pH- and Photoresponsive Liquid Plasticine.

Liquid marbles (LMs) can be prepared by adsorption of hydrophobic particles at the air-liquid interface of a water droplet. LMs have been studied for their application as microreaction vessels. However, their opaqueness poses challenges for internal observation. Liquid plasticines (LPs), akin to LMs, can be prepared by the adsorption of hydrophobic particles with a diameter of 50 nm or less, at the air-liquid interface of a water droplet. Unlike LMs, LPs are transparent, allowing for internal observation, thus presenting promising applications as reactors and culture vessels on a microliter scale. In this study, the surface of silica particles, approximately 20 nm in diameter, was rendered hydrophobic to prepare hydrophobic silica particles (SD 0 ). A small amount of poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) was then grafted onto the surface of SD 0 , yielding SD 1 . SD 0 particles exhibited consistent hydrophobicity irrespective of the environmental pH atmosphere. Under acidic conditions, SD 1 became hydrophilic due to the protonation of pendant tertiary amines in the grafted PDPA chains. However, SD 1 alone was unsuitable for LP preparation due to its high surface wettability regardless of atmospheric pH, attributable to the presence of PDPA-grafted chains. Therefore, to prepare pH-responsive LP, SD 1 and SD 0 were mixed (SD 1 /SD 0 = 3/7). Upon exposure to HCl gas, these LPs ruptured, with the leaked water from the LPs being absorbed by adjacent paper. Moreover, clear LPs, prepared using an aqueous solution containing a water-soluble photoacid generator (PAG), disintegrated upon exposure to light as PAG generated acid, leading to LP breakdown. In summary, pH-responsive LPs, capable of disintegration under acidic conditions and upon light irradiation, were successfully prepared in this study.