Layer-by-layer (LbL) self-assembly (SA) of polymers at surfaces is a powerful technique to functionalize surfaces. Due to its advantages, there has been growing interest in using LbL films in many application areas: e.g. medicine, electronics, sensor technology, photonics, etc. Using LbL, properties of multilayers (MLs) can be controlled by nature of film components, pH, ionic strength or temperature of the assembly/post-assembly solutions. In addition to its simplicity and low cost, LbL allows incorporation of functional molecules within MLs. This proposal examines strategies to introduce functionality to MLs through combination of synthetic and physicochemical ideas. Project 1 will focus on incorporation of dually responsive block copolymer micelles (BCMs) into hydrogen-bonded MLs to increase loading capacity of films for hydrophobic molecules. Tuning release of a dye from micellar cores will be investigated by changing environmental stimuli and regulating the hydrophobicity of core and corona blocks. Moreover, effect of two different coating techniques (dipping vs. spraying) on loading capacity of BCM films will be explored. Project 2 will investigate SA of selectively betainized block copolymers into micelles with zwitterionic corona and incorporation of such aggregates into MLs using LbL. Interactions of zwitterionic micelles (ZMs) with salts and polyelectrolytes will be explored in solution to develop strategies to include ZMs within MLs and explore such systems for potential multiple drug delivery applications. Project 3 will explore inclusion complexation as a driving force for LbL assembly of biopolymers with detailed structural analysis to broaden the range of molecules that can be incorporated into MLs. Project 4 will focus on preparation of polymer-inorganic LbL films with enhanced physical and mechanical properties. Results obtained from projects will contribute to fundamental understanding of structure-property relationship of MLs at surfaces.