Lignosulfonate-Assisted In Situ Deposition of Palladium Nanoparticles on Carbon Nanotubes for the Electrocatalytic Sensing of Hydrazine.

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.

The Influence of an Extended π Electron System on the Electrochemical Properties and Oxidizing Activity of a Series of Iron(III) Porphyrazines with Bulky Pyrrolyl Substituents.

The present study investigates four iron(II/III) porphyrazines with extending pyrrolyl peripheral substituents to understand the impact of introduced phenyl rings on the macrocycle's electrochemical and spectroelectrochemical properties as well as their activity in oxidation reactions. The electrochemical studies showed six well-defined redox processes and quasi-reversible one-electron transfers-two originating from the iron cation and four related to the ring. Adding phenyl rings to the periphery increased the electrochemical gap by 0.1 V. The UV-Vis spectra changes were observed at the applied potential of -1.3 V with the presence of additional red-shifted bands. The oxidizing studies showed increased efficiency in the oxidation reaction of the reference substrate in the cases of Pz1 and Pz2 in both studied oxygen atom donors. The calculated reaction rates in t-BuOOH were 12.0 and 15.0 mmol/min, respectively, for Pz1 and Pz2, compared to 6.4 for Pz3 and 1.8 mmol/min for Pz4. The study identified potential applications for these porphyrazines in mimicking cytochrome P450 prosthetic groups for oxidation and hydroxylation reactions in the future.

Synthesis, Electrochemical and Photochemical Properties of Sulfanyl Porphyrazine with Ferrocenyl Substituents.

Ferrocene is useful in modern organometallic chemistry due to its versatile applications in material sciences, catalysis, medicinal chemistry, and diagnostic applications. The ferrocene moiety can potentially serve many purposes in therapeutics and diagnostics. In the course of this study, (6-bromo-1-oxohexyl)ferrocene was combined with dimercaptomaleonitrile sodium salt to yield a novel maleonitrile derivative. Subsequently, this compound was subjected to an autocyclotetramerization reaction using the Linstead conditions in order to obtain an octaferrocenyl-substituted magnesium(II) sulfanyl porphyrazine. Following that, both compounds-the maleonitrile derivative and the porphyrazine derivative-were subjected to physicochemical characterization using UV-Vis, ES-TOF, MALDI-TOF, and one-dimensional and two-dimensional NMR spectroscopy. Moreover, the sulfanyl porphyrazine was subjected to various photophysical studies, including optical absorption and emission measurements, as well as the evaluation of its photochemical properties. Values of singlet oxygen generation quantum yields were obtained in different organic solvents. The electrochemical properties of the synthesized compounds were studied using cyclic voltammetry. According to the electrochemical results, the presence of electron-withdrawing oxohexyl groups attached to ferrocene afforded significantly more positive oxidation potentials of the ferrocene-based redox process up to 0.34 V vs. Fc+/Fc.

Improved Electrochemical Hydrogen Peroxide Detection Using a Nickel(II) Phthalimide-Substituted Porphyrazine Combined with Various Carbon Nanomaterials.

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 Synergistic Effect of Phthalimide-Substituted Sulfanyl Porphyrazines and Carbon Nanotubes to Improve the Electrocatalytic Detection of Hydrogen Peroxide.

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.

Glucose determination using amperometric non-enzymatic sensor based on electroactive poly(caffeic acid)@MWCNT decorated with CuO nanoparticles.

A novel non-enzymatic glucose sensor based on poly(caffeic acid)@multi-walled carbon nanotubes decorated with CuO nanoparticles (PCA@MWCNT-CuO) was developed. The described approach involves the complexation/accumulation of Cu(II) on PCA@MWCNT followed by electrochemical CuO deposition in an alkaline electrolyte. The morphology and surface characteristics of the nanomaterial were determined by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM), Raman spectroscopy, and inductively coupled plasma mass spectrometry (ICP-MS). A hybrid-support sensor device was then developed to assess the glucose concentration in different solutions. The sensitivity of the electrode is 2412 µA mM-1 cm-2. The electrode exhibited a broad linear range of 2 µM to 9 mM and a low limit of detection (LOD) of 0.43 µM (relative standard deviation, RSD = 2.3%) at + 0.45 V vs Ag/AgCl. The excellent properties obtained for glucose detection were most likely due to the synergistic effect of the combination of individual components: poly(caffeic acid), MWCNTs, and CuO. Good accuracy and high precision were demonstrated for quantifying glucose concentrations in human serum and blood samples (the recovery ranged from 95.0 to 99.5%). The GC/PCA@MWCNT-CuO sensor represents a novel, simple, and low-cost approach to the fabrication of devices for amperometric sensing of glucose.

