Engineered Proteins: Redox Properties and Their Applications

Abstract

Oxidoreductases and metalloproteins, representing more than one third of all known proteins, serve as significant catalysts for numerous biological processes that involve electron transfers such as photosynthesis, respiration, metabolism, and molecular signaling. The functional properties of the oxidoreductases/metalloproteins are determined by the nature of their redox centers. Protein engineering is a powerful approach that is used to incorporate biological and abiological redox cofactors as well as novel enzymes and redox proteins with predictable structures and desirable functions for important biological and chemical applications. The methods of protein engineering, mainly rational design, directed evolution, protein surface modifications, and domain shuffling, have allowed the creation and study of a number of redox proteins. This review presents a selection of engineered redox proteins achieved through these methods, resulting in a manipulation in redox potentials, an increase in electron-transfer efficiency, and an expansion of native proteins by de novo design. Such engineered/modified redox proteins with desired properties have led to a broad spectrum of practical applications, ranging from biosensors, biofuel cells, to pharmaceuticals and hybrid catalysis. Glucose biosensors are one of the most successful products in enzyme electrochemistry, with reconstituted glucose oxidase achieving effective electrical communication with the sensor electrode; direct electron-transfer-type biofuel cells are developed to avoid thermodynamic loss and mediator leakage; and fusion proteins of P450s and redox partners make the biocatalytic generation of drug metabolites possible. In summary, this review includes the properties and applications of the engineered redox proteins as well as their significance and great potential in the exploration of bioelectrochemical sensing devices. Antioxid. Redox Signal. 17, 1796-1822.

A Short Review of the Architecture and Computational Analysis in the Design of Graphene Based Bioelectronic Devices

“…• Enzyma�c fuel cell (3) • Microbial fuel cell (1) • Bioelectronic nose (7,8) • Bioelectronic tongue (7,8) • Bioelectronic eyes (7,8) • Fluidtrobe (80) • U tube concept (80) • Skin patches (4,5) • DNA extrac�on chip (4) • Glucose • monitoring (5,6) • Electrocardiography (ECG) (6) • Ac�ve exoskeleton (10) • Passive upper limb (10) • Passive lower limb (10) • Kidney mimic (9) • Liver mimic (9) • Heart mimic (9) • Lung mimic (9) (Anti-IgG) is anchored on gold nanoparticles (AuNPs). (40)(41)(42) The AuNPs are spread over a thermally reduced graphene oxide (TrGO) membrane as the channel material of the FET; these nanoparticles have shown specific recognition ability for IgG.…”

“…As illustrated in Fig. 1, bioelectronic devices can be used for power generation in the form of enzymatic and microbial biofuel cells, (1)(2)(3) and for testing and diagnostic purposes in the form of e-skin devices, nucleic acid amplification chips, DNA extraction chips, and glucose monitoring devices. (4)(5)(6) For applications in artificial perception, several types of bioelectronic devices such as the bioelectronic nose, brain, and tongue have been demonstrated.…”

“…(15,21,23,24) A similar principle has been extended to power generation, where an enzymatic biofuel cell has been developed in response to industrial demand. Such a bioelectronic device can generate energy in a sustainable manner by utilizing biocatalysts, either in the form of isolated enzymes (1,2) or in the presence of enzymes within microbial cells (3) to convert chemical energy into electricity. (1,3,25) After a breakthrough study on the preparation of graphene, which is a single-atom-thick sheet of carbon, by Novoselov and co-workers, (26) there has been tremendous effort to utilize this nanomaterial for the electronic coupling of redox enzymes.…”

“…Such a bioelectronic device can generate energy in a sustainable manner by utilizing biocatalysts, either in the form of isolated enzymes (1,2) or in the presence of enzymes within microbial cells (3) to convert chemical energy into electricity. (1,3,25) After a breakthrough study on the preparation of graphene, which is a single-atom-thick sheet of carbon, by Novoselov and co-workers, (26) there has been tremendous effort to utilize this nanomaterial for the electronic coupling of redox enzymes. (27)(28)(29)(30) Its ultrahigh in-plane electron conductivity, (31,32) high thermal conductivity, (33) and mechanical properties (31)(32)(33) make it a promising material not only for the channel of electronic devices (34)(35)(36) but also for the construction of bioelectrodes and biomembranes.…”

Unraveling Binding Effects of Cobalt(II) Sepulchrate with the Monooxygenase P450 BM-3 Heme Domain Using Molecular Dynamics Simulations

“…[1][2][3][4][5][6][7] A class of enzymes that targets these applications is cytochrome P450 monooxygenases, a super family of heme-containing proteins. [8][9][10][11][12][13][14] In the presence of reduction equivalents, they catalyze the oxidation of substrates 12 involved in biosynthesis and biodegradation pathways, or in xenobiotic metabolism.…”