Search Results (81)

Ultrafine fibers from poly(3-hydroxybutyrate) (PHB) and polyvinylpyrrolidone (PVP) and their blends with different component ratios in the range of 0/100 to 100/0 wt.% were obtained, and their structure and dynamic properties were studied. The polymers were obtained via electrospinning in solution mode. The structure, morphology, and segmental dynamic behavior of the fibers were determined using optical microscopy, SEM, EPR, DSC, and IR spectroscopy. The low-temperature maximum on the DSC endotherms provided information on the state of the PVP hydrogen bond network, which made it possible to determine the enthalpies of thermal destruction of these bonds. The PHB/PVP fiber blend ratio significantly affected the structural and dynamic parameters of the system. Thus, at low concentrations of PVP (up to 9%) in the structure of ultra-fine fibers, the distribution of this polymer occurs in the form of tiny particles, which are crystallization centers, which causes a significant increase in the degree of crystallinity (χ) activation energy (E_act) and slowing down of molecular dynamics (τ). At higher concentrations of PVP, loose interphase layers were formed in the system, which caused a decrease in these parameters. The strongest changes in the concentration of hydrogen bonds occurred when PVP was added to the composition from 17 to 50%, which was due to the formation of intermolecular hydrogen bonds both in PVP and during the interaction of PVP and PHB. The diffusion coefficient of water vapor in the studied systems (D) decreased as the concentration of glassy PVP in the composition increased. The concentration of the radical decreased with an increase in the proportion of PVP, which can be explained by the glassy state of this polymer at room temperature. A characteristic point of the 50/50% mixture component ratio was found in the region where an inversion transition of PHB from a dispersion material to a dispersed medium was assumed. The conducted studies made it possible for the first time to conduct a comprehensive analysis of the effect of the component ratio on the structural and dynamic characteristics of the PHB/PVP fibrous material at the molecular scale. Full article

Three liquid crystalline mixtures were investigated, consisting of compounds abbreviated as MHPOBC and 3F5FPhF6 with molar ratios 0.9:0.1 (MIX5FF6-1), 0.75:0.25 (MIX5FF6-2), and 0.5:0.5 (MIX5FF6-3). The presence of the smectic A*, smectic C*, and smectic C_A* phases was observed in all mixtures. The hexatic smectic X_A* phase, present in pure MHPOBC, disappeared quickly with an increasing admixture of 3F5FPhF6. Vitrification of smectic C_A* was observed for the equimolar mixture, with the glass transition temperature and fragility index comparable to the pure glassforming 3F5FPhF6 component. Partial crystallization to conformationally or orientationally disordered crystal phases was observed on cooling in two mixtures with a smaller fraction of 3F5FPhF6. Broadband dielectric spectroscopy was applied to study the relaxation times in smectic and crystal phases. Vogel–Fulcher–Tammann, Mauro–Yue–Ellison–Gupta–Allan, and critical-like models were applied for analysis of the α-relaxation time in supercooled smectic X_A* and smectic C_A* phases. Full article

The electrochemical behavior of copper (II) on glassy carbon from an eutectic mixture of choline chloride (ChCl) and ethylene glycol (EG) was investigated using cyclic voltammetry (CV). The redox and deposition processes were studied for electrolyte concentrations of 0.01 M and 0.5 M Cu(II), with particular attention paid to the effects of different Cu(II) concentrations on the copper deposition potential and morphology of the copper deposits. The CV results showed that the Cu(II) species are reduced to Cu(0) via two separate steps. Higher Cu(II) concentrations in the electrolyte triggered the formation of differently coordinated Cuⁿ⁺ complexes next to the electrode, which shifted the electrodeposition potential of Cu(I)/Cu(0) couples towards more positive values. The Cu deposits were obtained potentiostatically from 0.01 M and 0.5 M Cu(II)-ChCl:EG electrolyte and analyzed using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The different copper concentrations in electrolytes induced different morphologies of electrodeposited copper, where the mixture of irregular grains and carrot or needle-like dendrites was obtained from 0.01 M, and rose-like forms were obtained from 0.5 M electrolytes. This study is the first to identify these rose-like forms and the mechanism of their formation, which is discussed in detail. Full article

