Ovidiu-Teodor Matica

Chemically modified electrodes based on derivatives of 2-thioxothiazolidin-4-one were mentioned as possible solutions for heavy metal (HM) ions heterogeneous recognition. Such ligands form thin films with reversible responses in the ferrocene redox probe with a well-defined symmetrical peak and symmetrical values for the anodic and cathodic currents. Their selectivity in coordinating HM ions was proven. In this paper, a computer-added study was performed using density functional theory (DFT) based on two methods, B3LYP and ωB97XD, to arrive at a better inside of their structure. Properties related to their reactivity concerning experimental electrochemical behaviour and spectral results were calculated using specific molecular descriptors. DFT-calculated HOMO-LUMO energies were found in good linear correlation with experimental redox potential. The accuracy of the calculations was also proven by a good agreement between the energy calculated by the DFT method and the UV-Vis spectra for the studied ligands. Such a computational approach can be used to evaluate the properties of possible new ligands for such electrochemical applications. The strong correlation between DFT-predicted quantum parameters and experimental redox potentials underscores the relevance of these computational approaches in designing selective molecular sensors. The results obtained using the two functionals are in good agreement, although there are also situations and parameters for which the results are not identical. There is a symmetry of the values obtained by the electrochemical and spectral methods with those calculated by DFT.

Novel chemically modified electrodes (CMEs) based on azulene were prepared by electrooxidation of guaiazulene derivative 4-((5-isopropyl-3,8-dimethylazulen-1-yl)methylene)-2-phenyloxazol-5(4H)-one (G). G is based on guaiazulene non-alternating aromatic hydrocarbon exhibiting a less symmetrical structure compared to naphthalene skeletal derivative. Therefore, it can be used as a building block for the preparation of novel materials. To evaluate the chemical structure and surface images, the CMEs based on G (G-CMEs) were characterized by ferrocene redox probe, X-ray photon spectroscopy (XPS), and scanning electron microscopy (SEM). They were also tested for the analysis of synthetic samples of heavy metal (HM) ions. The influence of preparation conditions (electric charge and potential) on the properties of these CMEs was examined. This paper highlights the importance of electropolymerization conditions on electrodeposited film surfaces, especially on their analytical properties vs. Cd(II), Pb(II), Cu(II), and Hg(II) investigated ions. This study is relevant for further design and development of advanced materials based on azulenyl-phenyloxazolone for the HM analysis in water. A linear dependence of the peak currents for Pb(II) ion on the concentration in test aqueous solutions was obtained between 10⁻⁷ M and 5·10⁻⁵ M. The detection limits of 5·10⁻⁶ M; 10⁻⁷ M; 5·10⁻⁶ M; and 10⁻⁵ M were estimated for Cd(II), Pb(II), Cu(II), and Hg(II), respectively, for G-CMEs.

Rhodanine (R) is a heterocycle having complexing properties for heavy metal (HM) ions. Considering the similar electron-donating character of diethylaminobenzene and azulene, electrochemical characterization of (Z)-5-(azulen-1-ylmethylene)-2-thioxo-thiazolidin-4-one (R1) and 5-(4 diethylamino-benzylidene)-2-thioxo-thiazolidin-4-one (R2) was performed to establish their common features. Chemically modified electrodes based on R1 and R2 were compared for HM recognition. Evidence for the formation of films was provided by scanning and controlled potential electrolysis, and HM recognition experiments were performed using their films. Parallel studies for analysis of HMs by complexation in solution were performed by UV-Vis. The analogy between R1 and R2 created the premise for easier selection of compounds for certain applications. The performance of the chemically modified electrodes was evaluated as detection limits for HMs. The azulene monomer (R1) proved to be the best candidate for Pb(II) detection, being about eight times more sensitive than R2. However, in solution, R2 proved to be a good choice for optical measurements, having a higher absorption coefficient. These results support the two ligands having different behaviors in homogeneous and heterogeneous systems.

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.

