In 2025, seven fluorine-containing anticancer agents received approval from the US Food and Drug Administration, underscoring the continued and growing impact of strategic fluorination in modern oncology drug design. These newly authorized therapies represent a diverse portfolio spanning a broad spectrum of malignancies, molecular targets, and innovative mechanisms of action, further validating fluorine’s unique ability to enhance drug performance. Sunvozertinib (Zegfrovy®) was approved for the treatment of locally advanced or metastatic non-small cell lung cancer (NSCLC) harboring specific EGFR mutations. The combination of defactinib and avutometinib (Avmapki®) provides a much-needed targeted option for patients with KRAS-mutated recurrent low-grade serous ovarian cancer, addressing a historically challenging disease setting. Imlunestrant (Inluriyo®) offers a next-generation selective estrogen receptor degrader (SERD) as an effective endocrine therapy for estrogen receptor-positive, HER2-negative, ESR1-mutated advanced or metastatic breast cancer. Ziftomenib (Komzifti®) enables precision therapy for adults with relapsed or refractory (AML) carrying susceptible NPM1 mutations, representing a significant advancement in targeted hematologic oncology.Datopotamab deruxtecan (Datroway®), a novel TROP2-directed antibody–drug conjugate (ADC) with a topoisomerase I inhibitor payload, expands treatment options for previously treated hormone receptor-positive, HER2-negative metastatic breast cancer and for certain TKI-experienced NSCLC populations. Taletrectinib (Ibtrozi®), a potent next-generation ROS1 tyrosine kinase inhibitor, received approval for ROS1-positive NSCLC in both TKI-naïve and TKI-experienced patients, offering improved central nervous system penetration and activity against resistant mutations.Collectively, these seven agents vividly illustrate the remarkable versatility of fluorine incorporation in enhancing molecular potency, metabolic stability, binding selectivity, and overall pharmacokinetic performance across vastly different therapeutic modalities — from small-molecule kinase inhibitors and degraders to complex antibody–drug conjugates. The strategic placement of fluorine atoms or fluorinated groups in these molecules often leads to improved lipophilicity, stronger target engagement, reduced clearance, and better safety profiles.For each compound, we provide a comprehensive integrated discussion covering its discovery history, detailed biological mechanism of action, primary therapeutic applications, recommended clinical administration and dosing regimens, the specific role of fluorination in optimizing its pharmacological and physicochemical properties, as well as the detailed chemical synthesis routes employed in its industrial-scale production.
The catalytic properties of natural aluminosilicates from Ukrainian deposits modified with sulfuric acid were studied in glycerol ketalization with acetone. Bentonite (Bent, Dashukivske deposit), clinoptilolite (Cli, Sokyrnytske deposit) and trepel (Tr, Konoplianske deposit) were treated with sulfuric acid to increase their acidity and improve catalytic performance. The influence of catalyst loading, reaction temperature and glycerol:acetone molar ratio on glycerol conversion and initial rate of its consumption was investigated. It was found that catalytic activity strongly depends on structural, adsorption and acidic characteristics of aluminosilicates. The highest catalytic activity was observed for sulfuric acid-modified bentonite (H-Bent), which provided a maximum glycerol conversion of 81% at 45 °C, catalyst loading of 3 wt.% and glycerol:acetone molar ratio 1:25. H-Tr and H-Cli exhibited lower acti-vity, reaching 71% and 60% conversion, respectively, under the same conditions. The superior performance of H-Bent is associated with its higher specific surface area (243 m2/g), developed mesoporous structure and higher concentration of Brønsted and Lewis acid sites. Nitrogen adsorption-desorption analysis showed that all investigated samples belong to type IV isotherms, characteristic of micro- mesoporous materials. H-Bent had the highest total pore volume and mesopore surface area, while H-Cli contained a noticeable fraction of micropores. Pyridine adsorption studies revealed that H-Bent contains both Brønsted and Lewis acid sites of medium and high strength, whereas H-Tr and H-Cli are characterized mainly by weak and medium-strength Brønsted sites. Kinetic analysis demonstrated that the reaction order with respect to glycerol is close to one for H-Bent and two for H-Tr, indicating differences in rate-limiting step and reaction mechanism. The pseudo-Michaelis constants and maxi¬mum reaction rates were also determined, confirming the significantly higher catalytic efficiency of H-Bent compared to other investigated samples. Furthermore, the obtained results demonstrate that sulfuric acid-modified bentonite is a promising low-cost and environmentally friendly catalyst for glycerol valorization into cyclic ketals, which can be considered valuable fuel additives and intermediates for chemical industry.