The feasibility of producing high-quality zinc phosphate cement based on a frit-sintered mixture of ZnO, SiO₂, MgO, and Bi₂O₃ oxides, with the addition of phosphorous slag and an aqueous solution of orthophosphoric acid as the mixing liquid, was demonstrated. The raw materials used for zinc phosphate cement preparation were investigated using various physicochemical analysis methods. It was found that the phosphorous slag contains silicon oxide (37.6%), aluminum oxide (4.49%), calcium oxide (42.4%), magnesium oxide (2.19%), as well as fluorine (1.94%) and calcium fluoride (4.91%). The slag predominantly consists of an amorphous glassy phase with minor inclusions of crystalline components. During the sintering process, the addition of 1.5–3.0 wt.% phosphorous slag to the frit promotes the formation of low-melting eutectics due to the presence of fluorides, resulting in a 100 °C reduction in the sintering temperature. An optimal zinc phosphate cement powder composition was developed, comprising: ZnO—83.0%, MgO—9.0%, SiO₂—3.5%, Bi₂O₃—3.0%, and phosphorous slag—1.5%. The resulting sintered product exhibited a whiteness of 97.8%, which exceeds that of the reference sample by 2.6%. Upon mixing the powder with the mixing liquid, zinc ions are released first, initiating a chemical reaction that leads to the formation of zinc, magnesium, and aluminum phosphates. The compressive strength of the resulting composite cements ranged from 101.8 to 111.9 MPa, fully complying with the requirements for cement grade as specified in GOST 31578-2012. Full article

In this work, we simultaneously detected and predicted the concentration levels of serotonin (SE) and dopamine (DA) neurotransmitters (NTs) for in vitro mixtures, with measurements obtained using conventional glassy carbon electrodes (CGCEs) and differential pulse voltammetry (DPV). The NTs were estimated by deconvolving the multiplexed signals of both NTs using Principal Component Analysis with Gaussian Process Regression (PCA-GPR) and Partial Least Squares with Gaussian Process Regression (PLS-GPR), both with exponential–isotropic kernels. The average testing accuracies of estimation using PCA-GPR for DA alone, SE alone and their mixture (DA–SE) were 87.6%, 88.1%, and 96.7%, respectively. Using PLS-GPR, the testing accuracies of estimation for DA alone, SE alone, and their mixture (DA–SE) were 87.3%, 83.8%, and 95.1%, respectively. Furthermore, we explored methods of reducing the procedural complexity in estimating the NTs by finding reduced subsets of features for accurately detecting and predicting their concentrations. The reduced subsets of features found in the oxidation potential windows of the NTs improved the testing accuracy of the estimation of DA–SE to 97.4%. We thus believe that reducing complexity has the potential to increase the detection and prediction accuracies of NT measurements for practical clinical uses such as deep brain stimulation. Full article

