On-demand engineering of cell membrane receptors to nongenetically intervene in cellular behaviors is still a challenge. Herein, a membraneless enzyme biofuel cell-based self-powered biosensor (EBFC-SPB) was developed for autonomously and precisely releasing Zn2+ to initiate DNAzyme-based reprogramming of cell membrane receptors, which further mediates signal transduction to regulate cellular behaviors. The critical component of EBFC-SPB is a hydrogel film on a biocathode which is prepared using a Fe3+-cross-linked alginate hydrogel film loaded with Zn2+ ions. In the working mode in the presence of glucose/O2, the hydrogel is decomposed due to the reduction of Fe3+ to Fe2+, accompanied by rapid release of Zn2+ to specifically activate a Zn2+-responsive DNAzyme nanodevice on the cell surface, leading to the dimerization of homologous or nonhomologous receptors to promote or inhibit cell proliferation and migration. This EBFC-SPB platform provides a powerful \"sensing-actuating-treating\" tool for chemically regulating cellular behaviors, which holds great promise in precision biomedicine.

Enzymatic biofuel cells have become powerful tools in biosensing, which however generally suffer from the limited loading efficiency as well as low catalytic activity and poor stability of bioenzymes. Herein, the hierarchical porous metal-organic frameworks (MOFs) are synthesized using tannic acid (TA) for structural etching, which realizes co-encapsulation of glucose dehydrogenase (GDH) and nicotinamide adenine dinucleotide (NAD+ ) cofactor in zeolitic imidazolate framework (ZIF-L) and are further used as the biocatalytic microreactors to modify bioanode. In this work, the TA-controlled etching can not only expand the pore size of microreactors, but also achieve the reorientation of enzymes in their lower surface energy form, therefore enhancing the biocatalysis of cofactor-dependent enzyme. Meanwhile, the topological DNA tetrahedron is assembled on the microreactors, which acts as the microRNA-responsive \"lock\" to perform the cascade signal amplification of exonuclease III-assisted target recycling on bioanode and hybridization chain reaction (HCR) on biocathode. The proposed self-powered biosensor has achieved a detection limit as low as 2 aM (6 copies miRNA-21 in a 5 µL of sample), which is further successfully applied to identify cancer cells and clinical serums of breast cancer patients based on the different levels of miRNA-21, holding great potential in accurate disease identification and clinical diagnosis.

The potential application of biodevices based on enzymatic bioelectrocatalysis are limited by poor stability and electrochemical performance. To solve the limitation, modifying enzyme with functional polymer to tailor enzyme function is highly desirable. Herein, glucose oxidase (GOx) was chosen as a model enzyme, and according to the chemical structure of GOx cofactor (flavin adenine dinucleotide, FAD), we customize a biomimetic cofactor containing vinyl group (SFAD) for GOx, and prepared an GOx nanocapsule via in-situ polymerization. The characterization of particle size distribution, TEM, fluorescence and electrochemical performance indicated the successful formation of electroactive GOx nanocapsule with SFAD-containing polymeric network (n (GOx-SFAD-PAM)). The network can act as an electronic \"highway\" to link the active site with electrode, with capability to accelerate electron transfer as well as enhanced GOx stability. Further investigation of bioelectrocatalysis shows that n (GOx-SFAD-PAM)-based biosensor has low detection potential (-0.4 vs. Ag/AgCl), high sensitivity (64.97 μAmM-1cm-2), good anti-interference performance, quick response (3⁓5s) and excellent stability, and that n (GOx-SFAD-PAM)-based enzymatic biofuel cell (EBFC) has the high maximum power density (1011.21 μWcm-2), which is a 385-fold increase over that of native GOx-based EBFC (2.62 μWcm-2). This study suggests that novel enzyme nanocapsule with electroactive polymeric shell might provide a prospective solution for the performance improvement of enzymatic bioelectrocatalysis-based biodevices.

Development of reliable Enzymatic Biofuel Cells (EBFC)-based self-powered glucose biosensor for continuous, noninvasive monitoring without restriction on patient\'s movement is highly recommendable. However, its application to a large extent is limited by the relatively poor stability. Herein, we synthesized a highly flexible electrode for effective enzyme immobilization by encapsulating enzyme into the metal-organic frameworks (MOFs) and robustly anchored to the cellulose acetate (CA) nanofiber membrane. As is well-known, such nanostructured fiber materials are the first time to be synthesized for glucose biosensor, which encapsulated biomolecules in MOFs platform during the MOFs in-situ growth on the nanofiber membranes. The as-proposed biosensor demonstrated excellent stability over 15 h of continuous long-term monitoring. The remarkable stability of assembled self-powered glucose biosensor in this work could inspire the application of enzymatic biosensors in biometrics, chronic disease management and clinical diagnosis.

Laccases exhibit a wide range of applications, especially in the electrochemical field, where they are regarded as a potential biotic component. Laccase-based biosensors have immense practical applications in the food, environmental, and medical fields. The application of laccases as biocathodes in enzymatic biofuel cells has promising potential in the preparation of implantable equipment. Extensive studies have been directed towards the potential role of fungal laccases as biotic components of electrochemical equipment. In contrast, the potential of prokaryotic laccases in electrochemistry has been not fully understood. However, there has been recent and rapid progress in the discovery and characterization of new types of prokaryotic laccases. In this review, we have comprehensively discussed the application of different sources of laccases as a biocatalytic component in various fields of application. Further, we described the potential of different types of laccases in bioelectrochemical applications.

In this study, three-dimensional reduced graphene oxide/Au NPs/nitrogen-doped carbon nanotubes (RGO/Au NPs/N-doped CNTs) assembly supported on nickel foam was utilized as an anode for enzymatic biofuel cells (EBFCs). 3D RGO/Au NPs was obtained by electrodepositing reduced graphene oxide on nickel foam (Ni foam), while Au NPs were co-deposited during the process. Afterwards, nitrogen doped CNTs (N-CNTs) were allowed to grow seamlessly on the surfaces of 3D RGO/Au NPs via a simple chemical vapor deposition (CVD) process. In this nanostructure, Au NPs co-deposition and nitrogen doping offer more active sites for bioelectrocatalysis. Additionally, N-CNTs were demonstrated providing high specific surface area for enzyme immobilization and facilitating the electron transfer between glucose oxidase (GOx) and electrode. The resulting bioanode achieved efficient glucose oxidation with high current densities of 7.02mAcm-2 (0.3V vs. Ag/AgCl). Coupling with a Pt cathode, the fabricated glucose/air biofuel cell exhibited an open-circuit potential of 0.32V and generated a maximum power density 235µWcm-2 at 0.15V. This novel electrode substrate achieved high performance in current density at bioelectrochemical systems and could be useful for further exploiting the application of three dimensional carbon-based nanomaterials in EBFCs.