Surfactin is a typical kind of biosurfactant with a large diversity of structure, and its molecular structure is expected to play a crucial role in its adsorption dynamics. Adsorption kinetics of surfactin homologues at the n-hexadecane/aqueous solution interface is studied using a droplet-based microfluidic method. Molecular dynamics simulations are performed to illustrate the dependence of adsorption energy on the surfactin structure. Rapid reduction of dynamic interfacial tensions is obtained. The best fit to experimental results reveals that surfactin with shorter aliphatic chains, C13-surfactin and C14-surfactin, has larger rate constants of adsorption and desorption. Interfacial tensions are rapidly reduced in the case of the oil/water interface which is freshly formed, and the equilibrium adsorption is rapidly established approximately in 100–350 ms at concentrations above the critical micelle concentration. C15-surfactin that has a longer aliphatic chain adsorbs and desorbs slower, and the equilibration time of adsorption is slightly longer. Moreover, C15-surfactin has a strong tendency for adsorbing at the interface, which is in accordance with the larger adsorption energy obtained by molecular dynamics simulation, and aggregating behavior in solution. The present study provides insights on the surfactin structure and the dynamics of adsorption at the liquid/liquid interface.

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