Fluorine-containing heterocycles occupy a central position in pharmaceutical, agrochemical, and materials science due to their unique physicochemical properties and broad functional relevance. The pursuit of efficient and sustainable synthetic methodologies has catalyzed the emergence of photochemistry as a compelling alternative to conventional thermal, acid–base, or redox-based approaches. Indeed, many of the transformations highlighted in this review would be unattainable under traditional reaction conditions, underscoring the distinctive reactivity enabled by light-driven processes. This review surveys key advances over the past decade in the photochemical synthesis of fluorinated heterocyclic compounds. It begins with an overview of fundamental photochemical principles and the most commonly employed photocatalysts. The discussion then proceeds to categorize reactions into unimolecular, bimolecular, and trimolecular classes. Unimolecular (intramolecular) reactions typically involve the cyclization of strategically designed substrates capable of forming heterocyclic frameworks upon photoactivation. Unimolecular (intramolecular) reactions represent the most prevalent class, wherein two distinct components contribute complementary fragments to construct the target heterocycle. Trimolecular (three-component) photochemical reactions, by contrast, are exceedingly rare due to the inherent mechanistic, kinetic, and spatial constraints associated with three-body interactions under photochemical conditions. For each transformation discussed, we detail the photocatalyst employed, the irradiation source, reaction conditions, and the specific fluorination pattern introduced. Photochemistry redefines light not merely as an energy source but as a precise and sustainable reagent—unlocking synthetic pathways with elegance, selectivity, and minimal environmental impact. This work aims to serve as a comprehensive resource for researchers and practitioners seeking to harness photochemical strategies for the synthesis of fluorinated heterocycles, with an emphasis on catalytic efficiency, structural diversity, and ecological responsibility.
The features of calcium phosphate synthesis with an apatite structure from aqueous–alcoholic solutions were established. The phase composition and structure of the synthesized samples were confirmed by scanning electron microscopy, infrared spectroscopy, and X-ray diffraction analysis. The effect of the molar mass of monohydric alcohols on the morphology and size of apatite nanoparticles was systematically investigated. It was shown that an increase in the molar mass of the alcohol leads to particle growth, with the average size increasing from approximately 30 nm in a methanol medium to about 170 nm in an isoamyl alcohol solution, which is attributed to changes in polarity, viscosity, and nucleation conditions. Europium(III)-doped hydroxyapatite was synthesized via coprecipitation, ensuring the incorporation of Eu3+ ions into the apatite lattice without significant structural distortion. The apatite exhibited intense red emission with a maximum at ~613 nm corresponding to the 5D0 → 7F2 transition of Eu3+ ions, indicating a low-symmetry local environment. Additional emission bands at ~595 nm (5D0 → 7F1) and ~740 nm (5D0 → 7F4) were also observed. For the first time, polymer composite films based on polymethyl methacrylate filled with europium(III)-doped hydroxyapatite were prepared by the solution casting method. The resulting films retained the characteristic luminescent properties of the filler, demonstrating that the polymer matrix does not induce quenching of Eu3+ emission. The proposed approach enables the formation of homogeneous and optically transparent composite films with filler contents of up to 10 wt. %. The composite retained the characteristic luminescent properties of the inorganic filler, demonstrating the absence of significant quenching effects from the polymer matrix. The developed approach opens new opportunities for the fabrication of functional hybrid materials with controlled optical properties, which are promising for applications in biomedical imaging, sensing, and advanced photonic devices.
Metal-free catalysts based on carbon powder modified with reduced graphene oxide (rGO) were prepared and investigated in the ethylene hydrogenation reaction. The samples were characterized by Raman and FTIR spectroscopies, SEM, TEM, thermogravimetric analysis, and N2 adsorption-desorption. SEM and TEM analyses showed that rGO deposition leads to the formation of wrinkled graphene-derived structures covering the external surface of the carbon support. Raman spectra confirmed the presence of defect-rich sp²-hybridized carbon domains, while FTIR analysis revealed oxygen-containing functional groups associated with partially reduced graphene oxide. Textural analysis demonstrated that rGO incorporation mainly affects the external surface area without significantly changing the microporous structure of the support. The catalytic properties of the obtained materials were studied in ethylene hydrogenation within 50–400 °C under continuous-flow conditions. The pristine carbon powder provides the highest catalytic activity, whereas deposition of rGO results in a decrease in activity compared with the unmodified support. However, within the rGO/CP series, catalytic activity increased with increasing rGO loading, reaching 18% conversion for rGO(0.1)/CP at 400 °C. At the same time, normalization of the reaction rate to the mass of deposited rGO showed a decrease in specific activity at higher rGO contents, attributed to partial restacking of graphene sheets and blocking of active surface sites. The obtained results indicate that the catalytic behaviour of the investigated composites is governed by the balance between the intrinsic activity of carbon powder and the contribution of defect-rich graphene-derived domains. The findings highlight the importance of controlling graphene loading and surface accessibility in the design of efficient metal-free carbon catalysts.
