Interaction of gold nanorods with cysteine as well as 3-mercaptopropionic acid (MPA) has been investigated by isothermal titration calorimetry (ITC), in combination with electronic absorption spectroscopy and electron microscopy. The assembly process with MPA shows two steps, the first due to the binding of MPA to gold nanorods through the sulfur atom, and the second due to assembly of the MPA capped gold nanorods through the formation of cyclic hydrogen bonded dimers between the MPA molecules. In the case of cysteine only a single step is observed in ITC, due to the binding of the molecules to gold nanorods. (c) 2007 Elsevier B.V. All rights reserved.