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.

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Growing evidence implicates an association between psychosocial stress and oxidative stress (OxSt) although there are not yet reliable biomarkers to study this association. We used a Trier Social Stress Test (TSST) and compared the response of a healthy control group (HC; N=10) against the response of a schizophrenia group (SCZ; N=10) that is expected to have higher levels of OxSt. Because our previous study showed inconsistent changes in conventional molecular markers for stress responses in the neuroendocrine and immune systems, we analyzed the same serum samples using a separate reducing capacity assay that provides a more global measurement of OxSt. This assay uses the moderately strong oxidizing agent iridium (Ir) to probe a sample's reducing capacity. Specifically, we characterized OxSt by this Ir-reducing capacity assay (Ir-RCA) using two measurement modalities (optical and electrochemical) and we tuned this assay by imposing an input voltage sequence that generates multiple output metrics for data-driven analysis. We defined five OxSt metrics (one optical and four electrochemical metrics) and showed: (i) internal consistency among each metric in the measurements of all 40 samples (baseline and post TSST for N=20); (ii) all five metrics were consistent with expectations of higher levels of OxSt for the SCZ group (three individual metrics showed statistically significant differences); and (iii) all five metrics showed higher levels of OxSt Post-TSST (one metric showed statistically significant difference). Using multivariant analysis, we showed that combinations of OxSt metrics could discern statistically significant increases in OxSt for both the SCZ and HC groups 90 min after the imposed acute psychosocial stress.

Redox is a ubiquitous biological signaling modality that is providing opportunities for bioelectronics. Various experimental studies have demonstrated that catechols offer unique molecular electronic properties for redox-based bioelectronics because catechols can confer redox activity without conductivity. Here, we fabricated a catechol-containing hydrogel film at an electrode surface and characterized this film using dynamic spectroelectrochemical measurements and physics-based modeling (i.e., reaction–diffusion modeling). We show that (i) the flow of electrons through the catechol film involves a redox reaction network; (ii) the redox-state switching of the catechol node is gated by diffusible electron carriers (i.e., mediators) and synchronized to electron transfer at the electrode; and (iii) a physics-based reaction–diffusion model can be abstracted into readily measurable metrics that can be used to characterize the response characteristics of more complex experimental systems (i.e., systems that cannot be described from first principles). Finally, we performed a simple perturbation analysis to illustrate how theory can guide the selection of metrics capable of detecting interactions between the catechol-coated electrode and bio-relevant nodes of a redox interactome (i.e., metrics that are sensitive to redox network topology). Overall, this work provides a unifying framework to understand catechol-based electrode coatings and suggests how theory can guide the selection of metrics for data-driven analysis in emerging applications in redox bioelectronics.

We find that ideas in optical image encryption can be very useful for adaptive optics in achieving simultaneous phase and amplitude shaping of a laser beam. An adaptive optics system with simultaneous phase and amplitude shaping ability is very desirable for atmospheric turbulence compensation. Atmospheric turbulence-induced beam distortions can jeopardize the effectiveness of optical power delivery for directed-energy systems and optical information delivery for free-space optical communication systems. In this paper, a prototype adaptive optics system is proposed based on a famous image encryption structure. The major change is to replace the two random phase plates at the input plane and Fourier plane of the encryption system, respectively, with two deformable mirrors that perform on-demand phase modulations. A Gaussian beam is used as an input to replace the conventional image input. We show through theory, simulation, and experiments that the slightly modified image encryption system can be used to achieve arbitrary phase and amplitude beam shaping within the limits of stroke range and influence function of the deformable mirrors. In application, the proposed technique can be used to perform mode conversion between optical beams, generate structured light signals for imaging and scanning, and compensate atmospheric turbulence-induced phase and amplitude beam distortions.