A new coordination compound of Ni(II) with cyclohexylacetoacetate and N,N-diethylnicotinamide was synthesized and characterized by IR spectroscopy and X-ray analysis. The IR spectrum exhibits intense broad absorption bands corresponding to the stretching vibrations of the C=O and C=C bonds conjugated within the chelate ring (1625, 1502 cm⁻¹), as well as other absorption bands characteristic of β-dicarbonyl complexes, in particular a sharp band at 775 cm⁻¹ attributed to the out-of-plane bending vibration of the C–H bond in the chelate ring. In the high-frequency region of the spectrum, there are signals of stretching vibrations of the C-H bonds of alkyl groups (2855–2990 cm–1) and weak signals of stretching vibrations of the C-H of the pyridine ring (3080–3110 cm–1). The absorption bands of the amide group (νС=О 1620–1650 cm–1) and the pyridine ring (νС=С, νС=N 1500–1600 cm–1) of N,N‑diethylnicotinamide overlap with the vibration bands of the chelate rings and cannot be unambiguously assigned. The medium-intensity band at 1300 cm⁻¹, present in both the free ligand and the complex, is assigned to C–N stretching vibrations of the amide group. The low-intensity bands in the 600–400 cm⁻¹ region are assigned to Ni–N and Ni–O vibrations. According to X-ray data, the crystal system of NiL2NK2 complex is monoclinic, space group P21/с, a = 7.0360(15) Å, b = 13.233(4) Å, c = 23.619(5) Å, α = γ = 90º, β = 93.301(12)º. The structure corresponds to the formula [Ni(C10H15O3)2(C10H14N2O)2] and represents a mononuclear complex located in a special position relative to the inversion center. The central Ni atom has a O4N2 distorted octahedral environment. The axial positions of the coordination polyhedron are occupied by the nitrogen atoms of the pyridine ring of N,N‑diethylnicotinamide. The molecules of chelating ligands, coordinated through oxygen atoms, occupy an equatorial position with a trans configuration relative to each other. In the crystal, the complex molecules are bound by weak C-H…π interactions and form layers in the (001) plane, alternating with each other. The structure of the coordination polyhedron of the described compound is similar to the structure of adducts of β-dicarbonyl complexes of d‑metals with pyridine.
Academician of the National Academy of Sciences of Ukraine Anatoly Grigorovich Bilous, Doctor of Chemical Sciences, Professor, a well-known specialist in the field of physical and inorganic chemistry, solid state chemistry, physics of semiconductors and dielectrics. Anatoly Bilous was born on May 8, 1951 in the village of Grushka, Khmelnytskyi region. Graduated from NTUU «Kyiv Polytechnic Institute», Faculty of Radio Electronics (1974), postgraduate studies at the L. Ya. Karpov Physicochemical Institute (1977, Moscow). Defended his candidate’s thesis, «Influence and study of some ferroelectric and antiferroelectric metal oxides and assessment of their prospects for use in microwave technology,» at the Institute of Steel and Alloys in 1978 (Moscow). And since the same year to the present time, he has been working at the V.I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, and has been the head of the Department of Solid State Chemistry (since 1983). He defended his doctoral dissertation, «Synthesis, structure and properties of heterosubstituted oxides based on elements of groups III-V» in 1991. Scientific directions concern the study of the formation conditions, structure, and properties of complex oxide systems and the development of highly effective materials based on them. Together with the employees of the department, Bilous developed methods for controlling the properties of oxide systems similar in chemical composition - from dielectrics to cationic conductors and semiconductors, and established the regularities of the formation of macroparticles of oxide systems (aluminates, ferrites, zirconates, titanates) with a given particle shape. He obtained new functional materials: high-permeability and high-induction ferrites, new dielectrics for ultrasensitive equipment, superconducting materials, and ionic conductors by finding a correlation between the methods of production, structure, and properties of the material. A. Bilous is also engaged in scientific and pedagogical activities. He has prepared one Doctor of Chemical Sciences and about two dozen Candidates of Chemical Sciences and Doctors of Philosophy in the specialty «Chemistry». Scientific results have been published in the form of articles published in Ukraine and abroad, protected by copyright certificates of the USSR and patents of Ukraine. In 2018, A. Bilous and S. Kobylyanska published the monograph «Oxide Lithium-Conducting Solid Electrolytes». A.G. Bilous was awarded the title of Honored Worker of Science and Technology of Ukraine (2004); he is a laureate of the State Prize of Ukraine in the field of science and technology (2008) for the work «Intermetallics, hydrides and oxides as the basis of new energy-saving materials», the I. Pulyuy Prize of the National Academy of Sciences of Ukraine (2017). In 2019, he was awarded the Order of Prince Yaroslav the Wise, V degree.
