Entropy-driven pattern formation of hybrid vesicular assemblies made from molecular and nanoparticle amphiphiles.
Although an analogy has been drawn between them, organic molecular amphiphiles (MAMs) and inorganic nanoparticle (NP) amphiphiles (NPAMs) are significantly different in dimension, geometry, and composition as well as their assembly behavior. Their concurrent assembly can synergetically combine the inherent properties of both building blocks, thus leading to new hybrid materials with increasing complexity and functionality. Here we present a new strategy to fabricate hybrid vesicles with well-defined shape, morphology, and surface pattern by coassembling MAMs of block copolymers (BCPs) and NPAMs comprising inorganic NPs tethered with amphiphilic BCPs. The assembly of binary mixtures generated unique hybrid Janus-like vesicles with different shapes, patchy vesicles, and heterogeneous vesicles. Our experimental and computational studies indicate that the different nanostructures arise from the delicate interplay between the dimension mismatch of the two types of amphiphiles, the entanglement of polymer chains, and the mobility of NPAMs. In addition, the entropic attraction between NPAMs plays a dominant role in controlling the lateral phase separation of the two types of amphiphiles in the membranes. The ability to utilize multiple distinct amphiphiles to construct discrete assemblies represents a promising step in the self-assembly of structurally complex functional materials.
Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
Yijing
Y
Liu
Yanchun
Y
Li
Jie
J
He
Kaleb John
KJ
Duelge
Zhongyuan
Z
Lu
Zhihong
Z
Nie
D002462:Cell Membrane / Q000737:chemistry; D019277:Entropy; D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D046529:Microscopy, Electron, Transmission; D008954:Models, Biological; D013499:Surface Properties; D013501:Surface-Active Agents / Q000737:chemistry*; D022161:Transport Vesicles / Q000737:chemistry*
D013501:Surface-Active Agents; D006046:Gold