The development of sensing coatings, as important sensor elements that integrate functionality, simplicity, chemical stability, and physical stability, has been shown to play a major role in electrochemical sensing system development trends. Simple and versatile assembling procedures and scalability make polyelectrolytes highly convenient for use in electrochemical sensing applications. Polyelectrolytes are mainly used in electrochemical sensor architectures for entrapping (incorporation, immobilization, etc.) various materials into sensing layers. These materials can often increase sensitivity, selectivity, and electronic communications with the electrode substrate, and they can mediate electron transfer between an analyte and transducer. Analytical performance can be significantly improved by the synergistic effect of materials (sensing material, transducer, and mediator) present in these composites. As most reported methods for the preparation of polyelectrolyte-based sensing layers are layer-by-layer and casting/coating methods, this review focuses on the use of the latter methods in the development of electrochemical sensors within the last decade. In contrast to many reviews related to electrochemical sensors that feature polyelectrolytes, this review is focused on architectures of sensing layers and the role of polyelectrolytes in the development of sensing systems. Additionally, the role of polyelectrolytes in the preparation and modification of various nanoparticles, nanoprobes, reporter probes, nanobeads, etc. that are used in electrochemical sensing systems is also reviewed.

The focus of this work was to develop a simple electrochemical method for the determination of vitamin C (VitC) by using a specially constructed microelectrode made from pyrolytic graphite sheet (PGS). A procedure for quantifying VitC in a real sample was established. VitC shows a single quasi-reversible reaction. The method was optimized, and analytical determination was performed by using cyclic voltammetry and square wave voltammetry for electroanalytical purposes. The obtained results show a linear response of the PGS electrode in a wide concentrations range. For the lower concentration range, 0.18–7.04 µg L⁻¹, the sensitivity is 11.7 µAcm⁻²/mgL⁻¹, while for the higher concentration range, 10.6–70.4 µg L⁻¹, the sensitivity is 134 µAcm⁻²/mgL⁻¹, preserving the linearity of 0.998 and 0.999. The second objective was to determine the effect of the addition of five different types of “green” biowaste on plant growth, VitC content, and antioxidant activity in arugula (Eruca sativa L.) using the developed method. After three weeks of cultivation, small differences in growth and large differences in certain nutritional characteristics were observed. The addition of black coffee makes the soil slightly alkaline and causes a significant increase in VitC content and antioxidant activity.

Carbon nanotubes (CNTs) are widely used in electrochemical sensors due to their significant impact on the electroanalytical signal. However, there remain significant doubts regarding the origin of the improved electroanalytical response observed in CNT-based sensors, particularly concerning the precise role of CNTs in these systems. In particular, the origin of the electrochemical response is controversial, as it may be due to either electrocatalytic or non-electrocatalytic processes. The latter implies that the electroanalytical response is mainly governed by the mass transport phenomena within the porous CNT layer. This article briefly reviews the several comprehensive models based on the role of porosity (diffusion in a ‘thin-layer’) on the electrochemical behavior as well as on the electrocatalytic properties of CNTs to resolve conflicts arising from misinterpretations of the electroanalytical response of CNT-based sensors. However, even though there are some explanations and conclusions on this topic, they seem to be valuable for specific electroactive species, the type of CNTs and/or electrode architecture, the electrode surface, etc. Accordingly, general theories and conclusions are not yet defined, so different approaches to this topic are still needed, since the main phenomenological effects responsible for the nature of the electrochemical response of the electrodes modified with CNTs need to be determined in a rational way.