Chemically Triggered Dopant Release from Surface-Modified Polypyrrole Films

• DOI: 10.3390/surfaces8020023
• Publication Date: 2025-04-04T07:36:45Z
• Authors: Grant Richter; Allen Knepper; Paul J. Molino; Timothy W. Hanks

Polypyrrole (PPy) is cationic in its conducting form, requiring a charge-balancing counterion, or dopant. The release of bioactive dopants, driven by the reduction of PPy films, offers a route to controlled drug delivery. Thiol-terminated long chain poly (ethylene glycol) (PEG) reacts with a dodecylbenzene sulfonate (DBSA)-doped PPy, forming a dense overlayer and partially liberating DBSA via the chemical reduction of the film. The resulting PEG brush acts as a barrier to dopant diffusion from the film, but proteins have been shown to disrupt this layer, releasing the DBSA. The mechanism by which this disruption occurs has not been thoroughly investigated. In this study, dopant release from PEG-PPy composites was examined via systematic exposure to a variety of chemical stimuli, including macromolecules such as poly (ethylene imine), polyethylene glycol, and poloxamers, as well as small-molecular-weight alcohols, carboxylic acids, and amines. Dopant release was quantified by quartz crystal microbalance. Poly (ethylene imine) efficiently released DBSA, while anionic and uncharged macromolecules did not. All classes of small molecules triggered dopant release, with longer homologues magnifying the response. The mechanisms of dopant removal are dependent on the functional groups of the stimulating agent and include ion exchange and nucleophilic reduction of the polycationic backbone. Tosylate, salicylate, and penicillin dopants showed release behaviors similar to DBSA, demonstrating the generality of the PEG barrier.