The present invention provides, among other things, multilayer film coating compositions, coated substrates and methods thereof. In some embodiments, a structure includes a substrate； and a multilayer film coated on the substrate, wherein adjacent layers of the multilayer film are associated with one another via one or more non-covalent interactions, wherein the multilayer film comprises a first nucleic acid agent present at a loading density, and further wherein the multilayer film is characterized in that, when the structure is placed on a subject so that the multilayer film contacts cells, the first nucleic acid agent is released with a profile characterized by a feature selected from the group consisting of 1) being a burst-free release； 2) being a sustained release； and 3) exhibiting in vitro and/or in vivo biological effectiveness.
