How Does Interfacial Hydration Alter during Rod to Sphere Transition in DDAB/Water/Cyclohexane Reverse Micelles? Insights from Excited State Proton Transfer and Fluorescence Anisotropy.

Abstract

How does microscopic organization of an organized assembly alter during macroscopic structural transition? The question may be important to ascertain driving forces responsible for such transitions. Didodecyldimethylammonium bromide (DDAB)/water/cyclohexane reverse micelle is an attractive assembly that undergoes structural transition from rod to spherical shape when the amount of water loading, w0 ([water]/[surfactant]), exceeds a particular value (w0 ∼ 8). Here, we intend to investigate the effect of the morphological change upon interfacial hydration using steady-state and time-resolved fluorescence measurements. The anionic fluorophore 8-hydroxypyrene-1,3,6-trisulfonate (HPTS or pyranine) is expected to be trapped within the positively charged RM interface. The fluorophore can undergo excited-state proton transfer (ESPT) in the presence of water and, thus, is able to provide insight on the level of hydration within the interface. The ESPT process is markedly inhibited within the interface at low w0 and gradually favored with increase of w0. The time-resolved fluorescence decays could be best analyzed by assuming distribution of HPTS over two distinct interfacial regions- partly hydrated and mostly dehydrated. The relative population of the two regions varies distinctly at low w0 (<6) and high w0 (>6) regimes. Moreover, fluorescence anisotropy (steady-state and time-resolved) varies differently with respect to w0, before and after the transition point (w0 ∼ 8).