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The use of enzyme-based biosensors for the detection and quantification of analytes of interest such as contaminants of emerging concern, including over-the-counter medication, provides an attractive alternative compared to more established techniques. However, their direct application to real environmental matrices is still under investigation due to the various drawbacks in their implementation. Here, we report the development of bioelectrodes using laccase enzymes immobilized onto carbon paper electrodes modified with nanostructured molybdenum disulfide (MoS2). The laccase enzymes were two isoforms (LacI and LacII) produced and purified from the fungus Pycnoporus sanguineus CS43 that is native to Mexico. A commercial purified enzyme from the fungus Trametes versicolor (TvL) was also evaluated to compare their performance. The developed bioelectrodes were used in the biosensing of acetaminophen, a drug widely used to relieve fever and pain, and of which there is recent concern about its effect on the environment after its final disposal. The use of MoS2 as a transducer modifier was evaluated, and it was found that the best detection was achieved using a concentration of 1 mg/mL. Moreover, it was found that the laccase with the best biosensing efficiency was LacII, which achieved an LOD of 0.2 µM and a sensitivity of 0.108 µA/µM cm2 in the buffer matrix. Moreover, the performance of the bioelectrodes in a composite groundwater sample from Northeast Mexico was analyzed, achieving an LOD of 0.5 µM and a sensitivity of 0.015 µA/µM cm2. The LOD values found are among the lowest reported for biosensors based on the use of oxidoreductase enzymes, while the sensitivity is the highest currently reported.

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This work reports on Fe2O3 and ZnO materials for lactate quantification. In the synthesis, the bi-phase γ-/α-Fe2O3 and γ-/α-Fe2O3/ZnO nanoparticles (NPs) were obtained for their application in a lactate colorimetric sensor. The crystalline phases of the NPs were analyzed by XRD and XPS techniques. S/TEM images showed spheres with an 18 nm average and a needle length from 125 to 330 nm and 18 nm in diameter. The γ-/α-Fe2O3 and γ-/α-Fe2O3/ZnO were used to evaluate the catalytic activity of peroxidase with the substrate 3,3,5,5-tetramethylbenzidine (TMB), obtaining a linear range of 50 to 1000 µM for both NPs, and a 4.3 µM and 9.4 µM limit of detection (LOD), respectively. Moreover, γ-/α-Fe2O3 and γ-/α-Fe2O3/ZnO/lactate oxidase with TMB assays in the presence of lactate showed a linear range of 50 to 1000 µM, and both NPs proved to be highly selective in the presence of interferents. Finally, a sample of human serum was also tested, and the results were compared with a commercial lactometer. The use of ZnO with Fe2O3 achieved a greater response toward lactate oxidation reaction, and has implementation in a lactate colorimetric sensor using materials that are economically accessible and easy to synthesize.

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We report a hybrid catalytic system containing metallic PtSn nanoparticles deposited on multiwalled carbon nanotubes (Pt65Sn35/MWCNTs), prepared by the microwave-assisted method, coupled to the enzyme oxalate oxidase (OxOx) for complete ethylene glycol (EG) electrooxidation. Pt65Sn35/MWCNTs, without OxOx, showed good electrochemical activity toward EG oxidation and all the byproducts. Pt65Sn35/MWCNTs cleaved the glyoxilic acid C-C bond, producing CO2 and formic acid, which was further oxidized at the electrode. Concerning EG oxidation, the catalytic activity of the hybrid system (Pt65Sn35/MWCNTs+OxOx) was twice the catalytic activity of Pt65Sn35/MWCNTs. Long-term electrolysis revealed that Pt65Sn35/MWCNTs+OxOx was much more active for EG oxidation than Pt65Sn35/MWCNTs: the charge increased by 65%. The chromatographic results proved that Pt65Sn35/MWCNTs+OxOx collected all of the 10 electrons per molecule of the fuel and was able to catalyze EG oxidation to CO2 due to the associative oxidation between the metallic nanoparticles and the enzymatic pathway. Overall, Pt65Sn35/MWCNTs+OxOx proved to be a promising system to enhance the development of enzymatic biofuel cells for further application in the bioelectrochemistry field.

