Hydrogen-bonding induced alternating thin films of dendrimer and block copolymer micelle

The hydrogen-bonding induced alternating multilayer thin films of dendrimers and block copolymer micelles were demonstrated. The block copolymer micelles derived from amphiphilic poly(2-ethyl-2-oxazoline)-block-poly(epsilon-carprolactone) (PEtOz-PCL) in aqueous phase have a core-shell structure with a mean hydrodynamic diameter of 26 rim. The hydrogen bonding between the PEtOz outer shell of micelle and the carboxyl unit of poly(amidoamine) dendrimer of generation 4.5 (PAMAM-4.5G) at pH 3 was utilized as a driving force for the layer-by-layer alternating deposition. The multilayer thin film was fabricated on the poly(methyl methacrylate) (PMMA) thin film spin-coated on silicon wafer or glass substrate by the alternate dipping of PEtOz-PCL micelles and PAMAM dendrimers in aqueous solution at pH 3. The formation of multilayer thin film was characterized by using ellipsometry, UV-vis spectroscopy, and atomic force microscopy. The PEtOz outer shell of PEtOz-PCL micelle provided the pH-responsive hydrogen bonding sites with peripheral carboxylic acids of PAMAM dendrimer. The multilayer thin film was reversibly removed after dipping in aqueous solution at pH >= 5.6 due to dissociation of the hydrogen bonding between PEtOz shell of PEtOz-PCL micelle and peripheral carboxyl units of PAMAM dendrimer.