Redox is emerging as an alternative modality for bio‐device communication. In contrast to the more familiar ionic electrical modality: (i) redox involves the flow of electrons through oxidation–reduction reactions; (ii) the aqueous medium is an “insulator” to this electron flow since free electrons do not normally exist in water; and (iii) redox states are intrinsically digital (oxidized and reduced). By exploiting these unique features, a catechol‐based molecular memory film is reported. This memory is fabricated by electrochemically grafting catechol to a chitosan–agarose polysaccharide network to generate a redox‐active but non‐conducting matrix. The redox state of the grafted catechol moieties serves as the 2‐state memory. It is shown that these redox states: can be repeatedly switched by diffusible mediators (electron shuttles); can be easily read electrically or optically; are stable for at least 2 h in the absence of energy; are sensitive to biologically relevant oxidizing and reducing contexts; and can be switched enzymatically. This catechol‐based molecular memory film is a simple circuit element for redox linked bioelectronics.
Reduction–oxidation (redox) reactions provide a distinct modality for biological communication that is fundamentally different from the more‐familiar ion‐based electrical modality. Biology uses these two modalities for communication through different systems (immune versus nervous), and uses different mechanisms to control the flow of the charge carriers: the flow of soluble ions is controlled using structural barriers (i.e., membranes) and gates (e.g., membrane‐spanning protein channels), while the flow of insoluble electrons is controlled using redox‐reaction networks. Here, a simple electrochemical approach to pattern catechols onto a flexible polysaccharide hydrogel is reported and it is demonstrated that the patterned catechol regions serve as nodes for the mediated flow of electrons through redox reactions. Electron flow through this node involves the switching of binary redox states (oxidized and reduced) and this node's redox state can be detected (i.e., “read”) by passively observing its optical absorbance, or actively switching its redox‐state electrochemically. Further, this catechol node can be switched through biological mechanisms, and this enables the fabricated catechol node to be embedded within biochemical redox reaction networks to facilitate the spanning of bio‐electronic communication. Thus, it is envisioned that catechols can emerge as a molecular equivalent to a transistor for miniaturize‐able, deployable and sustainable redox‐linked bioelectronics.
more » « less- NSF-PAR ID:
- 10453461
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 31
- Issue:
- 11
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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