Search Results (12)

Li₃V₂(PO₄)₃ cathodes for Li-ion batteries (LIBs) were synthesized using a hydrothermal method with the subsequent annealing in an argon atmosphere to achieve optimal properties. The X-ray diffraction analysis confirmed the material’s single-phase nature, while the scanning electron microscopy revealed a granular structure, indicating a uniform particle size distribution, beneficial for electrochemical performance. Magnetometry and electron spin resonance studies were conducted to investigate the magnetic properties, confirming the presence of the relatively low concentration and highly uniform distribution of tetravalent vanadium ions (V⁴⁺), which indicated low lithium deficiency values in the original structure and a high degree of magnetic homogeneity in the sample, an essential factor for consistent electrochemical behavior. For this pure phase Li₃V₂(PO₄)₃ sample, devoid of any impurities such as carbon or salts, extensive electrochemical property testing was performed. These tests resulted in the experimental discovery of a remarkably high lithium diffusion coefficient D = 1.07 × 10⁻¹⁰ cm²/s, indicating excellent ionic conductivity, and demonstrated impressive stability of the material with sustained performance over 1000 charge–discharge cycles. Additionally, relithiated Li₃V₂(PO₄)₃ (after multiple electrochemical cycling) samples were investigated using scanning electron microscopy, magnetometry and electron spin resonance methods to determine the extent of degradation. The combination of high lithium diffusion coefficients, a low degradation rate and remarkable cycling stability positions this Li₃V₂(PO₄)₃ material as a promising candidate for advanced energy storage applications. Full article

An electrochemically active polymer, polythionine (PTN), was synthesized in natural deep eutectic solvent (NADES) via multiple potential scans and characterized using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). NADES consists of citric acid monohydrate, glucose, and water mixed in the molar ratio of 1:1:6. Electrodeposited PTN film was then applied for the electrostatic accumulation of DNA from salmon sperm and used for the sensitive detection of the anticancer drug epirubicin. Its reaction with DNA resulted in regular changes in the EIS parameters that made it possible to determine 1.0–100 µM of epirubicin with the limit of detection (LOD) of 0.3 µM. The DNA sensor developed was successfully applied for the detection of epirubicin in spiked samples of artificial and natural urine and saliva, with recovery ranging from 90 to 109%. The protocol of the DNA sensor assembling utilized only one drop of reactants and was performed with a minimal number of steps. Together with a simple measurement protocol requiring 100 µL of the sample, this offers good opportunities for the further use of the DNA sensor in monitoring the drug level in biological samples, which is necessary in oncology treatment and for the pharmacokinetics studies of new antitumor drugs. Full article

In the present paper, we describe several coleoid jaws discovered in the lower Toarcian black shales, cropping out along the Vilyui River (Yakutia, Russia). This is the first record of a Lower Jurassic coleoid jaw outside Europe and the first report of such a finding from the Mesozoic of Siberia. The described coleoid jaws demonstrate the same mode of preservation and morphology as the coeval jaws previously reported from Europe. Their preservation in Siberia became possible due to the widespread occurrence of black shale facies associated with the early Toarcian oceanic anoxic event (TOAE). Full article

The assembling of thiacalix[4]arene-based dendrimers in cone, partial cone, and 1,3-alternate configuration on the surface of a glassy carbon electrode coated with carbon black or multiwalled carbon nanotubes has been characterized using cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscopy. Native and damaged DNA were electrostatically accumulated on the modifier layer. The influence of the charge of the redox indicator and of the macrocycle/DNA ratio was quantified and the roles of the electrostatic interactions and of the diffusional transfer of the redox indicator to the electrode interface indicator access were established. The developed DNA sensors were tested on discrimination of native, thermally denatured, and chemically damaged DNA and on the determination of doxorubicin as the model intercalator. The limit of detection of doxorubicin established for the biosensor based on multi-walled carbon nanotubes was equal to 1.0 pM with recovery from spiked human serum of 105–120%. After further optimization of the assembling directed towards the stabilization of the signal, the developed DNA sensors can find application in the preliminary screening of antitumor drugs and thermal damage of DNA. They can also be applied for testing potential drug/DNA nanocontainers as future delivery systems. Full article

