Solute dynamics in block-copolymer reverse micelles: do water content and copolymer concentration alter the microenvironment?

Abstract

Solute dynamics has been explored 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. To this effect, nonradiative rate constants (knr) and reorientation times (τr) of two carbocyanine derivatives, 3,3'-diethyloxadicarbocyanine iodide (DODCI) and merocyanine 540 (MC 540) have been measured at different mole ratios of water to copolymer (W) and also at three copolymer concentrations. By examining the nonradiative rate constants and the reorientation times of the two solutes, the microenvironment offered by L64/water/p-xylene reverse micellar system has been investigated. It has been observed that there is no variation in the nonradiative rate constants as well as in the reorientation times of both DODCI and MC 540 with an increase in W and [L64]. Since knr represents activated twist motion about the double bonds for these solutes, it is sensitive to the local friction and likewise, τr also provides information about the microenvironment. Thus, the results of this study indicate that DODCI and MC 540 are located in the cores of the L64 reverse micelles that are made up of hydrated ethylene oxide blocks and the hydration levels are not altered despite an increase in the water content and copolymer concentration. In other words, there is no variation in the microenvironment offered by L64/water/p-xylene reverse micellar system upon increasing W and [L64].