Interaction of gold nanoparticles mediated by captopril and S-nitrosocaptopril: the effect of manganese ions in mild acid medium

We report herein results regarding reactivity and assembly of citrate-capped gold nanoparticles (AuNPs) mediated by captopril (cap) and S-nitrosocaptopril (NOcap), two angiotensin converting enzyme inhibitors and antihypertensive agents. The results were compared with that of cysteine (Cys), a thiol-containing amino acid found in plasma. The interparticle interactions were characterized by monitoring the evolution of the surface plasmon resonance band using the spectrophotometric method. The original gold nanoparticles were efficiently modified by small amounts of Mn+2 ions, which are adsorbed onto the surface of 15.4 nm citrate-capped gold nanoparticles, giving rise to manganese–gold nanoparticles (Mn–AuNPs) that, in mild acid medium, have proved to be highly sensitive and a rapid colorimetric detection method for thiols. Depending on the concentration of the Mn+2 ions the aggregation of AuNPs can be rapidly induced. The kinetics of the assembly process has been studied. Good first-order kinetics has been observed, with the exception of captopril-mediated nanoparticle aggregation at low concentration of either cap or acid. The rate of Cys-mediated assembly of gold nanoparticles in aqueous 10 mM acetic acid is more than 20-times faster than pure AuNPs and concentrations of Cys as low as 34 nM can be detected in less than 40 min under conditions of stable Mn–AuNPs. Similar effects were observed with cap or NOcap. The assembly–disassembly reversibility is shown with cap and NOcap and depends highly on pH.