The randomly immersed amphiphile (tri-butyl phosphate (tbp) in this case) self-assembles around the water nanodroplet as a result of dipole-dipole interactions between the polar headgroup and water hydrogen atoms. To investigate the self-assembly of amphiphiles around a water nanodroplet, we allowed the first 5 ns for tbp to self-assemble around the droplet. Subsequently, we plotted the density profiles of H 2 O and tbp relative to the center of mass (COM) of the droplet (Figure ) over the next 5 ns. This analysis was conducted in a system comprising a water nanodroplet in tbp and an oil solution (w/t/o) (Figure ), compared to a system containing a pure water droplet in oil (w/o). Interestingly, in the first 10 ns, the tbp properly self-assembles around the water droplet to form a monolayer structure, with a hydrophilic head group facing the water droplet and a hydrophobic tail toward the oil phase, shown by the minima at 25 Å in the density profile of the head group (P=O atoms) of tbp (Figure B, shown in grey color). A typical simulation snapshot showing the adsorption of tbp in the water droplet after 10 ns is shown in Figure A. The self-assembly of tbp on non-transporting ideal surfaces, along with its impact on surface heterogeneity and fluctuations, has been extensively studied in previous research. In our current non-ideal transporting systems, the H 2 O density profiles show a shift in the H 2 O density from the COM of the droplet to the surface of the droplet in the w/t/o system and relative droplet in the w/o system. The increased density at r > 15 Å in the w/t/o system arises from protrusions formed on the water-in-oil nanodroplet surface in the presence of tbp. (vide infra) The thermal fluctuations due to increased temperature further deform the nanodroplet causing an increase in the density of extracted water (r > 20 Å) relative to the 298 K (Figure ). The transport of water from the nanodroplet into the oil phase altered the self-assembly of tbp, as indicated by a decrease in the density of tbp molecules at the water-oil interface.