The scope of this work was to develop a thin-film composite (TFC) membrane for the separation of CO₂/CO mixtures, which are relevant for many processes of gas processing and gasification of carbon-based feedstock. Special attention was given to the development of highly permeable porous polysulfone (PSF) supports (more than 26,000 GPU for CO₂) since both the selective and support layers contribute significantly to the overall performance of the TFC membrane. The PSF porous support is widely used in commercial and lab-scale TFC membranes, and its porous structure and other exploitation parameters are set during the non-solvent-induced phase separation (NIPS) process. Since the casting solution properties (e.g., viscosity) and the interactions in a three-component system (polymer, solvent, and non-solvent) play noticeable roles in the NIPS process, polysulfone samples in a wide range of molecular weights (M_w = 76,000–122,000 g·mol⁻¹) with terminal hydroxyl groups were synthesized for the first time. Commercial PSF with predominantly terminal chlorine groups (Ultrason^® S 6010) was used as a reference. The PSF samples were characterized by NMR, DSC, and TGA methods, and the Hansen solubility parameters were calculated. It was found that increasing the ratio of terminal –OH over –Cl groups improved the “solubility” of PSF in N-methyl-2-pyrrolidone (NMP) and water. A direct dependence of the gas permeance of porous supports on the coagulation rate of the casting solution was identified for the first time. It was shown that the use of synthesized PSF (M_w = 76,000 g·mol⁻¹, M_w/M_n = 3.0, (–OH):(–Cl) ratio of 4.7:1) enabled a porous support with a CO₂ permeance of 26,700 GPU to be obtained, while the support formed from a commercial PSF Ultrason^® S 6010 (M_w = 68,000 g·mol⁻¹, M_w/M_n = 1.7, (–OH):(–Cl) ratio of 1:1.9) under the same conditions demonstrated 4300 GPU. The siloxane-based materials were used for the selective layer since the thin films based on rubbery polymers do not undergo the same accelerating physical aging as glassy polymers. Two types of materials were screened for the selective layer: synthesized polymethyltrifluoroethylacrylate siloxane-polydecylmethylsiloxane (50F3) copolymer, and polydimethylsiloxane (PDMS). 50F3 siloxane was studied for gas separation applications for the first time. It was shown that the permeance of composite membranes based on high-performance porous supports from the PSF samples synthesized was 3.5 times higher than that from similar composite membranes based on supports from a commercial Ultrason^® S 6010 PSF with a permeance value of 4300 GPU for CO₂. It was found that the enhanced gas permeance of composite membranes based on the highly permeable porous PSF supports developed was observed for both 50F3 polysiloxane and commercial PDMS. At the same time, the CO₂/CO selectivity of the composite membranes with a 50F3-selective layer (9.1–9.3) is 1.5 times higher than that of composite membranes with a PDMS-selective layer. This makes the F-containing 50F3 polysiloxane a promising polymer for CO₂/CO separation. Full article

Synthetic dyes of various classes are widely applied in food production. Reliable and simple methods of dye determination are in demand for food quality control. Novel, sensitive, and selective voltammetric sensors based on glassy carbon electrodes modified with mixtures of metal oxide nanoparticles (NPs) dispersed in water or surfactant media have been developed for the first time for Sunset Yellow FCF, Brilliant Blue FCF, and Quinoline Yellow. Mixtures of CeO₂ and SnO₂ NPs dispersed in surfactants or CeO₂ and Fe₂O₃ NPs are the best sensing layers for the determining of Sunset Yellow FCF and Quinoline Yellow or Brilliant Blue FCF. Full article

Medicinal plants contain a wide range of bioactive compounds including antioxidants. Thus, the evaluation of the antioxidant capacity of medicinal plant extracts used in phytotherapy is of practical interest. Water extracts from 11 plants obtained by sonication for 30 min were studied by cyclic voltammetry at bare glassy carbon electrode (GCE) and GCE modified with a mixture of 1 mg mL⁻¹ CeO₂ and SnO₂ nanoparticles (NPs) dispersed in 0.10 mM cetylpyridinium bromide. A two-step chronoamperometric approach (at 400 and 900 mV for 75 s each one) was developed to estimate the antioxidant capacity of medicinal plant extracts. A strong and very strong correlation level was obtained between the antioxidant capacity and total phenolic contents or antioxidant capacity toward 2,2-diphenyl-1-picrylhydrazyl (DPPH^•). Full article

