Synthesis and surface structure of thymine-functionalized, self-assembled monolayer-protected gold nanoparticles.

Thymine-functionalized SAM-protected gold nanoparticles with diameters of 2.2 +/- 0.3 nm and 7.0 +/- 1.0 nm were prepared via a modified two-phase transfer method. UV-vis spectra showed that particle size and solvent type, as well as surface charge, influenced the gold surface plasmon band absorption, along with the interaction between thymine terminal groups in the solution. Although the bulky thymine end groups interacted strongly on the particle surface, a well-ordered monolayer of thyminethiol derivatives with a long hydrocarbon chain was formed on the particle surface, exhibiting an ordered, all-trans conformation of the methylene backbone, similar to those of corresponding self-assembled monolayers (SAMs) generated from normal alkanethiols. A larger particle size and a longer reaction time facilitated the formation of more ordered thymine-terminated thiol SAMs. Thermal analysis indicated that reorientation of the SAMs during heat treatment occurred by two processes, caused possibly by the separate recrystallization of the hydrocarbon long chains and thymine units. More ordered SAMs with a higher thermal stability were formed on the larger particle surfaces when compared with those on the smaller ones. A greater density of molecular packing was found on the smaller particle surfaces. However, SAMs formed on the larger gold particles resembled 2D SAMs on the smooth, flat gold surfaces. XPS results confirmed the thymine structure as well as the chemical bond between gold and sulfur. One type of adsorbed sulfur species was observed for the smaller particles and two for the larger ones, but a slightly higher binding energy of thiolate was found for the smaller ones.