Time-Resolved Structural Analysis of Fast-Photoresponsive Surfactant Micelles by Stroboscopic Small-Angle Neutron...

Photoresponsive materials are garnering attention because of their applications toward building a sustainable society. A recently developed fast-photoresponsive amphiphilic lophine dimer (3TEG-LPD) responds rapidly to light, making it a promising candidate for drug-delivery systems. In this study, the mechanism of structural changes induced by ultraviolet (UV) irradiation in 3TEG-LPD micelles in an aqueous solution was investigated via an in situ time-resolved small-angle neutron scattering (SANS) technique. Since subsecond resolution was necessary to observe the structural changes in the 3TEG-LPD micelles, stroboscopic SANS analysis was employed to obtain scattering profiles with a time width of 0.5 s. The structural parameters were quantitatively determined by performing a model-fitting analysis of the SANS results. The stroboscopic SANS results showed that upon UV irradiation, the axial ratio and pseudo-aggregation number of the 3TEG-LPD micelles increased by 1.8 and 1.6 times, respectively, whereas the number of water molecules per surfactant molecule decreased. This finding suggested that the change in the shape of the micelles from spherical to ellipsoidal shape was accompanied by dehydration. Under the present UV irradiation conditions, this structural change of the micelle occurred rapidly during the first 30 s after the start of UV irradiation. Each structural parameter recovered exponentially and reversibly during the recovery process after the cessation of UV irradiation. The changes in these parameters were analyzed in terms of kinetics by comparing them with the changes in the molecular structure. We found that the change of the micelles proceeds approximately twice as fast as the association of the molecule. Furthermore, from the perspective of the critical packing parameter consideration, the SANS analysis revealed that the UV-induced changes in 3TEG-LPD micelles are dominated by the enthalpy contribution. This finding is expected to be useful for developing new materials for various applications.