LAUSR

Gold nanoparticles (AuNPs) exhibit strong fluorescent and electromagnetic properties, which can be enhanced upon clustering and used in therapeutic, imaging, and sensing applications. A combination of gold nanoparticles with lipid nanodiscs can be attractive for AuNP self-assembly and useful in biomedical applications. Using molecular dynamics simulations we show that lipid nanodiscs can serve as templates for AuNP clustering into rings and string-like structures. We demonstrate that equilibrium encapsulation of 1 nm hydrophobically modified AuNPs into lipid nanodiscs composed of a mixture of dipalmitoylphosphatidylcholine (DPPC) and dihexanoylphosphatidylcholine (DHPC) lipids occurs at the rim and results in formation of a ring of gold. The interior of the nanodisc is inaccessible to AuNPs due to the DPPC liquid crystalline order. With temperature increase the lipid order diminishes, initiating the nanodisc transformation into a vesicle, upon which encapsulated AuNPs cluster into a close-packed string or nanoring, thereby stalling the vesiculation process at a "round vase" or cup-like stage depending on the AuNP concentration. In contrast, encapsulation of AuNPs by an equilibrium lipid vesicle results in its deformation with randomly clustered AuNPs, in agreement with experimental observations. We characterize the AuNP cluster size and surface-to-surface pair distribution, both of which impact the AuNP luminescent properties. We investigate the effect of alkane tether length on the nanodisc stability and AuNP clustering inside the nanodiscs and vesicles. Our results show that lipid nanodiscs can enhance gold cluster formation, which can be further exploited in imaging applications.