Electrochemical DNA sensors are highly demanded for fast and reliable determination of antitumor drugs and chemotherapy monitoring. In this work, an impedimetric DNA sensor has been developed on the base of a phenylamino derivative of phenothiazine (PhTz). A glassy carbon electrode was covered with electrodeposited product of PhTz oxidation obtained through multiple scans of the potential. The addition of thiacalix[4]arene derivatives bearing four terminal carboxylic groups in the substituents of the lower rim improved the conditions of electropolymerization and affected the performance of the electrochemical sensor depending on the configuration of the macrocyclic core and molar ratio with PhTz molecules in the reaction medium. Following that, the deposition of DNA by physical adsorption was confirmed by atomic force microscopy and electrochemical impedance spectroscopy. The redox properties of the surface layer obtained changed the electron transfer resistance in the presence of doxorubicin due to its intercalating DNA helix and influencing charge distribution on the electrode interface. This made it possible to determine 3 pM–1 nM doxorubicin in 20 min incubation (limit of detection 1.0 pM). The DNA sensor developed was tested on a bovine serum protein solution, Ringer–Locke’s solution mimicking plasma electrolytes and commercial medication (doxorubicin-LANS) and showed a satisfactory recovery rate of 90–105%. The sensor could find applications in pharmacy and medical diagnostics for the assessment of drugs able to specifically bind to DNA. Full article

The synthesis of the NiCr₂O₄ compound with the spinel structure via the high-temperature solid-state reaction leads to different deviations of the cationic composition from the nominal depending on the atmosphere in the furnace chamber. The samples prepared from the same starting NiO and Cr₂O₃ compounds but in different atmospheres differ in phase composition and orbital and spin ordering temperatures. We find that a common route of synthesis in the air and a possible presence of the Ni₂O₃ in initial NiO lead to the incorporation of the Ni³⁺ ions into the octahedral sites regularly occupied by the Cr³⁺ ions. This results in a decrease in the orbital ordering and an increase in the Nèel temperatures. We propose that the Nèel temperature value serves as a measure of a departure of a composition from the nominal NiCr₂O₄. The lowest Nèel temperature among our series was T_N = 63 K which we consider the closest to the intrinsic quantity of the NiCr₂O₄ compound. Full article

New highly sensitive voltammetric DNA-sensors have been developed for the detection of cytostatic drug doxorubicin based on Azure A electropolymerized on various carbon nanomaterials, i.e., functionalized multi-walled carbon nanotubes (fMWCNTs) and carbon black (CB). Carbon materials promote electropolymerization of the Azure A dye applied as a matrix for DNA molecules saturated with methylene blue (MB) molecules. Interaction with the intercalator (doxorubicin) liberates the MB molecules and changes redox activity. The doxorubicin concentration ranges reached by cyclic voltammetry were from 0.1 pM to 100 nM (limit of detection, LOD, 0.03 pM) for the biosensor based on CB, and from 0.3 pM to 0.1 nM (LOD 0.3 pM) for that based on fMWCNTs. DNA-sensors were tested on spiked samples of artificial serum, and biological and pharmaceutical samples. The DNA-sensors can find further application in the monitoring of the doxorubicin residuals in cancer treatment, as well as for pharmacokinetics studies. Full article

Lichens often grow in microhabitats where they experience severe abiotic stresses. Some species respond to high UV radiation by synthesizing dark brown melanic pigments in the upper cortex. However, unlike the melanized structures of non-lichenized fungi, the morphology of the melanic layer in lichens remains unstudied. Here, we analyzed the morphology, ultrastructure, and elemental composition of the melanized layer in UV-exposed thalli of the lichen Lobaria pulmonaria (L.) Hoffm. Using light microscopy, we detected a pigmented layer sensitive to staining with 3,4-L-dihydroxyphenylalanine, a precursor of eumelanin, in the upper cortex of melanized thalli. Analysis of cross-sections of melanized thalli using scanning electron microscopy revealed that melanin-like granules are deposited into the hyphal lumens. Melanized thalli also possessed thicker hyphal cell walls compared to pale thalli. Energy-dispersive X-ray spectroscopy analysis of the elemental composition of the hyphal walls and extracted melanin indicated that the type of melanin synthesized by L. pulmonaria is eumelanin. Transmission electron microscopy was used to show that during melanization melanosome-like dark vesicles are transported to the cell surface and secreted into the cell walls of the fungal hyphae. Results from this study provide new insights into the effects of melanin synthesis on the microstructure of lichen thalli. Full article

