Copolymers with amphiphilic properties are important in numerous applications such as thin-film nanopatterning, bottom-up nanofabrication, demulsifying, antifoaming, extraction methods, to mention a few. We investigate the adsorption of charged random and block copolymers at the water-chloroform interface. The study is performed using interfacial tension measurements and molecular dynamics simulations and the goal is to shed light into the mechanisms that regulate the interfacial adsorption of copolymers. The models consider the polar, hydrophobic, and electrostatic forces, as well as the dielectric mismatch at the interface. The experiments show  that the random copolymers are interfacially more active than the equivalent block copolymers. The molecular simulations show that the high interfacial activity of random copolymers is due to their capability to spread more efficiently at the interface than the block copolymers. Interestingly, the block copolymers become interfacially active at high charge fractions when the molecules form large aggregates that exhibit a variety of shapes from circular aggregates to elongated stripes. Our study demonstrates that the interfacial activity of polymers can be controlled via the polymer molecular architecture.

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