Abstract
Partial Fischer esterification of poly(acrylic acid) allows tailoring of the hydrophobicity and charge density of multilayered films containing poly(allylamine hydrochloride) (PAH) and derivatized poly(acrylic acid) (d-PAA). As hydrophobicity and charge density strongly affect film permeability, control over these properties is vital for possible applications of PAH/d-PAA films as ion-separation membranes and sensors. The hydrophobicity of these films depends on both the extent of esterification and the nature of the derivatizing alcohol. Even though PAH/d-PAA films are composed of polyelectrolytes, the presence of hydrophobic ester groups results in advancing water contact angles as high as 101°. The hydrophobicity of these coatings allows them to effectively passivate underlying electrodes as shown by minimal peak currents in cyclic voltammograms (CVs) of Ru(NH3)63+ and Fe(CN)63-. Cross-linking of hydrophobic PAH/d-PAA films via heat-induced amidation stabilizes coatings over a wide pH range but does not significantly decrease the already low film permeability to Ru(NH3)63+ and Fe(CN)63-. Stabilization due to cross-linking does, however, allow base-promoted hydrolysis of the ester groups of PAH/d-PAA coatings. After hydrolysis, films are extremely hydrophilic and selectively permeable to Ru(NH3)63+ over Fe(CN)63- due to the high density of newly formed -COO- groups. In the case of some hydrolyzed films, the presence of small concentrations of Ca2+ results in dramatic current decreases in CVs of Ru(NH3)63+, suggesting possible use of these films in sensing applications.
Original language | English |
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Pages (from-to) | 931-937 |
Number of pages | 7 |
Journal | Langmuir |
Volume | 17 |
Issue number | 3 |
DOIs | |
State | Published - Feb 6 2001 |