Amplified vibrational circular dichroism as a manifestation of the interaction between a water soluble gold nanocluster and cobalt salt

Abstract

Vibrational circular dichroism (VCD) is a powerful tool for the structure determination of dissolved molecules. However, the application of VCD to nanostructures is limited up to now due to the weakness of the effect and hence the low signal intensities. Here we show that the addition of a small amount of cobalt(II) drastically enhances the VCD signals of a thiolate-protected gold cluster Au₂₅(Capt)₁₈ (Capt = captopril) in aqueous solution. An increase of VCD signal intensity of at least one order of magnitude is observed. The enhancement depends on the amount of CoCl₂ added but almost an order of magnitude enhancement is already observed at a cluster : CoCl₂ ratio of 1 : 1. In contrast, circular dichroism (CD) and infrared spectra hardly change. The increase in VCD intensity goes along with a qualitative change of the spectrum and the enhancement increases with time reaching a stable state only after several hours. The enhancement is due to an interaction between the cobalt(II) and the cluster, which also leads to quenching of its fluorescence. The behaviour is completely different for free captopril, where the addition of cobalt(II) salt does not affect the VCD spectrum.