Chemically modified electrodes (CMEs) based on 2-phenyl-4-((4,6,8-trimethylazulen-1-yl)methylene)oxazol-5(4H)-one (M) were obtained by irreversible electrooxidation of M in millimolar solutions in 0.1 M tetrabutylammonium perchlorate (TBAP) in acetonitrile. These CMEs were characterized by a ferrocene redox probe, electrochemical impedance spectroscopy (EIS), X-ray photon spectroscopy (XPS), and scanning electron microscopy (SEM). The influence of the preparation conditions (charge and potential) was examined. The CMEs were finally used for the analysis of synthetic samples of heavy metal (HM) ions. The paper highlights the importance of potential and electropolymerization charge on the film properties, with accent on recognition of HMs, in order to identify the best conditions for their detection in water. The observed findings are relevant for further design and development of advanced materials based on azulenyl-phenyloxazolone for the analysis of HMs in water.

Electrochemical and spectral studies of benzylidenerhodanine (BR) were performed in order to develop new sensors for heavy metals (HMs) based on chemically modified electrodes (CMEs). CMEs were obtained by cycling and by controlled potential electrolysis at different potentials and charges. Film formation was demonstrated by recording the CV curves of CMEs in transfer solutions containing ferrocene in 0.1 M TBAP/CH3CN. BR-CMEs were used for the analysis of HMs. Samples of Cd(II), Pb(II), Cu(II), and Hg(II), each possessing concentrations between 10−7 and 10−5 M, were analyzed by using CMEs prepared in different conditions. The most intense signal was obtained for the Pb(II) ion. These BR-CMEs can be used for the analysis of Pb(II) in monitored waters. An electrochemical study was performed at different concentrations of BR in 0.1 M TBAP/CH3CN on a glassy carbon electrode by differential pulse voltammetry, cyclic voltammetry, and rotating disk electrode voltammetry. The complexation ratio in the homogeneous solution has been established by the Mollard method in acetonitrile solutions.

The widespread use of Tebuconazole-based fungicides in phytosanitary treatments on a wide range of crops, on the one hand, and the lack of official reports on the amount of fungicide residues in nearby water basins, on the other hand, may lead to uncontrolled and hazardous contamination of water sources used by the resident population, and to serious effects on the environment and public health. Our study explores the acute toxicological risk of this fungicide on various organisms, from bacteria and yeast to fish, using a battery of tests (standardized Toxkit microbiotests and acute semi-static tests). By investigating the interaction between Tebuconazole and bacteria and yeast organisms, we observed that Gram-negative bacteria displayed a strong tolerance for Tebuconazole, while Gram-positive bacteria and yeasts proved to be very sensitive. The fish experiment was conducted on Chelon auratus juveniles exposed to five concentrations of the fungicide Tebustar EW (Tebuconazole, 250 g/L as active substance). After 96 h of exposure, the LC50 for C. auratus was 1.13 mg/L. In the case of the Toxkit microbiotests’ application, the following results were recorded: Spirodela polyrhiza EC50 = 2.204 mg/L (after 72 h exposure), Thamnocephalus platyurus EC50 = 0.115 mg/L (after 24 h), and Daphnia magna EC50 = 2.37 mg/L (after 24–48 h). With the exception of bacteria and yeast, the same response pattern was observed for all non-target species tested; the response range expressed by concentrations causing growth inhibition or mortality was small, ranging between very close values that are quite low, thereby demonstrating the high toxicity of Tebuconazole-based fungicides to the environment.

The present work is connected to the study of electrode conditioning issues for the chemically modified electrodes (CMEs) prepared based on 2,6-bis((E)-2-(thiophen-2-yl)vinyl)-4-(5-isopropyl- 3,8-dimethylazulen-1-yl) pyridine (L). L is irreversibly electrooxidized to polymers leading to L-CMEs. The recognition experiments are the final test of chosen parameters (electropolymerization potential and charge in controlled potential electrolysis (CPE), anodic limit of the overoxidation cycles (OC), number of OC, anodic limit of the equilibration cycles (EC), number of EC, pH of the buffer solutions for HMs accumulation, complexation time, potential and time of reduction). The evidence of film deposition resulted by the change of ferrocene symmetrical signal characteristics on bare electrode in ferrocene solution was the simplest way to prove the formation of L-CMEs. However, finding the best electrode equilibration conditions turned out to be a source of increasing the analytical performance for the CMEs, especially those dedicated to the detection of Pb. The paper underlines the importance of understanding the role of each varied parameter, and of carrying out a systematic study of each possible variable. Optimum conditions for Pb ions analysis, using this new thiophen-vinyl-pyridine-azulene based CMEs, have been established, in order to get the best conditions for its detection in water.

A recently synthesized azulene-tetrazole molecular receptor is proposed in this paper to continue the series of azulene substituted compounds that have been developed to build polyazulene-based materials for heavy metal (HM) ion detection. This study focuses on characterization of (E)-5-((6-t-butyl-4,8-dimethylazulen-1-yl) diazenyl)-1H-tetrazole (L) by electrochemical techniques in view of its use for designing electrochemical sensors for HM ion complexation. The character of redox processes was proved by cyclic, differential pulse, and rotating disk electrode voltammetry. An in-depth thermodynamic study of the complexation properties of the free ligand with Pb(II) and Cd(II) from aqueous solutions was performed, and the stoichiometry and stability constant values were determined. Chemically modified electrodes (CMEs) based on L (L-CMEs) prepared by controlled potential electrolysis (CPE) at different applied potentials and charges were characterized by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Their surface morphology was examined by scanning electron microscopy (SEM). The complexing properties of L-CMEs were investigated towards the detection of HM ions by anodic stripping and compared to the stability constants of the complexes in solution. Voltametric curves showed well-defined peaks for Pb (II), Cd (II), Cu (II) and Hg (II), but the responses differ from each other and vary depending on the ion concentrations in the accumulation solutions. The best results were obtained for Pb(II) and Cd(II) ions. The results obtained for Pb(II) are promising and can be used for its analysis in water solutions (detection limit of about 10−9 M).