This literature review deals with the electrophoretic deposition of bioactive glass coatings on metallic substrates to produce bone implants. Biocompatible metallic materials, such as titanium alloys or stainless steels, are commonly used to replace hard tissue functions because their mechanical properties are appropriate for load-bearing applications. However, metallic materials barely react in the body. They need a bioactive surface coating to trigger beneficial biological and chemical reactions in the physiological environment. Bioactive coatings aim to improve bone bonding, shorten the healing process after implantation, and extend the lifespan of the implant. Bioactive glasses, such as 45S5, 58S, S53P4, 13-93, or 70S30C, are amorphous materials made of a mixture of oxides that are accepted by the human body. They are used as coatings to improve the surface reactivity of metallic bone implants. Their high bioactivity in the physiological environment induces the formation of strong chemical bonding at the interface between the metallic implant and the surrounding bone tissue. Electrophoretic deposition is one of the most effective solutions to deposit uniform bioactive glass coatings at low temperatures. This article begins with a review of the different compositions of bioactive glasses described in the scientific literature for their ability to support hard tissue repair. The second part details the different stages of the bioactivity process occurring at the surface of bioactive glasses immersed in a physiological environment. Then, the mechanisms involved in the electrophoretic deposition of bioactive glass coatings on metallic bone implants are described. The last part of the article details the current developments in the process of improving the properties of bioactive glass coatings by adding biocompatible elements to the glassy structure. Full article

Neurotransmitters are essential chemical messengers required for proper brain function, and any changes in their concentrations can lead to neuronal diseases. Therefore, sensitive and selective detection is crucial. This study presents a fast and simple colorimetric method for dopamine detection using three reagent solutions: AgNP and MPA, Ag/Au nanocomposite, and mercaptophenylacetic acid. TEM images showed a narrow distribution of Ag and Au nanoparticles with average sizes of 20 nm and 13 nm, respectively, with gold nanoparticles bound to the edges of silver nanoparticles. A paper-based biosensor was created using manual wax printing for the colorimetric detection of dopamine. Visual detection onsite showed color changes with both the silver nanoparticles and mercaptophenylacetic acid mixture and the silver–gold nanoparticle composite. Electrochemical detection using a glassy carbon electrode modified with 8 mM mercaptophenylacetic acid demonstrated high selectivity and sensitivity towards dopamine, with a peak in the range of 0.7–0.9 V. Interferences were minimized, ensuring high sensitivity and selective detection of dopamine. Full article

This article introduces a new type of carbon paste electrode prepared from black raw shungite. In powdered form, this carbonaceous material was mixed with several nonpolar binders. The resulting shungite pastes were microscopically and electrochemically characterized. Mixtures of several pasting liquids with different contents of shungite powder were tested to select the optimal composition and compared with other types of carbon paste-based electrodes made of graphite and glassy carbon powder. In terms of physical and mechanical properties, shungite paste electrodes (ShPEs) formed a composite mass being like dense pastes from glassy carbon microspheres, having harder consistency than that of traditional graphitic carbon pastes. The respective electrochemical measurements with ShPEs were based on cyclic voltammetry of ferri-/ferro-cyanide redox pairs, allowing us to evaluate some typical parameters such as electrochemically active surface area, double-layer capacitance, potential range in the working media given, heterogeneous rate constant, charge-transfer coefficient, exchange current density, and open-circuit potential. The whole study with ShPEs was then completed with three different examples of possible electroanalytical applications, confirming that the carbon paste-like configuration with powdered shungite represents an environmentally friendly (green) and low-cost electrode material with good stability in mixed aqueous-organic mixtures, and hence with interesting prospects in electroanalysis of biologically active organic compounds. It seems that similar analytical parameters of the already established variants of carbon paste electrodes can also be expected for their shungite analogues. Full article

This work examines, first, the non-equilibrium character of the glassy state of polymer systems and its significance in the development of novel materials for important technological applications. Subsequently, it summarizes the essentials of the generalized lattice fluid approach for the description of this highly complex non-equilibrium behavior with an approximate and simple, yet analytically powerful formalism. The working equations are derived in a straightforward and consistent manner by clearly defining the universal and specific variables needed to describe the discussed properties. The role of the non-random distribution of molecular species and free volume in the glassy system is also examined, as is the role of strong specific interactions, such as hydrogen-bonding networks. This work also reports examples of applications in a variety of representative systems, including glass densification, retrograde vitrification, increase in glass-transition temperature in hydrogen-bonded polymer mixtures, and hysteresis phenomena in sorption–desorption from glassy polymer matrices. Full article

