This paper describes a miniaturized multisensor platform (MP-ISES) consisting of electrodes: a reference one (RE) and ion-selective electrodes (ISEs) for monitoring Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, and SCN⁻ ions and pH in human saliva. Gold electrode surface was modified by deposition of two layers: electrosynthesized PEDOT:PSS forming an intermediate layer, and ion-selective membrane. The developed ISEs were characterized by a wide linear range and sensitivity consistent with the Nernst model. The entire MP-ISEs are characterized by satisfactory metrological parameters demonstrating their applicability in biomedical research, in particular in measurements concerning determination of ionic profiles of saliva. Saliva samples of 18 volunteers aged from 20 to 26 participating in a month experiment had been daily collected and investigated using the MP-ISEs assigned individually to each person. Personalized profiles of ions (ionograms) in saliva, such as Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, SCN⁻, and H⁺, were obtained.

A new solid-contact potentiometric ion-selective electrode for the determination of SCN⁻ (SCN-ISE) has been described. Synthesized phosphonium derivative of calix[4]arene was used as a charged ionophore. The research included selection of the ion-selective membrane composition, determination of the ISEs metrological parameters and SCN-ISE application for thiocyanate determination in human saliva. Preparation of the ISEs included selection of a plasticizer for the ion-selective membrane composition and type of the electrode material. The study was carried out using ISE with liquid internal electrolyte (LE-ISE) and solid-contact electrodes made of glassy carbon (GC-ISE) and gold rods (Au-ISE). The best parameters were found for GC sensors for which the ion-selective membrane contained chloroparaffin as a plasticizer (S = 59.9 mV/dec, LOD = 1.6 × 10⁻⁶ M). The study of potentiometric selectivity coefficients has shown that the thiocyanate-selective sensor could be applied in biomedical research for determination of SCN⁻ concentration in human saliva. The accuracy of the SCN⁻ determination was verified by testing 59 samples of volunteers’ saliva by potentiometric sensors and UV-Vis spectrophotometry as a reference technique. Moreover, SCN⁻ concentrations in the smokers’ and non-smokers’ saliva were compared. In order to investigate the influence of various factors (sex, health status, taken medications) on the thiocyanate level in the saliva, more extensive studies on a group of 100 volunteers were carried out. Additionally, for a group of 18 volunteers, individual profiles of SCN⁻ concentration in saliva measured on a daily basis for over a month were collected.

There is growing interest for bioanalytical tools that might be designed for a specific user, primarily for research purposes. In this perspective, a new, highly stable potentiometric sensor based on glassy carbon/polyazulene/NH₄⁺-selective membrane was developed and utilized for urease activity determination. Urease–urea interaction studies were carried out and the Michaelis–Menten constant was established for this enzymatic reaction. Biofunctionalization of the ammonium ion-selective sensor with urease lead to urea biosensor with remarkably good potential stability (drift coefficient ~0.9 mV/h) and short response time (t_95% = 36 s). The prepared biosensor showed the Nernstian response (S = 52.4 ± 0.7 mV/dec) in the urea concentration range from 0.01 to 20 mM, stable for the experimental time of 60 days. In addition, some insights into electrical properties of the ion-to-electron transducing layer resulting from impedance spectroscopy measurements are presented. Based on the RCQ equivalent circuits comparison, it can be drawn that the polyazulene (PAz) layer shows the least capacitive behavior, which might result in good time stability of the sensor in respect to response as well as potential E⁰. Both the polyazulene-based solid-contact ion selective electrodes and urea biosensors were successfully used in trial studies for determination of ammonium ion and urea in human saliva samples. The accuracy of ammonium ion and urea levels determination by potentiometric method was confirmed by two reference spectrophotometric methods.