Orthogonal surface-grafted polymer gradients: A versatile combinatorial platform

Orthogonal polymer brush gradients are assemblies of surface-anchored macromolecules, in which two material properties of the grafted chains (e.g., grafting density, molecular weight) vary independently in orthogonal directions. Here, we describe the formation and applications of two such orthogonal assemblies, involving: (1) molecular weight and grafting density (MW/σ) gradients of a given polymer and (2) molecular weight gradients (MW1/MW2), of two different polymers. Each point on orthogonal gradient substrate represents a unique combination of the two surface properties being varied, thus facilitating systematic investigation of a phenomenon that depends on the two said properties. We illustrate this point by employing orthogonal structures to study systematically: (1) formation of polymer brush-nanoparticle composite assemblies, (2) protein adsorption and cell adhesion, and (3) chain conformations in tethered diblock copolymers exposed to selective solvents. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3384–3394, 2005