Can Critical Packing Parameter Depict Probe Rotation in Block-Copolymer Reverse Micelles?

Abstract

Rotational diffusion of two ionic probes, cationic rhodamine 110 (R110) and anionic fluorescein (FL), has been examined in reverse micelles formed with the triblock copolymer (EO)13-(PO)30-(EO)13 (L64), where EO and PO represent ethylene oxide and propylene oxide units, respectively, with small amounts of water in p-xylene. This study has essentially been undertaken to explore the influence of mole ratio of water to copolymer (W) as well as copolymer concentration on probe rotation. On the basis of fluorescence lifetimes and reorientation times, it has been established that both R110 and FL are located in the interfacial region of L64/water/p-xylene reverse micellar system. The average reorientation time decreases by 10-35% with an increase in W for both the probes at a given copolymer concentration. However, for a particular W, the average reorientation time increases by 10-30% as the concentration of the copolymer is enhanced. From the micellar structural parameters available in the literature, critical packing parameters have been calculated for the L64/water/p-xylene reverse micellar system, and it has been noticed that the average reorientation times of both the probes scale linearly with the critical packing parameter. In essence, the results of this study indicate that the probe mobility in the interfacial region of block copolymer reverse micelles is governed by the micellar packing.