Russian Journal of General Chemistry最新文献

Iodine- and bromine-containing tetrazolo[5,1-b][1,3]thiazinium halides were synthesized for the first time by electrophilic heterocyclization of 5-prenylsulfanyl- and 5-(3-butenyl)sulfanyl-1-methyltetrazoles under the action of iodine or bromine in various solvents. The structure of the obtained compounds was studied and confirmed by ¹H and ¹³C{¹H} NMR spectroscopy methods. The structure of 7-iodomethyl-3-methyl-6,7-dihydro-5H-tetrazolo[5,1-b][1,3]thiazinium polyiodide and non-covalent interactions (short contacts) cation···anion were characterized by single crystal X-ray diffraction analysis.

Alkylation of phthalimide with α,ω-dibromoalkanes in dimethylformamide in the presence of anhydrous potassium carbonate afforded a series of α,ω-diphthalimidoalkanes. Their subsequent hydrolysis in a potassium hydroxide solution, steam distillation of the diamine bases, and neutralization of the distillate with hydrochloric acid yielded the target α,ω-diaminoalkanes as dihydrochlorides with overall yields of 90–96%.

The possibility of creating stable fluorescent labels based on triblock copolymers P123 and F127 doped with quinoxalinone derivatives of D-π-A architecture is considered. The hydrophobicity of the micellar core is shown to be the key factor determining dye encapsulation efficiency as well as colloidal and spectral stability. The more hydrophobic P123 demonstrates superior solubilization capacity for all examined dyes, forming monodisperse nanoparticles that remain stable for at least 5 days. In contrast, F127-based systems exhibit a tendency toward aggregation and the formation of large structures. In P123 micelles, homologous dyes display similar emission spectra, indicating a similar microenvironment and conformation, whereas in F127 micelles significant spectral differences are observed for the same dyes. The optimal dye–carrier pair is the P123@4 system, which exhibits high luminescence intensity, high colloidal and spectral stability over time, and resistance to bovine serum albumin (BSA). These results are important for the development of effective fluorescent labels and theranostic platforms based on triblock copolymer micelles.

A one-pot three-component synthesis of previously undescribed 3-alkenyl(propargyl)sulfanyl-indeno[1,2-e][1,2,4]triazin-9-ones was developed for the first time. The direction of cyclization in the reaction of ninhydrin and thiosemicarbazide in the presence of a base and an alkyl halide was-established for the first time by single crystal XRD analysis using the-example of 3-allylsulfanylindeno[1,2-e][1,2,4]triazin-9-one. In some cases, subsequent heterocyclization was also achieved, in particular, for allyl sulfide under the action of bromine, for methallyl sulfide under the action of iodine and bromine, and for butenyl sulfide under the action of iodine.

The Orthopoxvirus genus (smallpox, monkeypox, etc.) remains a serious threat in the context of the cessation of mass vaccination. This review systematizes data from 2012–2025 on low-molecular-weight orthopoxvirus inhibitors, focusing on their targets and mechanisms of action. Licensed drugs (tecovirimat, cidofovir, brincidofovir) and promising compounds (NIOCH-14) are discussed. Particular attention is paid to new targets: viral replication proteins (D4, E9), transcription factors (F10), enzymes (I7L protease, resolvase, decapping ribonuclease D9), as well as cellular targets (DHODH, SAH hydrolase, BTK and PLK1 kinases). Key structural classes of inhibitors are analyzed: nucleoside analogs, monoterpenoid derivatives (camphor, fenchone), adamantane-based compounds, and heterocyclic systems. The shift from empirical screening to targeted design based on target structures is emphasized. The conclusion highlights significant progress in expanding the arsenal of targets and the chemical diversity of compounds, opening new avenues for developing effective therapies.

A one-pot approach was proposed for the synthesis of functionalized 1-alkenyl-3-methylimidazole-2-thiones (yields up to 30%) by intercepting the carbene, generated in situ from 1-methylimidazole and acylphenylacetylenes, with elemental sulfur.

