Understanding the Surface Chemistry of Thiolate-Protected Metallic Nanoparticles

Metallic nanoparticles (NPs) appear as promising materials to be used in biomedicine, as efficient catalysts and electrocatalysts, and as active elements in electronic and sensing devices. The most common strategy to protect these NPs is by using thiolate self-assembled monolayers (SAMs), a strategy that has proved to be useful to control the physical and chemical properties of extended solid surfaces. However, the knowledge of the structure and chemistry of thiol metal interfaces yet remains elusive, although it is crucial for understanding how NPs interact with molecules, biomolecules, and living cells and also for a better design of NP-based devices. This Perspective strives to show the complexity of the thiol-metal NP interface chemistry and how this changes with the nature of the metallic core.