In situ measurements of aggregation and disaggregation of Cu(II) complex at liquid/liquid interface

Aggregation of Cu(II)-5-(octadecyloxy)-2-(2-thiazolylazo)phenol (TARC18) complex at the heptane/water interface was measured directly by a centrifugal liquid membrane spectrometry and a two-phase microflow API-MS method. When the pH of an aqueous phase was increased from 4 to 6, the 1:1 complex of Cu(II)-TARC18, which was formed as a positively charged complex at the interface, formed further an aggregate, accompanied by the change of spectra suggesting its aggregation. The MS spectra of the interfacial species indicated the formation of 2:3 complex for Cu(II) and TARC18 under the conditions that the aggregate was formed. This observation allowed us to analyze the interfacial aggregation stoichiometrically: the aggregate of the 2:3 complex was formed from a 1:1 complex at the interface. The addition of purine base of adenine or guanine into the system resulted in the disruption of the aggregate by the formation of a new three-element complex of 1:1:1 for Cu(II), TARC18, and the base, showing a bathochromic shift in the spectra. Thus, the disaggregation experiment showed an interfacial molecular recognition ability of the Cu(II)-TARC18 aggregate for hydrophobic bases.