Water-soluble compositions containing up to 4.3% of a curcuminoid mixture with known biological activity were prepared based on amphiphilic copolymers of N-vinylpyrrolidone with (di)methacrylates of various chemical compositions and macromolecular architectures, as well as linear poly-N-vinylpyrrolidone. Dynamic light scattering revealed stable polymer structures in aqueous solution with sizes of approximately 100–1000 nm. Cyclic and square-wave voltammetry revealed differences in the electrooxidation energetics of curcumin– (co)polymer compositions depending on the nature of the polymer, in comparison with native curcumin. UV–Vis spectroscopy was employed to evaluate the stability of the curcuminoid mixture in neutral phosphate-buffered saline as a function of (co)polymer chemical composition; enhanced stability was observed in polymer matrices containing acrylic acid or poly(ethylene glycol) methyl ether methacrylate units. Quantum chemical (DFT) modeling of polymer–curcumin structures indicated the possibility of hydrogen bond formation between functional groups of the carrier and the active compound in both enol and keto forms. The keto–enol tautomerization of curcumin is facilitated in poly-N-vinylpyrrolidone due to cleavage of its intramolecular bond and is hindered in copolymers containing triethylene glycol dimethacrylate and acrylic acid units.

Three new Ni(II) coordination compounds with anions of 4,8-disulfo-2,6-naphthalenedicarboxylic acid (H₄dsndc) and 1,2-bis(4-pyridyl)ethylene (bpe), differing in dimensionality and structure, were obtained: the molecular complex [{Ni(H₂O)₅}₂(bpe)](dsndc), the one-dimensional coordination polymer [Ni(H₂O)₄(bpe)](H₂dsndc)·2H₂O, and the two-dimensional coordination polymer [{Ni(H₂O)₃}₂(bpe)₂(dsndc)]·2H₂O. The structures of the compounds were determined by single-crystal X-ray diffraction analysis. The compound [Ni(H₂O)₄(bpe)](H₂dsndc)·2H₂O was obtained in chemically and phase-pure form and characterized by a standard set of physicochemical methods (powder X-ray diffraction, elemental and thermogravimetric analyses, and IR spectroscopy).

The review is devoted to a unique approach that enables the formation of homogeneous chitosan hydrogels and films with oppositely charged biopolymers and inorganic nanoparticles in a self-organizing regime, controlled by regulated charging of the polysaccharide through the slow acidification by gluconic acid of the initial neutral solution, in which chitosan is added in an uncharged state. The acid is generated during the hydrolysis of non-toxic D-glucono-δ-lactone, widely used in the food industry. The prepared hydrogels and films are fundamentally differed from coacervates in their structure and properties, which also consist of polyelectrolyte complexes but in the form heterogeneous precipitate without any pronounced structural organization due to a rapid, uncontrollable cooperative processes. The review compares both methods, their experimental features, and differences in their mechanisms. Finally, examples of the functional materials that have been fabricated to date using controlled charging of chitosan are presented. The advantages of this approach are highlighted, including the process being carried out solely in aqueous solutions, without the addition of organic solvents, and at room temperature. Gelling is achieved only through physical interactions, eliminating the use of toxic cross-linking agents and reagents.

A protective effect of CeO₂ nanoparticles on human serum albumin (HSA) under nitrosative stress induced by peroxynitrite (ONOO^–) was demonstrated. The effect of nanodisperse CeO₂ and ONOO^– on the tryptophan fluorescence of purified HSA, as well as albumin isolated from biological fluids, blood plasma, peritoneal (ascitic), and synovial (joint) fluids, was examined for the first time by fluorescence spectroscopy. ONOO^– decreased the intrinsic fluorescence of HSA, whereas preliminary incubation of the protein with a CeO₂ sol markedly attenuated this effect. In the presence of nanodisperse CeO₂, the degree of oxidative modification of albumin induced by ONOO^– decreased by ~20%. The results further indicate the substantial potential of nanodisperse CeO₂ for biomedical applications.