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Biofunctional thin films with controlled bulk or surface properties have been made by the alternating adsorption of synthetic or natural macromolecules to various substrates. The wide variety of charged nanocomponents incorporated into these “polyelectrolyte multilayers” (PEMUs) includes biomolecules such as DNA, immunoglobulin, glucose oxidase, and cytochrome c. These biomolecular thin films offer applications as biosensors, nano-filtration, bioreactors,and protein capsules. Although multiple “electrostatic” interactions between synthetic and natural charged polymers might be presumed to modify protein conformations, individual interactions are actually quite weak, and under certain conditions, proteins embedded into PEMUs during the buildup process maintain a secondary structure close to their native form, which renders such PEMUs bioactive.