The study focuses on the investigation of the effect of yttrium ion modification on the structural, morphological, photoelectrochemical, electrocatalytic, and sensing properties of nanostructured titanium dioxide (TiO2) films. The Y-TiO2 films, with yttrium concentrations ranging from 0.5 to 5.0 at.%, were synthesized using a sol-gel method by annealing at 500 °C. Characterization was performed using XRD, photocurrent spectroscopy, and voltammetry. XRD analysis revealed that all synthesized samples maintained a single-phase anatase structure. It was established that yttrium acts as a structural stabilizer, effectively inhibiting crystallite growth; the average crystallite size decreased from 14.0–10.0 nm. However, increasing yttrium content led to partial amorphization of the TiO2. The photoelectrochemical results demonstrated a substantial increase in the photocurrent quantum yield and a bathochromic shift of the spectral maxima for modified films compared to pristine TiO2. The optimal yttrium concentration for maximizing photosensitivity was found to be 2.0 at.%. This enhancement is attributed to the creation of defect states and active centers that facilitate charge separation and extend the absorption range into the visible spectrum. Electrocatalytic investigations into the oxygen reduction reaction (ORR) in 0.9% NaCl solution showed that 1% Y-TiO2 electrodes exhibit the highest activity, characterized by a shift in the half-wave potential of oxygen reduction toward the anodic region and an expanded dynamic range. Higher yttrium concentrations led to a decrease in ORR activity, likely due to the screening of active sites by the inactive amorphous phase. The sensory properties were evaluated using anodic stripping voltammetry for the detection of lead ions (Pb2+) in liquids. The 1% Y-TiO2 electrodes demonstrated a linear response in the concentration range of 0.1–3.0 mg/L with a sensitivity of 0.01 mg∙L-1.
Molecular modeling plays a central role in modern computational chemistry, particularly in the early stages of drug discovery, where researchers must rapidly and reliably predict the biological activity of large sets of potential candidates. Quantitative Structure–Activity Relationship (QSAR) models are widely used for this purpose; however, their true predictive performance is often overestimated due to improper data splitting strategies. A key challenge arises when test sets contain molecular scaffolds absent from the training data, resulting in models that appear accurate under random splits but fail to generalize to unseen chemical space. This study investigates optimization strategies for QSAR modeling while explicitly accounting for molecular diversity. A dataset of 3,782 molecules with 3,291 computed descriptors and pChEMBL anesthetic activity values (5.01–8.52) for receptor TRPV1 was analyzed. The dataset contained 733 unique scaffolds, and 72 occurred exclusively in the test set under random 80/20 splitting, revealing substantial information leakage. Three splitting strategies were compared: standard K-Fold (R² = 0.54), scaffold-based Group K-Fold (R² = 0.31), and stratified scaffold-aware splitting (R² = 0.646–0.7201), the latter demonstrating the most realistic and stable performance. Multiple machine-learning approaches were evaluated, with Gradient Boosting achieving the best baseline accuracy. Optimization techniques included descriptor-level data augmentation (σ = 0.02), descriptor weighting by duplicating the most important features, and combined methods. The best model (R² = 0.7201, MAE = 0.41) was obtained by integrating augmentation with triple duplication of top-ranking descriptors. Several commonly used approaches—Morgan fingerprints, deep neural networks, PCA—yielded significantly weaker performance, highlighting the superior informativeness of physicochemical descriptors for this dataset. The resulting model demonstrates practical utility for early-stage virtual screening and prioritization of candidate molecules, providing a reliable tool for guiding medicinal chemistry decisions.
The reactivity of a mixed-ligand alkylamino-β-ketoenolato decanoatophthalocyaninate of hafnium was investigated by 1H NMR spectroscopy via substitution of axial ligands in reactions with para-isopropoxybenzoic acid and dibenzoylmethane. The initial complex PcHf(C₉H₁₉COO)L was shown to exhibit high reactivity. It was established that the presence of different axial ligands enables their selective or complete substitution depending on the nature of the reagent. In the reaction with para-isopropoxybenzoic acid, only the decanoate ligand is replaced, leading to the formation of a new mixed-ligand complex PcHf(C₁₀H₁₁O₃)L. The 1H NMR spectrum of the obtained complex displays signals of the phthalocyanine macrocycle protons (9.5–8.1 ppm) and the para-substituted benzoate fragment (7.5–7.4 ppm). Signals corresponding to the alkylamino-β-ketoenol ligand are observed in the region 7.2–5.5 ppm, as well as in the aliphatic region. The absence of signals corresponding to the decanoate chain protons (0.0–0.5 ppm) and the appearance of signals of the isopropyl methyl protons (2.27 ppm) confirm the completion of the ligand exchange reaction. In contrast, the reaction of PcHf(C₉H₁₉COO)L with dibenzoylmethane results in complete substitution of both axial ligands (decanoate and alkylamino-β-ketoenolate), yielding bis(dibenzoylmethanato)hafnium phthalocyaninate. The 1H NMR spectrum of the product shows no signals of either decanoate or alkylamino-β-ketoenolate protons and matches the previously reported spectrum of PcHf(dbm)₂. A stability series of chelate rings in the coordination sphere of hafnium phthalocyaninates was established. The strength of ligand binding to the central metal atom increases in the following order: aliphatic carboxylate < aromatic carboxylate < alkylamino-β-ketoenolate < β-diketonate. The obtained results expand the possibilities for the targeted synthesis of out-of-plane coordinated phthalocyanine complexes, enabling the tuning of their physicochemical properties (such as solubility and spectral characteristics) for potential applications in photodynamic therapy, organic semiconductors, and sensors.
