Abstract
A prevalent strategy for synthesizing patchy nanoparticles is through the self-assembly of triblock terpolymers in selective solvents. Since the thermodynamic and kinetic factors that govern the morphology of the particles produced in this way are not fully understood, this strategy usually demands trial-and-error methodologies. We investigate the fundamental mechanisms that produce multiple types of patchy nanoparticles and identify the conditions needed to program the shapes of the nanoparticles and predict their assembly. Our findings demonstrate that particle morphology can be described in a generic fashion by accounting for the energetic balance between the conformation of the polymer coils and the formation of interfaces. This allows us to forecast the synthesis of patchy nanoparticles for systems with different triblock terpolymers and solvents. Since the shape, size, and distribution of the patches influence the growth of larger microscale structures, we construct a library of elemental nanoparticles, or building blocks, suitable for the study of hierarchically larger self-assembled aggregates and useful for streamlining the design of functional materials. Our results provide new insights into the intriguing mechanisms that determine the morphology of soft nanoscale objects, whether synthetic or naturally occurring.
Highlights
The hierarchical self-assembly of ABC triblock terpolymers in solution is a successful bottom-up methodology for constructing functional materials with nanoscale resolution, including decorated nanoparticles with precisely tailored structural motifs.1–3 In this methodology, the self-assembly process is mediated by polymer–solvent phase separation, which induces the formation of nanoscopic aggregates such as micelles
A description of the experimental conditions is included in the Electronic supplementary information (ESI),† and the characteristics of the polymers are provided in Tables 1 and 2.† The range of parameters we consider significantly exceeds the corresponding range of experimental and computational conditions reported to date
The morphologies at each stage account for memory effects at the previous stage and are consistent with metastable structures, that cannot be obtained from direct solubilization of the triblock copolymer, as we show in Fig. 7 of the ESI.†
Summary
The hierarchical self-assembly of ABC triblock terpolymers in solution is a successful bottom-up methodology for constructing functional materials with nanoscale resolution, including decorated nanoparticles with precisely tailored structural motifs. In this methodology, the self-assembly process is mediated by polymer–solvent phase separation, which induces the formation of nanoscopic aggregates such as micelles. The second term of [4] is purely entropic and can be thought as the constrained localization of the joints linking blocks A with B, and B with C in the interfacial regions This entropic loss can be expressed in terms of their configurational volume, defined as the ratio between the volume available to the joints in the core–shell (and shell–corona) interfaces and the total volume of the nanoparticle Vnp. Typically the formation of the patchy nanoparticles involves a multistage solubilization approach, where the selectivity of the solvent is changed to guide the system towards local energy minima.. To examine the influence of composition on the conformational and interfacial free energy of the assembled nanoparticles, it is necessary to determine the radii of gyration and the end-to-end distances of the different blocks in the polymer coil and the interfacial areas between the core, shell, corona,. A description of the experimental conditions is included in the ESI,† and the characteristics of the polymers are provided in Tables 1 and 2.† The range of parameters we consider significantly exceeds the corresponding range of experimental and computational conditions reported to date (see ESI Fig. 1†).
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