Orthogonal redox and optical stimuli can induce independent responses for catechol-chitosan films

Zhao, Zhiling; Kim, Eunkyoung; Chen, Chen-Yu; Rzasa, John R.; Zhang, Qian; Li, Jinyang; Yang, Tao; Bentley, William E.; Lumb, Jean‐Philip; Kohler, Bern; Payne, Gregory F.

doi:10.1039/d2qm00106c

Cited by 4 publications

(2 citation statements)

References 38 publications

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“…The fact that the counterions are soluble in the medium while the electrons are not soluble creates a complex linkage between electron and ion flow, and this linkage has been difficult to understand. Using MEP, we observed that melanin-containing films (like Cat–Chit films ,, ) are redox-active and can repeatedly exchange electrons with diffusible mediators. − It remains to be seen if/how measured redox activities are related to ionic and electronic conductivities.…”

Section: Integrating Electrochemistry Into Materials Science and Biologymentioning

confidence: 99%

Electro-Biofabrication. Coupling Electrochemical and Biomolecular Methods to Create Functional Bio-Based Hydrogels

et al. 2023

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Twenty years ago, this journal published a review entitled "Biofabrication with Chitosan" based on the observations that (i) chitosan could be electrodeposited using low voltage electrical inputs (typically less than 5 V) and (ii) the enzyme tyrosinase could be used to graft proteins (via accessible tyrosine residues) to chitosan. Here, we provide a progress report on the coupling of electronic inputs with advanced biological methods for the fabrication of biopolymer-based hydrogel films. In many cases, the initial observations of chitosan's electrodeposition have been extended and generalized: mechanisms have been established for the electrodeposition of various other biological polymers (proteins and polysaccharides), and electrodeposition has been shown to allow the precise control of the hydrogel's emergent microstructure. In addition, the use of biotechnological methods to confer function has been extended from tyrosinase conjugation to the use of protein engineering to create genetically fused assembly tags (short sequences of accessible amino acid residues) that facilitate the attachment of function-conferring proteins to electrodeposited films using alternative enzymes (e.g., transglutaminase), metal chelation, and electrochemically induced oxidative mechanisms. Over these 20 years, the contributions from numerous groups have also identified exciting opportunities. First, electrochemistry provides unique capabilities to impose chemical and electrical cues that can induce assembly while controlling the emergent microstructure. Second, it is clear that the detailed mechanisms of biopolymer self-assembly (i.e., chitosan gel formation) are far more complex than anticipated, and this provides a rich opportunity both for fundamental inquiry and for the creation of high performance and sustainable material systems. Third, the mild conditions used for electrodeposition allow cells to be co-deposited for the fabrication of living materials. Finally, the applications have been expanded from biosensing and lab-on-a-chip systems to bioelectronic and medical materials. We suggest that electro-biofabrication is poised to emerge as an enabling additive manufacturing method especially suited for life science applications and to bridge communication between our biological and technological worlds.

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Section: Integrating Electrochemistry Into Materials Science and Biologymentioning

confidence: 99%

Electro-Biofabrication. Coupling Electrochemical and Biomolecular Methods to Create Functional Bio-Based Hydrogels

et al. 2023

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“…The melanin synthesized by these fungi is commonly either secreted or attached to the cell wall, making it a significant but often overlooked by‐product; and it is likely to be released into wastewater. Recognizing the numerous applications of melanin, [8] it presents itself as an abundant biological resource molecule with the potential for use in the circular economy.…”

Section: Introductionmentioning

confidence: 99%

Melanin, A Fungal Photosensitizer for Cellulose Oxidizing AA9‐LPMO Enzymes

Monclaro,

Gonçalves,

Magri

et al. 2023

ChemCatChem

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Melanin is a class of hetero‐polymer pigments commonly found in nature and widely in fungi. Often referred to as the “animal lignin“, melanin is a very abundant bioresource and features many catalytically interesting properties. We conceived that, upon light absorbance, the polymer could promote long‐distance electron donation to fuel redox enzymatic catalysis or controlled in‐situ generation of H2O2. Here, we report on a fungal photo‐biocatalytic system extracted from the commercially relevant A. nidulans, where photoactivated melanin acts as an electron donor for the cellulose‐degrading AnAA9A and TtAA9E metalloenzymes. Furthermore, there was a stable and significant accumulation of H2O2 when melanin was irradiated by visible light; having the peroxide functioning as a co‐substrate for the AA9 LPMO enzymes. Oxidized cellulose‐derived oligosaccharides were detected in the dark and under light conditions, confirming the potential of melanin to reduce AA9s. When placed under light conditions, they provided hydrogen peroxide as a co‐substrate for AA9s. The use of light to tune the in‐situ generation of H2O2 by natural pigments might be pivotal to enable also another peroxide‐dependent enzymatic catalysis.

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Constraint Coupling of Redox Cascade and Electron Transfer Synchronization on Electrode‐Nanosensor Interface for Repeatable Detection of Tumor Biomarkers

Xie,

Jin,

Wang

et al. 2023

Small Methods

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Quantitative analysis of up‐regulated biomarkers in pathological tissues is helpful to tumor surgery yet the loss of biomarker extraction and time‐consuming operation limited the accurate and quick judgement in preoperative or intraoperative diagnosis. Herein, an immobilization‐free electrochemical sensing platform is developed by constraint coupling of electron transfer cascade on electrode‐nanosensor interface. Specifically, electrochemical indicator (Ri)‐labeled single‐stranded DNA on electroactive nanodonor (polydopamine, PDA) can be responsively detached by formation of DNA complex through the recognition and binding with targets. By applying the oxidation potential of Ri, nanosensor collisions on electrode surface trigger a cascade redox cycling of PDA and Ri through synchronous electron transfer, which boost the amplification of current signal output. The developed nanosensor exhibit excellent linear response toward up‐regulated biomarkers (miRNA‐21, ATP, and VEGF) with low detection limits (32 fM, 386 pM, and 2.8 pM). Moreover, background influence from physiological interferent is greatly reduced by restricted electron transfer coupling on electrode. The practical applicability is illustrated in sensitive and highly repeatable profiling of miRNA‐21 in lysate of tumor cells and tumor tissue, beneficial for more reliable diagnosis. This electrochemical platform by employing electron transfer cascades at heterogeneous interfaces offers a route to anti‐interference detection of biomarkers in tumor tissues.

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Orthogonal redox and optical stimuli can induce independent responses for catechol-chitosan films

Abstract: Catechol-based materials possess diverse properties that are especially well-suitable for redox-based bioelectronics. Previous top-down, systems-level property measurements have shown that catechol-polysaccharide films (e.g., catechol-chitosan films) are redox-active and allow electrons...

Cited by 4 publications

References 38 publications

Electro-Biofabrication. Coupling Electrochemical and Biomolecular Methods to Create Functional Bio-Based Hydrogels

Electro-Biofabrication. Coupling Electrochemical and Biomolecular Methods to Create Functional Bio-Based Hydrogels

Melanin, A Fungal Photosensitizer for Cellulose Oxidizing AA9‐LPMO Enzymes

Constraint Coupling of Redox Cascade and Electron Transfer Synchronization on Electrode‐Nanosensor Interface for Repeatable Detection of Tumor Biomarkers

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