A new coordination compound of Ni(II) with cyclohexylacetoacetate and N,N-diethylnicotinamide was synthesized and characterized by IR spectroscopy and X-ray analysis. The IR spectrum exhibits intense broad absorption bands corresponding to the stretching vibrations of the C=O and C=C bonds conjugated within the chelate ring (1625, 1502 cm⁻¹), as well as other absorption bands characteristic of β-dicarbonyl complexes, in particular a sharp band at 775 cm⁻¹ attributed to the out-of-plane bending vibration of the C–H bond in the chelate ring. In the high-frequency region of the spectrum, there are signals of stretching vibrations of the C-H bonds of alkyl groups (2855–2990 cm–1) and weak signals of stretching vibrations of the C-H of the pyridine ring (3080–3110 cm–1). The absorption bands of the amide group (νС=О 1620–1650 cm–1) and the pyridine ring (νС=С, νС=N 1500–1600 cm–1) of N,N‑diethylnicotinamide overlap with the vibration bands of the chelate rings and cannot be unambiguously assigned. The medium-intensity band at 1300 cm⁻¹, present in both the free ligand and the complex, is assigned to C–N stretching vibrations of the amide group. The low-intensity bands in the 600–400 cm⁻¹ region are assigned to Ni–N and Ni–O vibrations. According to X-ray data, the crystal system of NiL2NK2 complex is monoclinic, space group P21/с, a = 7.0360(15) Å, b = 13.233(4) Å, c = 23.619(5) Å, α = γ = 90º, β = 93.301(12)º. The structure corresponds to the formula [Ni(C10H15O3)2(C10H14N2O)2] and represents a mononuclear complex located in a special position relative to the inversion center. The central Ni atom has a O4N2 distorted octahedral environment. The axial positions of the coordination polyhedron are occupied by the nitrogen atoms of the pyridine ring of N,N‑diethylnicotinamide. The molecules of chelating ligands, coordinated through oxygen atoms, occupy an equatorial position with a trans configuration relative to each other. In the crystal, the complex molecules are bound by weak C-H…π interactions and form layers in the (001) plane, alternating with each other. The structure of the coordination polyhedron of the described compound is similar to the structure of adducts of β-dicarbonyl complexes of d‑metals with pyridine.
In the work, a bimetallic cobalt-titanium oxide CoTiO3 with a perovskite structure was synthesized by a simple method of spontaneous hydrolysis with subsequent thermal annealing. The influence of the presence of hydrogen peroxide during synthesis and annealing temperature on the phase composition, structural, morphological and surface characteristics of the obtained materials was studied using X-ray phase analysis, scanning electron microscopy and porometry. It was shown that the formation of the crystalline phase of perovskite CoTiO3 occurs at annealing temperatures of 500 °C and above. Increasing the annealing temperature from 400 to 800 °C leads to particle enlargement from ~50 nm to 200–400 nm and a concomitant increase in crystallinity. The electrochemical properties of CoTiO3 were studied by galvanostatic cycling in half-cells with lithium and sodium anodes in the voltage range of 0.01–3 V and current densities from 0.1 to 5 A/g. It was found that the increase in crystallinity of CoTiO3 due to an increase in the annealing temperature to 800 °C has a positive effect on the stability of the specific capacity, improves the rate characteristics and reduces the number of activation charge-discharge cycles. In lithium-ion cells, the maximum specific capacity of CoTiO3, which reaches 218 mAh/g after 190 cycles at a current density of 0.1 A/g, and the best stability during cycling and discharge at high current densities are characteristic of samples annealed at a temperature of 800 °C. The specific capacity of CoTiO3 in the sodium-ion system is almost 2 times lower and is less dependent on the annealing temperature. It is shown that the nature of the alkali metal cation significantly affects the capacitive and kinetic characteristics of CoTiO3, respectively, the better electrochemical properties of CoTiO3 in the lithium system are associated with a higher diffusion ability and smaller kinetic limitations of the Li+ cation compared to the larger Na+ cation.
