Anisotropic Hydrogel Thickness Gradient Films Derivatized to Yield Three-Dimensional Composite Materials

We report the preparation of in-plane density gradients of amino-terminated molecules and gold particles through derivatization of laterally varying thickness gradients of poly(acrylic acid) (PAA) or poly(acrylamide) (PAAm) films. PAA and PAAm gradients were formed by Zn(II)-catalyzed electropolymerization of acrylic acid (AA) or acrylamide (AAm) in the presence of an in-plane electrochemical potential gradient applied to Au or indium−tin−oxide (ITO) working electrodes. PAA thickness gradients were converted into density gradients of fluorocarbons or biocompatible groups by derivatizing with NH<sub>2</sub>CH<sub>2</sub>(CF<sub>2</sub>)<sub>6</sub>CF<sub>3</sub> or an Arg-Gly-Asp (RGD)-containing peptide, respectively. X-ray photoelectron spectroscopy (XPS) and XPS imaging were used to characterize the modified PAA gradients. Transition regions as narrow as 104 μm were achieved for fluorocarbon gradients. PAAm gradients were treated with gold particles to form a density gradient of gold particles. Surface plasmon resonance imaging and scanning electron microscopy (SEM) as well as UV−visible absorption measurements were used to characterize the gold particle density gradients. It is likely that the gold particles were attached both on the surface and inside the PAAm film.