Amorphous, glassy or disordered materials play important roles in developing structural materials from metals or ceramics, devices from semiconductors or medicines from organic compounds. Their local structure is frequently similar to crystalline ones. A computer program is presented here that runs under the Windows operating system on a PC to extract pair distribution function (PDF) from electron diffraction in a transmission electron microscope (TEM). A polynomial correction reduces small systematic deviations from the expected average Q-dependence of scattering. Neighbor distance and coordination number measurements are supplemented by either measurement or enforcement of number density. Quantification of similarity is supported by calculation of Pearson’s correlation coefficient and fingerprinting. A rough estimate of fractions in a mixture is computed by multiple least-square fitting using the PDFs from components of the mixture. PDF is also simulated from crystalline structural models (in addition to measured ones) to be used in libraries for fingerprinting or fraction estimation. Crystalline structure models for simulations are obtained from CIF files or str files of ProcessDiffraction. Data from inorganic samples exemplify usage. In contrast to previous free ePDF programs, our stand-alone program does not need a special software environment, which is a novelty. The program is available from the author upon request. Full article

This work presents the electrochemical determination of cholecalciferol (Vitamin D₃) in water-organic mixtures using a glassy carbon electrode (GCE) and commercial screen-printed carbon electrodes (SPCEs). The electrocatalytic behavior of Vitamin D₃ on the surface of the working electrode produced a well-defined oxidation peak at +0.95 V (vs. Ag|AgCl, 3.0 mol L⁻¹) and +0.7 V (vs. Ag-SPCE pseudo-reference electrode) for the GCE and SPCE, respectively, in 0.1 M LiClO₄ prepared in 50% ethanol. The nature of the organic solvent needed for the solubilization of Vitamin D₃ was evaluated, together with the concentration of the supporting electrolyte, the ratio of the water-organic mixture, the voltametric parameters for the cyclic voltammetry (CV), and square-wave voltammetry (SWV) analyses. Under the optimized conditions, a linear correlation between the anodic peak current and the concentration of Vitamin D₃ was obtained over the range of 0.47 to 123 µmol L⁻¹ and 59.4 to 1651 µmol L⁻¹ for the GCE and SPCE, respectively. The determined limits of detection (LOD) were 0.17 (GCE) and 19.4 µmol L⁻¹ (SPCE). The methodology was successfully applied to commercial supplement tablets of Vitamin D₃. Additionally, this work shows the possibility of using non-modified GCE and SPCE for routine analysis of Vitamin D₃. Full article

Due to the multitude of physiological functions, ferulic acid (FA) has a wide range of applications in the food, cosmetic, and pharmaceutical industries. Thus, the development of rapid, sensitive, and selective detection tools for its assay is of great interest. This study reports a new electroanalytical approach for the quantification of ferulic acid in commercial pharmaceutical samples using a sulphur-doped graphene-based electrochemical sensing platform. The few-layer graphene material (exf-SGR) was prepared by the electrochemical oxidation of graphite, at a low applied bias (5 V), in an inorganic salt mixture of Na₂S₂O₃/(NH₄)₂SO₄ (0.3 M each). According to the morpho-structural characterization of the material, it appears to have a high heteroatom doping degree, as proved by the presence of sulphur lines in the XRD pattern, and the C/S ratio was determined by XPS investigations to be 11.57. The electrochemical performances of a glassy carbon electrode modified with the exf-SGR toward FA detection were tested by cyclic voltammetry in both standard laboratory solutions and real sample analysis. The developed modified electrode showed a low limit of detection (30.3 nM) and excellent stability and reproducibility, proving its potential applicability as a viable solution in FA qualitative and quantitative analysis. Full article