Bromide counterion as a spectroscopic sensor at the interface of cetyltrimethylammonium micelles

Abstract

The strong UV absorption of the bromide in aqueous solution undergoes a remarkable red shift of more than 10 nm induced by the addition of the salts that constitute a saline buffer. The maximum absorption wavelength of the bromide is displaced from approximately 194 nm in ultrapure water to wavelengths above 200 nm, depending on the composition of the solution. The bromide spectrum as counterion of the cetyltrimethylammonium in the surfactant CTAB also shows sensitivity to the aggregation behavior of the tensioactive, being able to detect intermolecular interactions even at concentrations lower than the critical micelle concentration. And, when the micelles are assembled, the bromide absorption detects the interfacial rearrangements caused by the incorporation of ions. To know more about those interfacial features, the pyrene molecular probe was used, taking advantage of the extensive knowledge of its spectroscopy. Pyrene verifies the existence of changes in the interfacial organization which confirm that the sensitivity of the bromide spectrum is based on the ability of the ion to detect its microenvironment, and therefore reaffirms that its absorption spectrum can be used as a local sensor. The present work encourages the use of bromide as a sensor ion in the UV region between 190 and 210 nm, which would avoid the introduction of external molecular probes that could disturb the system.