Investigation of Water Splitting Reaction by a Multicopper Oxidase through X‐ray Absorption Nanospectroelectrochemistry

Sedenho, Graziela C.; Neckel, Itamar T.; Colombo, Rafael N. P.; Pacheco, Jéssica C.; Bertaglia, Thiago; Crespilho, Frank N.

doi:10.1002/aenm.202202485

Cited by 5 publications

(13 citation statements)

References 26 publications

(49 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In fact, enzymes can be directly incorporated into electrodes and serve as catalysts to promote the reaction efficiency in many electrochemical energy and signal conversion systems. [26,156] However, these enzyme-based electrodes tend to denature and lose their catalytic activity in harsh environment. Apart from the low pH, temperature, and toxin tolerance, the low electron transfer capability and limited density of active sites are also important factors hindering the popularization of natural enzymes in conventional electrocatalysis.…”

Section: Biomimetic Catalytic Sites Creationmentioning

confidence: 99%

Biologically Assisted Construction of Advanced Electrode Materials for Electrochemical Energy Storage and Conversion

Guo

Zhang

Lei

et al. 2023

Advanced Energy Materials

View full text Add to dashboard Cite

Bio‐organisms with various architectures and versatile physiological functions provide a substantial bibliography for electrode design. To elucidate how bio‐organisms and bio‐schemes take effect in advanced electrode materials, this review sorts bio‐assisted construction into two categories, namely, biotemplating synthesis and biomimetic artificial fabrication. The former section summarizes unique characteristics of different biotemplates for electrode preparation, including “bottom‐up” structural designability of biomolecules, metabolism involving, and genetic alterable properties of biological cells, as well as, the structural regularity and integrity of bio‐tissues, with the aim to provide guidelines for manipulating bioarchitectures and endow biotemplating synthesis of electrodes with more designability. The later describes recent efforts in using bio‐prototypes to enhance the essential properties associated with advanced electrodes, including mechanical properties, wettability, mass transport, electron/charge transfer, and catalytic activity, with intensive concerns on the function principles of biomimetic designs in electrochemical systems. Then, advances in applications of bioderived and biomimetic electrode materials are summarized emphasizing how bio‐structures/components and bionic designs help to enhance the charging/discharging and electrocatalytic performance in specific electrochemical energy storage and conversion systems. Finally, future trends with prospects and challenges for developing new bioderived/biomimetic electrode materials, as well as, related conceptual innovation on bionics, are discussed in the last section.

show abstract

Section: Biomimetic Catalytic Sites Creationmentioning

confidence: 99%

Biologically Assisted Construction of Advanced Electrode Materials for Electrochemical Energy Storage and Conversion

Guo

Zhang

Lei

et al. 2023

Advanced Energy Materials

View full text Add to dashboard Cite

show abstract

“…More recently, laccase and BOD have been reported to be reversible bioelectrocatalysts for H 2 O/O 2 redox reaction at small overpotentials in specific pH conditions. [32][33][34] This versatility is attributed to the presence of three-dimensional copper sites coordinated to histidine residues inside the highly stable protein structure. [7,34,35] The catalytic site of MCOs contains active Cu(II) ions, named Type 1 (Cu T1 ) Cu, Type 2 (Cu T2 ) Cu and Type 3 (Cu T3 ).…”

Section: Multicopper Oxidasesmentioning

confidence: 99%

“…[32][33][34] This versatility is attributed to the presence of three-dimensional copper sites coordinated to histidine residues inside the highly stable protein structure. [7,34,35] The catalytic site of MCOs contains active Cu(II) ions, named Type 1 (Cu T1 ) Cu, Type 2 (Cu T2 ) Cu and Type 3 (Cu T3 ). [29] Cu T1 is the primary center, at which electrons are accepted from natural substrates, redox mediators, or directly from the electrode surface.…”

Section: Multicopper Oxidasesmentioning

confidence: 99%

“…[8] In contrast, for the water oxidation reaction, a high-valent character of the copper ions is required for the formation of the OÀ O bond (Figure 3D). [34] Besides the active site coordination, the conformation and dynamics of MCOs play important roles in their catalytic activities. The enzyme immobilization can impact the electron transfer rate and the bioelectrocatalytic activity depending on ChemCatChem the electrode surface features.…”

Section: Multicopper Oxidasesmentioning

confidence: 99%

“…The coordination environment and metal oxidation state are central role to the metalloenzymes' catalytic mechanism. As copper is crucial in many biological and synthetic catalysts, these aspects have been extensively discussed for MCOs, [7,8,34] as well as for copper complexes, [121,122] that impact the understanding of copper sites in metalloenzymes and the development of new bioinspired electrocatalysts and the discovery of new reaction pathways and electron transfer mechanisms.…”

Section: The Role Of the Coordination Environment: The Copper Casementioning

confidence: 99%

See 2 more Smart Citations

Insights from Enzymatic Catalysis: A Path towards Bioinspired High‐Performance Electrocatalysts

2023

Self Cite

View full text Add to dashboard Cite

Enzymes, especially some metalloenzymes, are exceptional catalysts for redox reactions with technological applications in several fields, including energy conversion systems and producing fuels and value‐added chemicals. Because of that, they have inspired the development of synthetic catalysts to obtain high‐performance materials. However, several fundamental aspects should be better understood to achieve this goal, such as enzyme catalysis and the role of the three‐dimensional catalytic site. Therefore, this review addresses key structural and activity aspects of some remarkable metalloenzymes and discusses three‐dimensional catalysis as an approach to enzyme catalysis. Also, the case of the multicopper oxidase enzymes is shown as an example of how the three‐dimensional coordination environment of the copper ions in the active site can impact catalysis.

show abstract

Secondary Structure in Enzyme‐Inspired Polymer Catalysts Impacts Water Oxidation Efficiency

Sedenho,

Nascimento,

Zamani

et al. 2024

Advanced Science

Self Cite

View full text Add to dashboard Cite

Protein structure plays an essential role on their stability, functionality, and catalytic activity. In this work, the interplay between the β‐sheet structure and its catalytic implications to the design of enzyme‐inspired materials is investigated. Here, inspiration is drawn from the active sites and β‐sheet rich structure of the highly efficient multicopper oxidase (MCO) to engineer a bio‐inspired electrocatalyst for water oxidation utilizing the abundant metal, copper. Copper ions are coordinated to poly‐histidine (polyCuHis), as they are in MCO active sites. The resultant polyCuHis material effectively promotes water oxidation with low overpotentials (0.15 V) in alkaline systems. This activity is due to the 3D structure of the poly‐histidine backbone. By increasing the prevalence of β‐sheet structure and decreasing the random coil nature of the polyCuHis secondary structures, this study is able to modulates the electrocatalytic activity of this material is modulated, shifting it toward water oxidation. These results highlight the crucial role of the local environment at catalytic sites for efficient, energy‐relevant transformations. Moreover, this work highlights the importance of conformational structure in the design of scaffolds for high‐performance electrocatalysts.

show abstract

Investigation of Water Splitting Reaction by a Multicopper Oxidase through X‐ray Absorption Nanospectroelectrochemistry

Abstract: Research data are not shared.

Cited by 5 publications

References 26 publications

Biologically Assisted Construction of Advanced Electrode Materials for Electrochemical Energy Storage and Conversion

Biologically Assisted Construction of Advanced Electrode Materials for Electrochemical Energy Storage and Conversion

Insights from Enzymatic Catalysis: A Path towards Bioinspired High‐Performance Electrocatalysts

Secondary Structure in Enzyme‐Inspired Polymer Catalysts Impacts Water Oxidation Efficiency

Contact Info

Product

Resources

About