Covalently bonded layer-by-layer assembly of multifunctional thin films based on activated esters.

We demonstrate that chemically stable, multifunctional polymer thin films can be obtained using the layer-by-layer (LbL) deposition based on covalent bonds between adsorbing chains. Poly(pentafluorophenyl-4-vinylbenzoate) (P1) or poly(pentafluorophenylacrylate) (P2) polymers were assembled with poly(allyl amine) (PAAm) to yield LbL multilayer films through amide bond formation by the reaction between activated esters of P1 or P2 and amine groups in PAAm, which was quantitatively monitored by Fourier transform infrared spectroscopy (FT-IR). It was found that the difference in the solubility of P1 and P2 against ethanol, which was used as the solvent for PAAm, during the LbL deposition yields different reaction conversion for the activated esters in either P1 or P2: the reaction conversion of P2 is higher than the conversion with P1. In addition, free (or unreacted) activated esters and amine groups remaining in the PAAm/P1 LbL film were further utilized for the incorporation of multiple functional materials (5-((2-aminoethyl)amino)naphthalene-1-sulfonic acid (EDANS) and Rhodamine B dyes in the present case) by post-treatments in order to further tailor the film properties. It was also demonstrated that the surface functional groups (activated esters) in the LbL films can also be utilized for surface patterning with one functional material, followed by functionalization with a second functional material during the post-treatment throughout the whole film. Finally, the PAAm/P1 and PAAm/P2 LbL films were shown to be quite stable in the extreme pH range, and free-standing films can easily be obtained by the treatment of the films with mild acidic conditions. The versatility of incorporating multiple functional materials into a single multilayer film as well as the excellent physicochemical stability of the covalently bonded multilayer free-standing films proves to be quite useful to design flexible and multifunctional thin film structures for many chemical and biological applications.