Controlled Formation of Gold Nanoparticle Dimers Using Multivalent Thiol Ligands

Approaches for the controlled formation of gold nanoparticle dimers are investigated. These are based on a locally confined surface modification of gold nanoparticles followed by bridging two particles with an organic linker. A key factor in these approaches is the use of multivalent ligands. Citrate-stabilized gold nanoparticles are immobilized on a glass surface and mono- and multivalent thiol ligands are investigated regarding their ability to inactivate the nanoparticles sites facing away from the glass. A successful locally confined functionalization is only possible if multivalent ligands are used in this step. The application of monovalent ligands results in less stable particles without a permanent regioselective functionalization. This result can be explained by the dynamic equilibrium between bound and free ligands. Subsequently, the sites of the nanopartides previously bound to the glass surface are functionalized with thiol ligands additionally bearing a reactive group. Approaches using dithiol linkers, diamine linkers, and coupling complementary functionalized particles are investigated. The highest yield of stable dimers is obtained from conditions where nanoparticles which are regioselectively functionalized with an N-hydroxysuccinimide ester are reacted with complementary amino-functionalized particles. The application of nanoparticles with activated carboxyl groups is essential since standard carboxyl activation agents induce an aggregation of the nanoparticles due to a reaction with remaining citrate molecules on the nanoparticle surface which reduces significantly electrostatic stabilization. This versatile approach using complementary regioselective with multivalent ligands functionalized nanoparticles may be also used for the coupling of particles with different size, shape, or composition, as well as a control of the interparticle distance.