Portable glucose biosensor based on polynorepinephrine@magnetite nanomaterial integrated with a smartphone analyzer for point-of-care application.

This work describes a novel nanoplatform based on polynorepinephrine (PNE) grafted on magnetite nanoparticles (Fe3O4) with glucose oxidase (GOx) from Aspergillus niger (Fe3O4@PNE-GOx). The system was integrated with a smartphone analyzer as a potential point-of-care testing (POCT) biosensor for glucose measurement. Covering the magnetite surface with the biomimetic polymer polynorepinephrine significantly increased the effectiveness of enzyme immobilization which was 38.40 mg g-1, compared with 17.30 mg g-1 on the bare surface of magnetite. The Fe3O4@PNE-GOx nanoplatform was deposited on a screen-printed electrode (SPE) and then used with the world's smallest ready-to-go potentiostat and a smartphone in tandem for glucose measurement. This biosensor displayed abroad range of linearity (0.2-24 mM), a low detection limit (6.1 µM), and good sensitivity (97.34 µA mM-1 cm-2). Moreover, it exhibited a fast electrocatalytic response (8 s), and long-term stability (up to 20 weeks). It was used to detect glucose in real samples such as human serum, human blood, infusion fluid, and commercial glucose solutions. The results obtained indicate that the proposed biosensor may be an attractive system for point-of-care testing (POCT), or in various industries, using asmartphone and potentiostat in tandem.

Lignosulfonate-assisted synthesis of platinum nanoparticles deposited on multi-walled carbon nanotubes for biosensing of glucose.

It is presented in this work that lignosulfonate (LS) can be preferentially adsorbed on the surface of multi-walled carbon nanotubes (MWCNT) giving rise to the functional platform for platinum nanoparticles (NPt) deposition. The novel MWCNT/LS/NPt hybrid material has been characterized by X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS). The morphology of the MWCNT/LS/NPt electrodes has been investigated by atomic force microscopy (AFM). The electrochemical studies of MWCNT/LS/NPt hybrid material revealed strong electrocatalytic properties towards hydrogen peroxide. In addition, the effects of lignosulfonate amount adsorbed at the MWCNT on the voltammetric response of the hydrogen peroxide were discussed and used to select the optimal and effective conditions for the synthesis of the electrode material. An amperometric biosensor for glucose was developed based on the covalent linkage of glucose oxidase (GOx) at the MWCNT/LS/NPt. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for glucose. The linear range of the glucose determination was 50-1400 µM and LOD was quantified as 15.67 µM.

Azaporphyrins Embedded on Carbon-Based Nanomaterials for Potential Use in Electrochemical Sensing-A Review.

Phthalocyanines and porphyrazines as macrocyclic aza-analogues of well-known porphyrins were deposited on diverse carbon-based nanomaterials and investigated as sensing devices. The extended π-conjugated electron system of these macrocycles influences their ability to create stable hybrid systems with graphene or carbon nanotubes commonly based on π-π stacking interactions. During a 15-year period, the electrodes modified by deposition of these systems have been applied for the determination of diverse analytes, such as food pollutants, heavy metals, catecholamines, thiols, glucose, peroxides, some active pharmaceutical ingredients, and poisonous gases. These procedures have also taken place, on occasion, in the presence of various polymers, ionic liquids, and other moieties. In the review, studies are presented that were performed for sensing purposes, involving azaporphyrins embedded on graphene, graphene oxide or carbon nanotubes (both single and multi-walled ones). Moreover, possible methods of electrode fabrication, limits of detection of each analyte, as well as examples of macrocyclic compounds applied as sensing materials, are critically discussed.

Voltammetric sensor based on long alkyl chain tetraalkylammonium ionic liquids comprising ascorbate anion for determination of nitrite.