The work presents studies on the synthesis of new heterometallic complexes of La(III) and Co(II), Ni(II), Cu(II) with succinic acid and pyridine (Py). Mixed-ligand, heterometallic coordination compounds of the general composition [М2La2(C4Н4O4)5·4Py]·4Н2О (МІІ=Со, Ni, Cu) were obtained. Their thermal properties were studied and the ability of heterocomplexes to form complex oxides was determined. The complexes were characterized using elemental analysis and thermogravimetric method. Assessment of their thermal stability showed that the thermal decomposition of the synthesized heterocomplexes proceeds in stages and has a multistage nature. Their thermolysis proceeds through the stages of elimination of water molecules (100–220°C), then pyridine (185–310°C), which is accompanied by exothermic effects on the DTA curves, and to the complete thermal decomposition of heterometallic coordination compounds. In the temperature range from 260°C to 700°C, intensive decomposition of complexes occurs, due to the destruction of the organic part, which is accompanied by exothermic effects. During the thermolysis of heterocomplexes at 800°C, 900°C, 1000°C, oxide powders were obtained. Their composition was controlled by X-ray phase analysis. Phase identification was carried out by comparing experimental diffraction patterns with the ICDD PDF-2 databases. It is shown that the compounds [М2La2(C4Н4O4)5·4Py]·4Н2О (M=Co, Cu) decompose at a temperature of 900°С mainly to complex oxides LaСоО3 and La2СuО4 with small impurities of La(OH)3 and non-stoichiometric cupric oxide CuxO, respectively. The thermal destruction of the complex [Ni2La2(C4Н4O4)5·4Py]·4Н2О is accompanied by the formation of the dominant phase of lanthanum nickelates La2NiО4 and LaNiO3, and a small content of NiO and La(OH)3 oxides as side phases was also found. Thus, the heterometallic complexes Co2La2(C4Н4O4)5·4Py]·4Н2О, [Ni2La2(C4Н4O4)5·4Py]·4Н2О and [Cu2La2(C4Н4O4)5·4Py]·4Н2Оcan be used as precursors to obtain complex oxides – cobaltate, nickelate, or lanthanum cuprate with lower energy costs than in solid-phase synthesis.
The work presents a comprehensive selection of conditions for the synthesis of nanosized Copper particles in an aqueous oxidizing environment using a biocompatible amino acid – L-Сysteine as a stabilizer, a reducing agent – sodium tetraborate, and the application of the method of mathematical experimental planning the Scheffe method. The use of the mathematical planning method made it possible to predict the additive effect of the ratio between precursors in the studied medium on the value of the optical absorption edge of the obtained colloidal solutions of copper nanoparticles, their stability over time and the effect on test cultures of microorganisms P.aeruginosa, C.albicans, B.subtilitis. The ratio between the starting reagents that lead to the formation of stable colloidal solutions of copper nanoparticles at pH=6 and temperature of 20°C in an oxidizing reaction medium has been established. A mathematical model was constructed in the form of a projection onto the plane of an equilateral triangle of the dependence of the value of the optical absorption edge of colloidal solutions of metallic copper nanoparticles on the ratio between the precursors. A mathematical equation was obtained – a fourth-degree polynomial that describes the dependence of the value of the optical absorption edge of colloidal solutions of copper nanoparticles on the ratio between three independent variables – crystal-forming components of time-stable particles in the reaction medium. The antibacterial activities of a series of test solutions were investigated by the micromethod of serial dilutions in accordance with the procedures of the European Committee for Susceptibility Testing against reference strains of bacteria (P.aeruginosa, C.albicans, B.subtilitis.). Using the Scheffe mathematical model, the concentration regions and ratios between the components of the studied system were determined, which had the highest impact on the action of test cultures of microorganisms.
α-Aminocyclopropanecarboxylic acid (ACC) and its derivatives are widely distributed in the plant kingdom, fulfilling diverse roles ranging from regulation of plant life cycles to defensive mechanisms. The sterically constrained structure of ACC has proven invaluable in the design of numerous drugs, particularly hepatitis C virus (HCV) NS3/4A protease inhibitors. Indeed, ACC has been instrumental in the development of multiple generations of potent HCV treatments, with ongoing efforts focused on further improvements and refinements. The inherent steric constraints of these derivatives present a significant challenge for their synthesis, especially in enantiomerically pure form. This article provides a comprehensive overview of synthetic methodologies reported in the literature for the preparation of ACC and its derivatives. The synthetic strategies discussed herein are organized based on key transformations, including dialkylation of nucleophilic glycine equivalents, cyclopropanation of carbenoid glycine equivalents, and addition reactions to dehydroamino acids. Particular emphasis is placed on asymmetric approaches that enable the preparation of these tailor-made amino acids in enantiomerically pure form. Furthermore, aspects of Self-Disproportionation of Enantiomers (SDE) relevant to enantioselective catalysis are highlighted. By compiling these methodologies, we aim to provide a comprehensive resource and a source of inspiration for researchers in synthetic and medicinal chemistry, as well as drug discovery.
