We then characterized how the increase in thermal fluctuations impacts the surface morphology by quantifying the surface area of water droplets at three different temperatures (298, 350, and 400 K) in the presence of tbp as a function of time, as illustrated in Figure C. The surface area of a pure spherical droplet with a radius of 20 Å, calculated using the formula A = 4πr 2 , was subtracted from the surface area of the intact triangulated droplet surface, excluding the dangling and extracted water molecules. At elevated temperatures, the self-assembled amphiphiles not only increase the roughness of the droplet surface by forming protruding structures, but also accelerate the droplet disintegration rate (vide infra). As a result, the droplets start to break into smaller clusters at a much faster rate compared to normal temperature conditions. This is also observed in the faster decay of ∆A, as shown in Figure . In this figure, the negative values of ∆A indicate that the triangulated mesh droplets have a surface area slightly smaller than that of a perfect sphere, due to shape heterogeneity caused by water dynamics and the amphiphiles on the surface. The deformation induced by tbp resulted in an increase in the droplet surface area compared to a droplet in oil without tbp. The increase in system temperature further amplified shape heterogeneity, as evidenced by the significant reduction in nanodroplet surface area over time, as shown in Figure C. This increase in surface area is related to the formation of protruding water structures and in turn possibly related to the experimentally observed enhanced reactivity on the water surfaces. C. Nanodroplet heterogeneity Upon the addition of amphiphile, there was an increase in the heterogeneity of the droplet water structure, leading to more extracted and surface-dangling water molecules. To understand the evolution of perturbations in the hydrogen-bonding structure of a water droplet induced by surface-assembled tbp, we conducted a comprehensive cluster analysis of the hydrogen-bonding network of water. This analysis allowed us to compare the hydrogen-bonding network in the presence of tbp to that in a pure system without tbp. The evolution of the number of water clusters with time is shown in tion of tbp caused the water droplet to disintegrate, reducing water connectivity to nH2O = 2.5 within the first 10 ns of the simulation. The increase in temperature further decreased nH2O = 2.15 at 350K to ∼ 1.85 at 400 K (Figure ). Comprehensive calculations of the average H 2 O coordination, associated with the most predominant water cluster (excluding extracted and dangling water molecules via cluster analysis), are shown in Figure C. The coordination of the largest water cluster (n max,H2O ) evolved constantly over time. Similar trends are obtained at different temperatures (Figure ). The results suggest that the time decay of disruptions within the water network (in terms of the average water coordination number) in the w/t/o system primarily arises from the dangling and extracted water molecules, while the coordination of the intact core nanodroplet remains constant, fluctuating around a stable water coordination number. Nonetheless, this average coordination number of the intact core nanodroplet (n max,H2O ) decreased both in the presence of amphiphile (Figure ) and due to the action of temperature (Figure ), due to increased heterogeneity within the hydrogen bonding network of water.