Conductive polymers and their composites are excellent materials for coupling biological materials and electrodes in bioelectrochemical systems. It is assumed that their relevance and introduction to the field of bioelectrochemical devices will only grow due to their tunable conductivity, easy modification, and biocompatibility. This review analyzes the main trends and trends in the development of the methodology for the application of conductive polymers and their use in biosensors and biofuel elements, as well as describes their future prospects. Approaches to the synthesis of such materials and the peculiarities of obtaining their nanocomposites are presented. Special emphasis is placed on the features of the interfaces of such materials with biological objects.

Microbial biofilms present one of the most widespread forms of life on Earth. The formation of microbial communities on various surfaces presents a major challenge in a variety of fields, including medicine, the food industry, shipping, etc. At the same time, this process can also be used for the benefit of humans—in bioremediation, wastewater treatment, and various biotechnological processes. The main direction of using electroactive microbial biofilms is their incorporation into the composition of biosensor and biofuel cells This review examines the fundamental knowledge acquired about the structure and formation of biofilms, the properties they have when used in bioelectrochemical devices, and the characteristics of the formation of these structures on different surfaces. Special attention is given to the potential of applying the latest advances in genetic engineering in order to improve the performance of microbial biofilm-based devices and to regulate the processes that take place within them. Finally, we highlight possible ways of dealing with the drawbacks of using biofilms in the creation of highly efficient biosensors and biofuel cells.

The effect of carbon nanomaterials (carbon nanotubes, thermally expanded and pyrolytic graphite) on the bioelectrochemical activity of Gluconobacter oxydans bacterial cells was studied during sorption contact with nanomaterials. For bacterial immobilization, the surface of a working bioelectrode was modified via the application of bacterial suspension in the studied nanomaterial and chitosan. The bioelectrochemical electrode characteristics (the amplitude of generated potential, cyclic volt–ampere characteristics, resistance) were estimated before and in the process of bacterial interaction with ethanol (3-electrode measurement scheme). Modification of the spectral graphite electrode by carbon nanotubes allowed a decrease in the resistance of the charge transfer by 48% and an increase in the oxidation current on cyclic volt—ampere characteristics at a voltage of 200 mV by 21% as compared with nonmodified electrode. The thermally expanded and pyrolytic graphite increased the bioelectrode resistance to 4050 and 8447 Ohm cm², respectively. Mathematical modeling demonstrated that from 75 to 100% of biomaterial (depending on the used nanomaterial) were involved in the process of electricity generation with the selected method of the bacterial immobilization. The use of data obtained during the development of microbial biosensors and electrodes of biofuel cells is discussed.

Electropolymerized neutral red, thionine, and aniline were used as part of hybrid nanocomposite conductive polymers, to create an amperometric reagent-less biosensor for glucose determination. The structure of the obtained polymers was studied using infrared (IR) spectroscopy and scanning electron microscopy. Electrochemical characteristics were studied by cyclic voltammetry and impedance spectroscopy. It was shown that, from the point of view of both the rate of electron transfer to the electrode, and the rate of interaction with the active center of glucose oxidase (GOx), the most promising is a new nanocomposite based on poly(neutral red) (pNR) and thermally expanded graphite (TEG). The sensor based on the created nanocomposite material is characterized by a sensitivity of 1000 ± 200 nA × dm³/mmol; the lower limit of the determined glucose concentrations is 0.006 mmol/L. The glucose biosensor based on this nanocomposite was characterized by a high correlation (R² = 0.9828) with the results of determining the glucose content in human blood using the standard method. Statistical analysis did not reveal any deviations of the results obtained using this biosensor and the reference method. Therefore, the developed biosensor can be used as an alternative to the standard analysis method and as a prototype for creating sensitive and accurate glucometers, as well as biosensors to assess other metabolites.

The possibility of the developing a biochemical oxygen demand (BOD) biosensor based on electroactive biofilms of activated sludge grown on the surface of a graphite-paste electrode modified with carbon nanotubes was studied. A complex of microscopic methods controlled biofilm formation: optical microscopy with phase contrast, scanning electron microscopy, and laser confocal microscopy. The features of charge transfer in the obtained electroactive biofilms were studied using the methods of cyclic voltammetry and electrochemical impedance spectroscopy. The rate constant of the interaction of microorganisms with the extracellular electron carrier (0.79 ± 0.03 dm³(g s)⁻¹) and the heterogeneous rate constant of electron transfer (0.34 ± 0.02 cm s⁻¹) were determined using the cyclic voltammetry method. These results revealed that the modification of the carbon nanotubes’ (CNT) electrode surface makes it possible to create electroactive biofilms. An analysis of the metrological and analytical characteristics of the created biosensors showed that the lower limit of the biosensor based on an electroactive biofilm of activated sludge is 0.41 mgO₂/dm³, which makes it possible to analyze almost any water sample. Analysis of 12 surface water samples showed a high correlation (R² = 0.99) with the results of the standard method for determining biochemical oxygen demand.