Grzegorz Milczarek

The demetallation reaction of sulfanyl magnesium(II) porphyrazine with N-ethylphthalimide substituents, followed by remetallation with manganese(II) salts, yields the corresponding manganese(III) derivative (Pz3) with high efficiency. This novel manganese(III) sulfanyl porphyrazine was characterized by HPLC and analyzed using UV-Vis, MS, and FT-IR spectroscopy. Electrochemical experiments of Pz3 conducted in dichloromethane revealed electrochemical activity of the new complex due to both manganese and N-ethylphthalimide substituents redox transitions. Subsequently, Pz3 was deposited on multiwalled carbon nanotubes (MWCNTs), and this hybrid material was then applied to glassy carbon electrodes (GC). The resulting hybrid electroactive electrode material, combining manganese(III) porphyrazine with MWCNTs, showed a significant decrease in overpotential of H₂O₂ oxidation compared to bare GC or GC electrodes modified with only carbon nanotubes (GC/MWCNTs). This improvement, attributed to the electrocatalytic performance of Mn³⁺, enabled linear response and sensitive detection of H₂O₂ at neutral pH. Furthermore, a glucose oxidase (GOx)-containing biosensing platform was developed by modifying the prepared GC/MWCNT/Pz3 electrode for the electrochemical detection of glucose. The bioelectrode incorporating the newly designed Pz3 exhibited good activity in the presence of glucose, confirming effective electronic communication between the Pz3, GOx and MWCNT surface. The linear range for glucose detection was 0.2–3.7 mM.

This paper presents a novel modified electrode for an amperometric hydrazine sensor based on multi-walled carbon nanotubes (MWCNTs) modified with lignosulfonate (LS) and decorated with palladium nanoparticles (NPds). The MWCNT/LS/NPd hybrid was characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The electrochemical properties of the electrode material were evaluated using cyclic voltammetry and chronoamperometry. The results showed that GC/MWCNT/LS/NPd possesses potent electrocatalytic properties towards the electro-oxidation of hydrazine. The electrode demonstrated exceptional electrocatalytic activity coupled with a considerable sensitivity of 0.166 μA μM⁻¹ cm⁻². The response was linear from 3.0 to 100 µM L⁻¹ and 100 to 10,000 µM L⁻¹, and the LOD was quantified to 0.80 µM L⁻¹. The efficacy of the modified electrode as an electrochemical sensor was corroborated in a study of hydrazine determination in water samples.

A metal-free porphyrazine derivative with peripheral phthalimide substituents was metallated with a nickel(II) ion. The purity of the nickel macrocycle was confirmed using HPLC, and characterized by MS, UV–VIS, and 1D (¹H, ¹³C) and 2D (¹H–¹³C HSQC, ¹H–¹³C HMBC, ¹H–¹H COSY) NMR techniques. The novel porphyrazine was combined with various carbon nanomaterials, such as carbon nanotubes—single walled (SWCNTs) and multi-walled (MWCNTs), and electrochemically reduced graphene oxide (rGO), to create hybrid electroactive electrode materials. The carbon nanomaterials’ effect on the electrocatalytic properties of nickel(II) cations was compared. As a result, an extensive electrochemical characterization of the synthesized metallated porphyrazine derivative on various carbon nanostructures was carried out using cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). An electrode modified with carbon nanomaterials GC/MWCNTs, GC/SWCNTs, or GC/rGO, respectively, was shown to have a lower overpotential than a bare glassy carbon electrode (GC), allowing for the measurement of hydrogen peroxide in neutral conditions (pH 7.4). It was shown that among the tested carbon nanomaterials, the modified electrode GC/MWCNTs/Pz3 exhibited the best electrocatalytic properties in the direction of hydrogen peroxide oxidation/reduction. The prepared sensor was determined to enable a linear response to H₂O₂ in concentrations ranging between 20–1200 µM with the detection limit of 18.57 µM and sensitivity of 14.18 µA mM⁻¹ cm⁻². As a result of this research, the sensors produced here may find use in biomedical and environmental applications.

