is not well-solvated, nanoparticles segregate from PS and form unique radial assemblies. In tetrahydrofuran (THF), which is a good solvent for both nanoparticles and PS, nanoparticles are homogeneously distributed in the polymer matrix. Furthermore, we demonstrated that the morphology of nanoparticle-encapsulating polymer assemblies significantly affects their magnetic relaxation properties, emphasizing the importance of the self-assembly structure and nanoparticle arrangement as well as the size of the assemblies.
Synthetic polymer membranes, critical to diverse energy-efficient separations, are subject to permeability-selectivity trade-offs that decrease their overall efficacy. These trade-offs are due to structural variations (e.g., broad pore size distributions) in both nonporous membranes used for Angstrom-scale separations and porous membranes used for nano to micron-scale separations. Biological membranes utilize well-defined Angstrom-scale pores to provide exceptional transport properties and can be used as inspiration to overcome this trade-off. Here, we present a comprehensive demonstration of such a bioinspired approach based on pillar[5]arene artificial water channels, resulting in artificial water channel-based block copolymer membranes. These membranes have a sharp selectivity profile with a molecular weight cutoff of ~ 500 Da, a size range challenging to achieve with current membranes, while achieving a large improvement in permeability (~65 L m−2 h−1 bar−1 compared with 4–7 L m−2 h−1 bar−1) over similarly rated commercial membranes.
We report the size-controlled self-assembly of polymersomes through the cooperative self-assembly of nanoparticles and amphiphilic polymers. Polymersomes densely packed with magnetic nanoparticles in the polymersome membrane (magneto-polymersome) were fabricated with a series of different sized iron oxide nanoparticles. The distribution of nanoparticles in a polymersome membrane was size-dependent; while small nanoparticles were dispersed in a polymer bilayer, large particles formed well-ordered superstructure at the interface between the inner and outer layer of a bilayer membrane. The yield of magneto-polymersomes increased with increasing the diameter of incorporated nanoparticles. Moreover, the size of polymersomes was effectively controlled by varying the size of incorporated nanoparticles. This size-dependent self-assembly was attributed to the polymer chain entropy effect and the size-dependent localization of nanoparticles in polymersome bilayers. The transverse relaxation rates (r2) of magneto-polymersomes increased with increasing the nanoparticle diameter and decreasing the size of polymersomes, reaching 555 ± 24 s−1mM−1 for 241 ± 16 nm polymersomes, which is the highest value reported to date for superparamagnetic iron oxide nanoparticles.
Gold nanoshells covered with sharp rods called “spiky gold nanoshells” are synthesized by employing a silver-assisted seed-growth method for heterogeneous nanoparticle syntheses at polymer/water interfaces. It is found that silver ions in the growth solution play an important role in forming uniform gold shells as well as regulating the surface morphology. The optical properties of spiky gold nanoshells are investigated by single-particle scattering measurements, single-particle surface-enhanced Raman scattering measurements, and finite-difference time-domain modeling. The scattering intensities from isolated spiky nanoshells are significantly enhanced compared to those of conventional smooth shells. Moreover, due to the abundant hot spots on spiky nanoshells, the SERS signal is readily observed from single spiky shells with a very small intensity variation (35%), whereas there is no detectable signal from isolated smooth shells. These results demonstrate that our synthetic method provides a straightforward way to organize metal nanoparticles into well-defined assemblies with enhanced scattering properties.
Here, we report a simple method to control the location of nanoparticles in colloidal block-copolymer assemblies by using nanoparticles modified with mixed surface ligands. The binary self-assembly of amphiphilic polymers of polystyrene-b-poly(acrylic acid) (PS-b-PAA) and gold nanoparticles (AuNPs) modified with a hydrophobic ligand, dodecanethiol (DT), led to polymer micelles with nanoparticles segregated in the core of polymer micelles. On the other hand, AuNPs modified with mixed ligands of mercaptoundecanol (MUL) and DT were distributed at the PS−PAA interface, reducing the interfacial energy between the two polymers. This result was in good agreement with the prediction by the surface energy calculations. We also showed that the AuNPs with mixed ligands can decorate preformed polymer assemblies by the interfacial self-assembly. Furthermore, we demonstrated the compartmentalization of two different types of nanoparticles in colloidal polymer assemblies based on the strategy.
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