On the role of water activity on the formation of a protein-rich coffee ring in an evaporating multicomponent drop

Abstract

The coffee-ring effect is a universal feature of evaporating sessile droplets with pinned contact line, wherein solutes or particles are advected to the droplet's edge due to evaporation-driven flows. While existing models have successfully described this phenomenon in particle-laden droplets, they often assume that the evaporative flux, and thus hydrodynamics, are decoupled from solute transport. This assumption breaks down in complex fluids, such as protein or polymeric solutions, where the solute can influence evaporation through changes in water activity. Here, we investigate model respiratory droplets primarily composed of water, salt, and a type of the glycoprotein mucin. Using fluorescence microscopy, we observe the formation of a well-defined protein ring at the droplet edge as water evaporates. The growth and morphology of this ring exhibit a strong dependence on ambient relative humidity ($H_r$), revealing dynamics that existing models cannot capture. Specifically, we find that protein accumulation at the edge is governed by the feedback between local solute concentration and evaporation rate. To account for this, we develop a minimal theoretical model based on the lubrication approximation, incorporating the coupling between hydrodynamics and solute transport through the evaporation rate. Our framework reproduces key features of the experimental observations and suggests a physical basis for the $H_r$-dependent stability and infectivity of respiratory droplets containing viruses.