Previous studies performed on 2-(azulen-1-yldiazenyl)-5-phenyl-1,3,4-thiadiazole (T) showed that T is a ligand with complexing properties towards heavy metals (HMs) in solution and can be attached to electrode surfaces. Films of T were deposited on glassy carbon to obtain chemically modified electrodes (T-CMEs), either through scanning or using controlled potential electrolysis in tetrabutylammonium perchlorate in acetonitrile. They were investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and spectroelectrochemistry. All methods provided evidence for showing the formation of insulating films, with properties depending on their electropolymerization potential. CV and EIS studies of T-CMEs in tetrabutylammonium perchlorate in acetonitrile as supporting electrolyte, and in the presence of a ferrocene redox probe resulted in a thickness of ~10 µm, an active surface area about 6 times higher than the geometrical one, and conductivity of about 10⁻⁶ S/cm. This characterization performed using voltammetric techniques reveals the symmetry of the reversible anodic and cathodic redox CV peaks for the polymer, while spectroelectrochemistry shows the intensification of the charge transport process through polarons, due to the anodic polarization of the film.

The spectral properties of several azulene-oxazolone derivatives containing a phenyloxazolone moiety linked to a substituted azulene ring via a C=C double bond were studied in different solvents of varying polarity. The solvatochromism and the ability of azulene-oxazolone derivatives to recognize heavy metal ions were investigated. In order to estimate the contribution of the non-specific and specific solute–solvent interactions, multiple linear regression analysis using Kamlet–Taft, Catalan and Laurence parameters was applied. These azulene derivatives demonstrate positive solvatochromism. The methyl and isopropyl substituents at the seven-membered azulene ring determine the highest red shifts of the absorption maxima of these azulenyl-vinyl-oxazolones. According to Catalan and Laurence models, the solvent polarizability is a more significant parameter in describing the solvatochromic properties of the azulene-oxazolone derivatives. The azulene-oxazolone compounds under study showed a good response to heavy metal cations (Cd²⁺, Hg²⁺, Cu²⁺ and Pb²⁺).

The electrochemical study of 2‐Sulfanylidene‐1,3‐thiazolidin‐4‐one (rhodanine, R) was performed on a glassy carbon working electrode by using three methods: differential pulse voltammetry (DPV), cyclic voltammetry (CV), and linear sweep voltammetry (LSV) at rotating disk electrode voltammetry (RDE). The CV, DPV, and LSV at RDE curves for R were recorded at different concentrations in 0.1 M TBAP/CH₃CN. Polymeric films were formed by successive cycling at different potentials and by controlled potential electrolysis. The film formation was proved by recording the CV curves of the chemically modified electrodes (CMEs) in transfer solutions containing ferrocene in 0.1 M TBAP/CH₃CN. The obtained CMEs were used for the detection of heavy metal ions. Synthetic samples of heavy metal ions (Cd (II), Pb (II), Cu (II), Hg (II)) of concentrations between 10⁻⁷ and 10⁻⁵ M were analyzed using CMEs prepared in different conditions. The most intense signal was obtained for Pb(II) ion (estimated detection limit = 10⁻⁷ M), which shows that these CMEs can be used for Pb(II) ion detection. The ability of R to form complexes with Pb(II) ion was also tested by UV‐Vis spectrometry. The obtained results showed the formation of Pb(II)R₂ as the most stable complex.

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.

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).

Chemically modified electrodes (CMEs) based on polymeric films of E-5-((5-isopropyl-3,8-dimethylazulen-1-yl) diazenyl)-1H-tetrazole (L) deposited on the surface of the glassy carbon electrode have been used for the recognition of heavy metal (Me) ions. The electrochemical study of L was done by three methods: differential pulse voltammetry (DPV), cyclic voltammetry (CV), and rotating disk electrode voltammetry (RDE). The CV, DPV, and RDE studies for L were performed at different concentrations in 0.1 M tetrabutylammonium perchlorate solutions in acetonitrile. The polymeric films were formed by successive cycling or by controlled potential electrolysis (CPE). The film formation was proven by recording the CV curves of the CMEs in ferrocene solution. The CMEs prepared at different charges or potentials were used for detection of heavy metal ions. Synthetic samples of heavy metal ions (Cd(II), Pb(II), Cu(II), Hg(II)) of concentrations between 10⁻⁸ and 10⁻⁴ M were analyzed. The most intense signal was obtained for Pb(II) ion (detection limit of about 10⁻⁸ M). Pb(II) ion can be detected by these CMEs in waters at such concentrations. The ability of the ligand L to form complexes with Pb(II) and Hg(II) ions was also tested by UV-Vis spectrometry. The obtained results showed the formation of Me(II)L₂ complexes.