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The two-dimensional (2D) assembly of gold nanoparticles (AuNPs) in a confined geometry is a rare phenomenon that has not been experimentally verified for complex systems. In this study, this process was investigated in detail using two types of block copolymers with hydrophobic and hydrophilic blocks and a series of AuNPs of three different sizes protected by hydrophobic ligands. In aqueous solutions, the selected block copolymers self-assembled into vesicular nanostructures with a hydrophobic domain in the wall, which functions as a confined geometrical space for hydrophobic AuNPs (i.e., it exerts a confinement effect and restricts the movement of AuNPs). Small-angle X-ray scattering studies revealed that AuNPs of different sizes assembled differently in the same confined geometry of the vesicular wall. In addition, optimal conditions for the formation of a regular NP array in the hydrophobic domain were determined. The AuNPs successfully self-assembled into a regular 2D lattice structure, forming a shell around the vesicle, when their size matched the thickness of the hydrophobic domain of the vesicular nanostructure. This study provides guidelines for the fabrication of nanoparticle arrays with controlled structures, which could enhance the functionality of materials and their physical properties.

Conformational control of two-dimensional gold nanoparticle arrays in a confined geometry within a vesicular wall