A sulfanyl porphyrazine derivative with peripheral phthalimide moieties was metallated with cobalt(II) and iron(II) metal ions. The purity of the macrocycles was confirmed by HPLC, and subsequently, compounds were characterized using various analytical methods (ES-TOF, MALDI-TOF, UV–VIS, and NMR spectroscopy). To obtain hybrid electroactive electrode materials, novel porphyrazines were combined with multiwalled carbon nanotubes. The electrocatalytic effect derived from cobalt(II) and iron(II) cations was evaluated. As a result, a significant decrease in the overpotential was observed compared with that obtained with bare glassy carbon (GC) or glassy carbon electrode/carbon nanotubes (GC/MWCNTs), which allowed for sensitive determination of hydrogen peroxide in neutral conditions (pH 7.4). The prepared sensor enables a linear response to H₂O₂ concentrations of 1–90 µM. A low detection limit of 0.18 μM and a high sensitivity of 640 μA mM⁻¹ cm⁻² were obtained. These results indicate that the obtained sensors could potentially be applied in biomedical and environmental fields.

The adsorption behavior of walnut shells in the presence of colloidal gold for thallium(I) ions from aqueous solution was investigated. The thallium content in the samples before and after contact with walnut shells was determined by differential pulse anodic stripping voltammetry. The adsorption capacity was studied in relation to the function of equilibrium time, the amount of adsorbent, the concentration of thallium, and pH. For the sake of comparison, the sorptive properties of walnut shells were compared to soapnut powder. The obtained results clearly indicate that both walnut shells and soap nuts are effective sorbents for thallium(I) ions (removal efficiency over 90%). The best results of sorption were achieved at pH = 7.5 after contact time of 30 min. The addition of colloidal gold stabilised by lignosulfonate as the co-adsorber enhances the sorption ability of walnut shells to over 99%.

Grain products and the associated industry have a notable economic and social impact all over the world. The toxicological safety of grain products is a nutritional prerogative. This study focused on the determination of thallium content in grain product samples collected from a commercial brand commonly available in Poland. The samples were analyzed with the use of differential pulse anodic stripping voltammetry (DPASV) with graphene oxide based on glassy carbon. The stripping anodic peak current of thallium was linear over its concentration range from 9.78 × 10⁻⁹ to 97.8 × 10⁻⁹ M. The limit of detection (LOD) was calculated according to the formula LOD = (κ × SDa)/b, where κ is 3.3, SDa is the standard deviation of the intercept, and b is the slope. The determined value of LOD was 1.229 µg L⁻¹ (6.01 × 10⁻⁹ M). The proposed method was successfully applied for the determination of thallium ions in samples of actual grain products. The obtained results confirmed that thallium was present in the studied cereal samples (average content at 0.0268 ± 0.0798 mg/kg). Thallium has a half-life of 60 days; therefore, the consumption of foods with thallium content of approximately 0.08 mg/kg has the potential for harmful bioaccumulation in the body. Thallium contamination in cereal products should be a critical parameter for health environmental regulations.

The synthesis of manganese lignosulfonates by a two-step method has been reported. It was based on the conversion of technical sodium derivative of lignosulfonate to its hydrogen form i.e., lignosulfonic acid and its further reaction with manganese hydroxide. The obtained product was electroactive, and could be applied as the precursor of electroactive manganese oxide. The product showed a reversible redox activity in the potential range of 0 to 1 V vs. an Ag/AgCl reference electrode. The electroactivity of the obtained product can be tentatively assigned to the redox activity of both the electrodeposited MnO_x and the presence of lignosulfonate-derived quinones since the energy dispersive spectroscopy (EDS) confirmed the presence of organic matter in the deposit. It also showed substantial electrocatalytic activity towards the anodic oxidation of hydrogen peroxide. This suggests that manganese lignosulfonates could be a valuable compound for the electrochemical preparation of electroactive layers that are suitable in the development of electrochemical sensors.