Dedication: To Casey and Calley Means, fearless science and health advocates, for their inspiring work in redefining wellness and empowering individuals to take charge of their metabolic destinies. Micro-/nanoplastics represent a ubiquitous environmental contaminant with potential adverse effects across all living organisms. Ongoing research consistently reveals new and expands upon existing concerns regarding plastic exposure. Notably, emerging evidence suggests a link between plastic exposure and premature cognitive decline in older adults, potentially contributing to the onset or exacerbation of neurodegenerative diseases associated with dementia. Furthermore, endocrine-disrupting chemicals derived from plastics have been implicated in hormonal imbalances, potentially resulting in the masculinization of female development and the feminization of male development. If unmitigated, these impacts could precipitate a substantial and unforeseen environmental health crisis. This Perspective employs a chemistry-based approach to elucidate plastic-related health issues and introduces the concept of bioavailable plastic, i.e. plastic particles smaller than 2.5 μm capable of biological barrier penetration. We highlight lipophilicity as the key physicochemical property responsible for the uptake of these particles within organisms particularly their accumulation in adipose tissues, including the brain. Furthermore, we propose a solvation-assisted desorption mechanism whereby oligomeric molecules released from plastics in fatty tissues generate mono- and dicarboxylic acids that mimic endogenous fatty acids. These exogenous fatty acids can integrate into phospholipid and glycolipid biosynthesis becoming components of cell membranes and myelin sheaths. These considerations should stimulate research aimed at neurological health protection in an increasingly plastic-laden environment, though the broader implications of this integration are of significant concern. Mechanistic understanding of the link between bioavailable plastic exposure and central nervous system disorders is crucial for informing transformative policy changes and preventive measures to safeguard future generations’ health. To empower readers with actionable strategies for reducing plastic exposure, we offer several recommendations. Notably, limiting the consumption of fatty animal products, especially pork fat (salo) is advised. While salo is a culturally significant food, it appears to be a major reservoir for plastic particles, particularly those smaller than 200 nm, i.e. bioavailable plastic. These nanoparticles, due to their ability to traverse biological barriers in humans, pose a considerable risk. This Perspective seeks to underscore the critical need for comprehensive research into the long-term health effects of microplastics highlighting their pervasive presence and potential hidden dangers.
In this work, the possibility of electrochemical synthesis of tantalum silicides, in particular Ta2Si, using chloride-fluoride melts NaCl–KCl–K2TaF7–K2SiF6 as an electrolytic medium was investigated. The influence of key process parameters, such as temperature, melt composition and potential, on the phase composition and morphology of the final products was studied. Based on thermodynamic calculations that take into account the Gibbs energy of formation of the corresponding compounds, as well as a complex of voltammetric studies, including cyclic voltammetry, the mechanism of electrochemical reduction of tantalum and silicon ions to Ta2Si was established. This confirms the effectiveness of using chloride-fluoride melts for the direct synthesis of tantalum silicides. It was experimentally shown that the ratio of the volumetric concentrations of tantalum and silicon in the melt does not affect the stoichiometry of the cathodic reduction products. Regardless of the initial ratio, the main product of electrolysis is Ta2Si, which indicates the thermodynamic advantage of the formation of this particular phase under the studied conditions. Electrolysis on nickel cathodes produced Ta2Si powders and coatings that differ in morphology and particle size. The phase composition and morphology of the synthesized products were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of current density on the deposition rate and quality of the obtained materials was studied. In particular, in a NaCl–KCl melt containing 2 wt.% K2SiF6 and 5 wt.% K2TaF7, at a current density in the range of 0.1–0.2 A/cm² and a temperature of 700 °C, powders with a porous structure consisting of agglomerates of small dendritic particles were obtained. The optimal current density range of 0.03–0.08 A/cm² for the deposition of homogeneous and dense Ta2Si coatings with characteristic globular elements has been determined. The results obtained demonstrate the significant potential of electrochemical synthesis from chloride-fluoride melts for obtaining tantalum silicides with controlled phase composition and morphological characteristics, which opens up prospects for their application in various high-tech industries, including microelectronics, wear-resistant and corrosion-resistant coatings, and high-temperature materials.
