Entropic factors and structural motifs of triblock-terpolymer-based patchy nanoparticles

N Moreno and B Sutisna and E Fried, NANOSCALE, 12, 22059-22069 (2020).

DOI: 10.1039/d0nr06192a

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.

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