Water fraction dependence of the aggregation behavior of hydrophobic fluorescent solutes in water-tetrahydrofuran

Tsuji, Hayato*; Nakahata, Masaki*; Hishida, Mafumi*; Seto, Hideki*; Motokawa, Ryuhei   ; Inoue, Takeru*; Egawa, Yasunobu*

This work investigates the water-fraction dependence of the aggregation behavior of hydrophobic solutes in water-tetrahydrofuran (THF) and the elucidation of the role of THF using fluorescence microscopy, dynamic light scattering, neutron and X-ray scattering, as well as photoluminescence measurements. Based on the obtained results, the following model is proposed: hydrophobic molecules are molecularly dispersed in the low-water-content region (10-20 vol %), while they form mesoscopic particles upon increasing the water fraction to 30 vol percent. This abrupt change is due to the composition fluctuation of the water-THF binary system to form hydrophobic areas in THF, followed by THF-rich droplets where hydrophobic solutes are incorporated and form loose aggregates. Further increasing the water content prompts the desolvation of THF, which decreases the particle size and generates tight aggregates of solute molecules. This model is consistent with the luminescence behavior of the solutes and will be helpful to control the aggregation state of hydrophobic solutes in various applications.