A synthetic strategy branched polymer building blocks that allow the rapid construction of patchy nanoparticles is presented. Hyperbranched polydendrons with mixtures of PEG and thiol-functional dendrons nanoprecipitate to form isolated zones that are imaged with gold nanoparticles.

Gold nanoparticles with variable hydrophobicity have been prepared in three different size regimes following established methods. The control of hydrophobicity was achieved by complexation of the 18-crown-6-CH-thiolate ligand shell with potassium ions. Potassium dependent phase transfer of these particles from dispersion in water to chloroform was demonstrated, and the equilibrium partitioning of the particles in water-chloroform liquid/liquid systems was quantified by optical spectroscopy. The gradual complexation of the ligand shell with potassium ions was further monitored by zeta potential measurements. Potassium dependent insertion of nanoparticles into the phospholipid bilayer membrane of vesicles in aqueous dispersion has been demonstrated by cryogenic transmission electron microscopy (cryo-TEM). Nanoparticle-dependent potassium ion transport across the vesicle membrane has been established by monitoring the membrane potential with fluorescence spectroscopy using a potential sensitive dye.

It is shown that plasmonic gold nanoparticles functionalised with a thiolated 18-crown-6 ligand shell agglomerate spontaneously from aqueous dispersion at elevated temperatures. This process takes place over a narrow temperature range, is accompanied by a colour change from red to purple-blue and is fully reversible. Moreover, the temperature at which it occurs can be adjusted by the degree of complexation of the crown ether moiety with appropriate cations. More complexation leads to higher transition temperatures. The process has been studied by UV/Vis spectroscopy, electron microscopy, dynamic light scattering and zeta potential measurements. A thermodynamic rationale is provided to suggest an entropy-driven endothermic agglomeration process based on attractive hydrophobic interactions of the complexed crowns that are competing against electrostatic repulsion of the charged ligand shells.

Selective unidirectional transport of barium ions between droplets in a water-in-chloroform emulsion is demonstrated. Gold nanoparticles (GNPs) modified with a thiolated crown ether act as barium ion complexing shuttles that...