The detection of small molecules interacting with DNA is important for the assessment of potential hazards related to the application of rather toxic antitumor drugs, and for distinguishing the factors related to thermal and oxidative DNA damage. In this work, a novel electrochemical DNA sensor has been proposed for the determination of antitumor drugs. For DNA sensor assembling, a glassy carbon electrode was modified with carbon black dispersed in DMF. After that, pillar [5]arene was adsorbed and Methylene blue and Neutral red were consecutively electropolymerized onto the carbon black layer. To increase sensitivity of intercalator detection, DNA was first mixed with water-soluble thiacalixarene bearing quaternary ammonium groups in the substituents at the lower rim. The deposition of the mixture on the electropolymerized dyes made it possible to detect doxorubicin as model intercalator by suppression of the redox activity of the polymerization products. The DNA sensor made it possible to determine 0.5 pM–1.0 nM doxorubicin (limit of detection 0.13 pM) with 20 min of incubation. The DNA sensor was successfully tested on spiked samples of human plasma and doxorubicin medication. Full article

In this work, we investigated aggregation of native DNA and thiacalix[4]arene derivative bearing eight terminal amino groups in cone configuration using various redox probes on the glassy carbon electrode. It was shown that sorption transfer of the aggregates on the surface of the electrode covered with carbon black resulted in changes in electrostatic interactions and diffusional permeability of the surface layer. Such changes alter the signals of ferricyanide ion, methylene green and hydroquinone as redox probes to a degree depending on their specific interactions with DNA and own charge. Inclusion of DNA in the surface layer was independently confirmed by scanning electron microscopy, electrochemical impedance spectroscopy and experiments with doxorubicin as a model intercalator. Thermal denaturing of DNA affected the charge separation on the electrode interface and the signals of redox probes. Using hydroquinone, less sensitive to electrostatic interactions, made it possible to determine from 10 pM to 1.0 nM doxorubicin (limit of detection 3 pM) after 10 min incubation. Stabilizers present in the commercial medications did not alter the signal. The DNA sensors developed can find future application in the assessment of the complexes formed by DNA and macrocycles as delivery agents for small chemical species. Full article

Electrochemical DNA sensors offer unique opportunities for the sensitive detection of specific DNA interactions. In this work, a voltametric DNA sensor is proposed on the base of glassy carbon electrode modified with carbon black, adsorbed acridine yellow and DNA for highly sensitive determination of doxorubicin antitumor drug. The signal recorded by cyclic voltammetry was attributed to irreversible oxidation of the dye. Its value was altered by aggregation of the hydrophobic dye molecules on the carbon black particles. DNA molecules promote disaggregation of the dye and increased the signal. This effect was partially suppressed by doxorubicin compensate for the charge of DNA in the intercalation. Sensitivity of the signal toward DNA and doxorubicin was additionally increased by treatment of the layer with dimethylformamide. In optimal conditions, the linear range of doxorubicin concentrations determined was 0.1 pM–1.0 nM, and the detection limit was 0.07 pM. No influence of sulfonamide medicines and plasma electrolytes on the doxorubicin determination was shown. The DNA sensor was tested on two medications (doxorubicin-TEVA and doxorubicin-LANS) and showed recoveries of 102–105%. The DNA sensor developed can find applications in the determination of drug residues in blood and for the pharmacokinetics studies. Full article

The determination of antibiotics in food is important due to their negative effect on human health related to antimicrobial resistance problem, renal toxicity, and allergic effects. We propose an impedimetric aptasensor for the determination of kanamycin A (KANA), which was assembled on the glassy carbon electrode by the deposition of carbon black in a chitosan matrix followed by carbodiimide binding of aminated aptamer mixed with oligolactide derivative of thiacalix[4]arene in a cone configuration. The assembling was monitored by cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscopy. In the presence of the KANA, the charge transfer resistance of the inner interface surprisingly decreased with the analyte concentration within 0.7 and 50 nM (limit of detection 0.3 nM). This was attributed to the partial shielding of the negative charge of the aptamer and of its support, a highly porous 3D structure of the surface layer caused by a macrocyclic core of the carrier. The use of electrostatic assembling in the presence of cationic polyelectrolyte decreased tenfold the detectable concentration of KANA. The aptasensor was successfully tested in the determination of KANA in spiked milk and yogurt with recoveries within 95% and 115%. Full article