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Biofuel cells use chemical reactions and biological catalysts (enzymes or microorganisms) to produce electrical energy, providing clean and renewable energy. Enzymatic biofuel cells (EBFCs) have promising characteristics and potential applications as an alternative energy source for low-power electronic devices. Over the last decade, researchers have focused on enhancing the electrocatalytic activity of biosystems and on increasing energy generation and electronic conductivity. Self-powered biosensors can use EBFCs while eliminating the need for an external power source. This review details improvements in EBFC and catalyst arrangements that will help to achieve complete substrate oxidation and to increase the number of collected electrons. It also describes how analytical techniques can be employed to follow the intermediates between the enzymes within the enzymatic cascade. We aim to demonstrate how a high-performance self-powered sensor design based on EBFCs developed for ethanol detection can be adapted and implemented in power devices for biosensing applications.

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The assessment of water quality is critical to implement preventive and emergency interventions aimed to limit/avoid environmental contamination and human exposure to toxic compounds. While established high-resolution techniques allow quantitative and qualitative determination of contaminants, their widespread application is not feasible due to cost, time, and need for trained personnel. In this context, the development of easy-to-implement approaches for preliminary detection of contaminants is of the utmost importance. Herein, a portable self-powered microbial electrochemical sensor enabling online monitoring of Cr(VI) is reported. The biosensor employs a bio-inspired redox mediating system to allow extracellular electron transfer between a bacterial isolate from chromium-contaminated environments and the electrode, providing a clear response to Cr(VI) presence. The biosensor shows good linearity (R2 = 0.983) and a limit of detection of 2.4 mg L-1 Cr(VI), with a sensitivity of 0.31 ± 0.02 µA cm-2 mgCr(VI)-1 L. The presented microbial bioanode architecture enhanced biosensor performance thanks to the improved "electrical wiring" between biological entities and the abiotic electrode surface. This approach could be easily implemented in engineered electrode surfaces, such as paper-based multi-anodes that maximize bacterial colonization, further improving biosensor response. Graphical abstract.

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Electrochemical ethanol oxidation was performed at an innovative hybrid architecture electrode containing TEMPO-modified linear poly(ethylenimine) (LPEI) and oxalate oxidase (OxOx) immobilized on carboxylated multi-walled carbon nanotubes (MWCNT-COOH). On the basis of chromatographic results, the catalytic hybrid electrode system completely oxidized ethanol to CO2 after 12 h of electrolysis. The fact that the developed system can catalyze ethanol electrooxidation at a carbon electrode confirms that organic oxidation catalysts combined with enzymatic catalysts allow up to 12 electrons to be collected per fuel molecule. The Faradaic efficiency of the hybrid system investigated herein lies above 87%. The combination of OxOx with TEMPO-LPEI to obtain a novel hybrid anode to oxidize ethanol to carbon dioxide constitutes a simple methodology with useful application in the development of enzymatic biofuel cells.

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MWCNT-COOH, TEMPO-modified linear poly(ethylenimine), and alcohol (ADH) and aldehyde (AldDH) dehydrogenase immobilization on electrode surfaces yields a hybrid, tri-catalytic architecture that can catalyze complete ethanol electro-oxidation. The chromatographic results obtained for the tri-catalytic hybrid electrode system show that ethanol is totally oxidized to CO2 after 12 h of electrolysis, confirming that organic oxidation catalysts combined with enzymatic catalysts enable collection of up to 12 electrons from ethanol. The Faradaic efficiency lies above 60% for all of the electrode systems investigated herein. Overall, this study illustrates that surface-immobilized, polymer hydrogel-based hybrid multi-catalytic systems exhibit high oxidation rates and constitute a simple methodology with useful application in the development of enzymatic biofuel cells.

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