An electrochemical sensor was fabricated utilizing ionic liquids possessing cations with long alkyl chains such as trimethyl octadecylammonium and behenyl trimethylammonium and ascorbate anion. The ionic liquids were drop-coated onto the electrode. Thin modifying layers were prepared. Cyclic voltammetric investigations revealed electrostatic interactions between the electrochemical probes and the modified surface, proving that a positive charge was established at the film surface. Hence, negatively charged species such as nitrite can be pre-concentrated on the surface of presented modified electrodes. The fabricated electrodes have been used as a voltammetric sensor for nitrite. Due to the electrostatic accumulation properties of long alkyl cation, the assay exhibits a remarkable improvement in the voltammetric response toward nitrite oxidation. The influence of pH on the electrode response was thoroughly investigated, and the mechanism of the electrode was established. The developed sensor showed a linear electrochemical response in the range 1.0-50 µM with a detection limit of 0.1 µM. The electrode revealed good storage stability, reproducibility, and anti-interference ability. The determination of nitrite performed in curing salts brought satisfactory results.

Application of the electropolymerized poly(3,4-ethylenedioxythiophene) sorbent for solid-phase microextraction of bisphenols.

A new, simple, and effective procedure using poly(3,4-ethylenedioxythiophene)/lignosulfonate electropolymerized sorbent solid-phase microextraction (PEDOT/LS-SPME) combined with LC-MS/MS for determination of bisphenols in environmental water samples was developed. Various parameters influencing the performance of the analytical procedure including the type of sorbent, electropolymerization time, sorbent preconditioning time, extraction time, desorption (time and solvent), and sample pH were investigated and optimized. Under optimal conditions the proposed method allowed us to achieve good precision (n = 5) between 6.0 and 12.1%. The limits of detection were equal to 0.17 µg L-1 for BPA, 0.16 µg L-1 for BPF, 0.07 µg L-1 for BPE, 0.05 µg L-1 for BPB, and 0.027 µg L-1 for BPAF. The proposed method was successfully applied for the determination of bisphenols in aqueous environmental samples.

Thallium in color tattoo inks: risk associated with tattooing.

BACKGROUND: Allergic reactions to metals and metal salts used in tattoo pigments occur surprisingly frequently. For this reason, this study focused on the determination of thallium (Tl) in the samples of color tattoo inks. These inks are commonly used in tattooing processes worldwide. MATERIAL AND METHODS: The samples were analyzed with the use of differential pulse anodic stripping voltammetry. The stripping anodic peak current of Tl was linear over its concentration range of 0.5-6.0 µg/l, which corresponds to 2.45×10-9-2.94×10-8 M. The determined value of the limit of detection (LOD) was equal to 0.149 µg/l (7.29×10-10 M). RESULTS: The obtained results revealed a wide range of Tl contents in tattoo inks, i.e., 0.0029-0.4275 µg/g. The content of this metal varied substantially depending on the pigment used in tattoo inks. CONCLUSIONS: Thallium was identified and determined in all tested samples. Its content depends on the country of origin but it does not depend directly on the color. The lowest content of Tl was found in the pink ink and the highest in the violet ink (from Israel), and a similar content was also found in the yellow ink (from Israel). The use of colored inks in larger quantities (a dense pattern and a larger surface area covered) may potentially pose a health risk. The danger of Tl poisoning from tattooing depends on the type of the ink (color) and its origin. As Tl is not considered a micronutrient, introducing such a Tl content into the body may be associated with a potentially harmful accumulation of this metal in body organs, causing various types of ailments and toxic effects primarily on the nervous, skeletal and circulatory systems. The obtained results suggest that tattooists may be exposed to the toxic effects of Tl in tattoo inks. The analytical data presented in the paper may constitute the basis for determining the acceptable limits of toxic Tl contents in tattoo inks. Med Pr. 2020;71(4):405-11.

A nanocomposite consisting of reduced graphene oxide and electropolymerized ß-cyclodextrin for voltammetric sensing of levofloxacin.

A glassy carbon electrode (GCE) was modified with a nanocomposite prepared from polymerized ß-cyclodextrin (ß-CD) and reduced graphene oxide (rGO). The modified GCE is shown to enable the voltammetric determination of traces of levofloxacin (LEV) by various electrochemical techniques. Experimental factors affecting the results including the amount of the substrates in preparation of the nanocomposite, accumulation time, the scan rate and pH value of the electrolyte were optimized. The modified GCE, best operated at a working potential of 1.00 V (vs. Ag/AgCl), has two linear response ranges, one for low LEV concentrations (100 pmol L-1 to 100 nmol L-1), and one for higher LEV concentrations (100 nmol L-1 to 100 µmol L-1). The limit of detection and sensitivity are calculated to be 30 pmol L-1 and 467.33 nA µmol L-1 cm-2, respectively. The modified GCE demonstrates a number of advantages such as high sensitivity and selectivity, low LOD, excellent reproducibility, high surface-to-volume ratio, and good electrocatalytic activity towards LEV. The sensor was successfully applied to the determination of LEV in spiked human serum samples. Graphical abstract.