The results of studies for thermal dehydration processes of protonated and hydrated phosphates of divalent metals and their ammonia and ammonium derivatives that were described by reversible and irreversible reactions, were generalized. It was shown the influence of pressure and temperature on conditions for obtaining intermediate and final thermolysis products of Mn2+, Co2+, Cu2+, Zn2+, Cd2+, Sr2+ phosphates. Thermal transformations of phosphates were studied by thermal analysis on a Q-1500D derivatograph using dynamic and quasi-isothermal heating regime. The methodology for determining the chemical nature of phosphates thermolysis included obtaining samples of intermediate dehydration products at typical points of thermal analysis curves and their studying by chemical analysis, quantitative paper chromatography. The IR spectra were taken on a Specord 75-IR spectrophotometer, and X-ray phase analysis was carried out on a DRON-UM1 diffractometer. The sequence of thermal transformations of hydrated heterometallic monophosphates of divalent metals and their ammonia and ammonium derivatives has been determined to assess the temperature ranges for obtaining of anhydrous complex phosphates with controlled cationic and anionic composition. The optimal temperature regimes for obtaining of dehydrated phosphates of Cu2+, Zn2+, Co2+, Сd2+, Ni2+ with individual composition have been determined in the process of thermolysis in various types of their compounds: – crystallohydrates of orthophosphates (M3(РО4)2∙nH2O) into anhydrous phosphates M3(РО4)2; – crystallohydrates of hydrogen phosphates and double ammonium phosphates (MHPO4·nH2O, MNH4PO4·nH2O) into anhydrous diphosphates M2P2O7; – crystallohydrates of basic phosphates (M2ОHPO4·nH2O) into oxyphosphates M4O(PO4)2; – aquaamminoorthophosphates [M3(NH3)x(H2O)y(PO4)2]∙nH2O into anhydrous phosphates M3(РО4)2; – double aquaamminoorthophosphates [M13-xM2х(NH3)y(H2O)z(PO4)2]∙nH2O into anhydrous double phosphates M13-xM2х(PO4)2; – triple aquaamminoorthophosphates [M13-x-уM2хM3y(NH3)y(H2O)z(PO4)2]∙nH2O into anhydrous triple phosphates M13-x-yM2хM3y(PO4)2.
The article provides an overview of the life and creative scientific path of Anton Dumanskyi – a well-known chemist of our country, who is widely known abroad in the field of colloidal chemistry, a corresponding member of the USSR Academy of Sciences, a member of the Ukrainian SSR Academy of Sciences, professor, doctor of chemistry, an honored scientist of the Ukrainian SSR, an honored scientist of the Kazakh SSR, the director of the Institute of General and Inorganic Chemistry of the Ukrainian Academy of Sciences in the forties and fifties of the last century. A brief description of the scientific directions and achieved results of the research carried out in the field of colloidal chemistry is given, the role of his research for the development of domestic chemical science and the national economy is determined. Anton Dumanskyi is one of the founders of colloidal chemistry in our country. Of particular importance are his works on the application of the method of physicochemical analysis to the study of the properties of colloidal systems. Dumanskyi was awarded the Mendeleev Prize for a series of works on this issue. He paid great attention to the study of the basic physicochemical properties of lyophilic disperse systems and clearly substantiated the idea of a bound liquid as a measure of lyophilicity. With a group of his students, he solved a number of theoretical problems in a short time: he determined the general patterns of interaction of high polymers with various liquids and studied the mechanism of this process; he developed new methods for the quantitative determination of bound water and the general principles of lyophilization of dispersed phases; he found out the influence of bound water on the dielectric properties of disperse systems. Dumanskyi’s research, which is related to the technology of many branches of the food industry, is especially fruitful. He is the author of over 250 scientific works, including a number of monographs and manuals. Under the guidance and advice of Dumanskyi, over 50 candidates and about 20 doctors of science were trained. He had government awards – orders and medals. In 1980, after the 100th birth anniversary of academician A.V. Dumanskyi, his name was assigned to the Institute of Coloid Chemistry and Water Chemistry of the Natiomal Academy of Sciences of Ukraine.
3D printing allows one the production of membranes of any shape and size according to consumer requirements. The work solves the problem of studying the separation properties of filtration membranes, which, unlike the known ones, were obtained via one stage. Polylactic acid (polylactide, PLA) and its mixture with a pore former − sucrose served as the ink for the 3D printer. The fused deposition modelling technique was used for printing. The membranes imcluded three layers, and each layer consisted of parallel strips, the width of which was determined by the diameter of the extruder nozzle (0.4 mm). The pores that provide filtration can be located at the joints of the strips. The membranes almost completely retain bovine serum albumin (BSA) macromolecules. The pore size is estimated to be 6−17 nm, in other words, the membranes show ultrafiltration properties. The membranes were used to concentrate polyphenols from an extract of orange peels and to recovery cationic and anionic dyes (methylene blue and reactive black 5, respectively) from aqueous solutions. It was found that the highest selectivity of the membranes is realized at a pressure of 0.5 (polyphenols, 90−98%), 1.5 (anionic dye, 90−96%) and 2.5 bar (cationic dye, 83−87%). Filtration leads to decolorization of weakly colored solutions. It was found that the membrane obtained from a mixture of PLA and a pore former is characterized by higher productivity, selectivity, and resistance against organic contaminants than a membrane made of pure polymer. It is assumed that the difference between the behaviour of the membranes is due to the peculiarities of the thermal destruction of PLA during printing, which occurs at 200
