Multivalent-Ion-Mediated Stabilization of Hydrogen-Bonded Multilayers


  • This work was supported by the Australian Research Council under the Federation Fellowship and Discovery Project schemes, and by the Victorian State Government under the STI Initiative. We thank E. Tjipto and Q. Li (CNST) for atomic force microscopy measurements. Supporting Information is available online from Wiley InterScience or from the author.


Hydrogen-bonding interactions are an important alternative to electrostatic interactions for assembling multilayer thin films of uncharged components. Herein, a new method is reported for rendering such films stable at pH values close to physiological conditions. Multilayer films based on hydrogen bonding are assembled by the alternate deposition of poly[(styrene sulfonic acid)-co-(maleic acid)] (PSSMA) and poly(N-isopropylacrylamide) (PNiPAAm) at pH 2.5. The use of PSSMA results in multilayers that contain free styrene sulfonate groups, as these moieties do not interact with the PNiPAAm functional groups. Subsequent infiltration of a multivalent ion (Ce4+ or Fe3+) leads to an increase in the total film mass, with little impact on the film morphology, as determined by using atomic force microscopy. To examine the film stability, the resulting films have been exposed to elevated pH (7.1). While there is substantial swelling of the multilayers (25 % and 55 % for Ce4+- and Fe3+-stabilized films, respectively), film loss is negligible. This provides a stark contrast with non-stabilized films, which disassemble almost immediately upon exposure to pH 7.1. This method represents a simple and effective strategy for stabilizing hydrogen-bonded structures non-covalently. Further, the multivalent ions also render the films responsive to changes in the local redox environment, as demonstrated by film disassembly after exposure of Fe3+-treated films to iodide solutions.