Bio-inspired magnetite/lignin/polydopamine-glucose oxidase biosensing nanoplatform. From synthesis, via sensing assays to comparison with others glucose testing techniques.

Glucose monitoring has become a crucial part of diabetes care, and is also of importance in the food industry. However, the measurements are subject to certain limitations and errors. These may result from many factors, including the strip manufacturing process, inappropriate storage, temperature, coding, aging, etc. Here, we discuss the measurement of glucose in real samples using techniques such as photometric assay, glucometers, and using a proposed biosensor. Biosensor platforms based on the multicomponent material magnetite/lignin/polydopamine-glucose oxidase with the addition of ferrocene and a dedicated carbon paste electrode (CPE/Fe3O4/Lig/PDA/GOx/Fc) were fabricated for glucose detection in real, commercially available glucose-based samples. To determine the morphological features of the materials, Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), atomic force microscopy (AFM) and zeta potential measurements were carried out. Moreover, to determine the effectiveness of glucose oxidase immobilization the Bradford assays was applied. Analysis of glucose-based products was carried out based on photometric measurements using an AU480 Chemical Analyzer from Beckam Coulter, with the use of three glucometers (Wellion Calla light® WELL 900LB, CERA-CHEK 1Code®Model G400, iXell®Rev.04/10-PL), and with the use of our proposed CPE/Fe3O4/Lig/PDA/GOx/Fc biosensor. Tests on real samples demonstrated the repeatability of the results. The results showed that this biosensor has excellent potential for application in the determination of glucose in various commercial products.

Electrode Modified by Reduced Graphene Oxide for Monitoring of Total Thallium in Grain Products.

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.

Electrocatalysis of NADH oxidation using electrochemically activated fluphenazine on carbon nanotube electrode.

Electrocatalytic determination of NADH using a hybrid surface-modified electrode with multi-wall carbon nanotubes (MWCNTs) and a novel electrogenerated redox mediator is described. The redox mediator precursor - fluphenazine (Flu) was adsorbed on MWCNT-modified glassy carbon (GC) electrode which was then subjected to electrochemical activation in 0.1 M H2SO4 using cyclic voltammetry (CV) over a range of potentials -0.2 to 1.5 V vs. Ag/AgCl (6 scans at 100 mV s(-1)). Cyclic voltammograms of Flu indicated the formation of a stable electroactive material presenting one reversible redox couple at the formal potential of -0.115 vs. Ag/AgCl in a phosphate buffer (pH7.0) as a supporting electrolyte. The peaks increased linearly with increasing scan rate indicating electroactive molecules anchored to the electrode surface. The GC/MWCNT/Flu electrode efficiently catalyzed the oxidation of NADH with a decrease in the overpotential of about 600 mV and 150 mV compared to the bare GC and GC/MWCNT electrode, respectively. This modified electrode was successfully used as the working electrode in the chronoamperometric analysis. The peak current response to NADH was linear over its concentration range from 15 µM to 84 µM, and correlation coefficient 0.998. The limits of detection (5 µM) and quantitation (15 µM) were evaluated.

One-step synthesis of lignosulfonate-stabilized silver nanoparticles.

Softwood lignosulfonate (SLS) was used as a reducing agent for one-step synthesis of silver nanoparticles (SLS-AgNPs) in an aqueous solution at room temperature. In this reaction SLS acts also as a stabilizing agent and as a result, stable colloids of silver nanoparticles are formed during the reaction with the average particle size of 41 nm. The obtained SLS-AgNPs were characterized by UV-vis spectrophotometry, size distribution and AFM imaging after casting on mica. Due to metal ion complexing capability of lignosulfonates, the SLS-AgNPs appeared to be capable of colorimetric detection of metal ions (especially nickel). Additionally, the SLS-AgNPs could be assembled into thin films on conducting substrates (ITO glass) using electrophoretic deposition. XPS spectroscopy was used to characterize such films and revealed a strong interaction of silver atoms with some carbon atoms of the SLS.