Journal of Physical Chemistry B, Vol.122, No.27, 6966-6974, 2018
Anomalous Spectral Modulation of 4-Aminophthalimide inside Acetonitrile/AOT/n-Heptane Microemulsion: New Insights on Reverse Micelle to Bicontinuous Microemulsion Transition
The behavior of acetonitrile/sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane microemulsion, whether it remains as reverse micelle (RM) or bicontinuous microemulsion (BMC), has been controversial and even termed as a "problem system". Herein, we investigate the microemulsion using spectral and dynamical responses of a hydrophilic solvatochromic fluorophore 4-aminophthalimide (4-AP) at different w(s) values (=[acetonitrile]/[AOT]). Interestingly, we found that emission parameters of 4-AP within the microemulsion vary differently at low and high w(s )( )regimes. The quantum yield (phi(f)) and lifetime (tau(f)) of 4-AP first increase up to w(s) = similar to 1 and, thereafter, decrease upon a further increase in the w(s) values. The emission maximum of 4-AP significantly shifts to a higher wavelength from 445 nm at w(s) = 0 to 475 nm at w(s) = 8. Interestingly, unlike aqueous RMs, the emission maximum at w(s) = 1 matches with the emission maximum in neat acetonitrile and the emission maximum shifts to even longer wavelength at a higher w(s). Steady-state anisotropy also shows a break around w(s) = 1; anisotropy decreases very sharply from w(s) = 0 to 1 and, thereafter, remains nearly constant. Solvation dynamics becomes progressively faster with an increase in the acetonitrile content only in the low w(s) regimes but remains almost independent of w(s) after w(s) > 2. All of the results collectively indicate that the morphology of the microemulsion may change at an intermediate w(s) (similar to 1); below this, the system behaves like reverse micelles, and above this, the system may remain as BMC. The conjecture was further supported by dynamic light scattering measurements, where we observed a gradual increment of the average size at the low acetonitrile content (up to w(s) = 1) but, thereafter, the size distribution becomes multimodal and sizes cannot be estimated correctly.