Dmitriy V. Maltsev  Alexander A. Spasov  Pavel M. Vassiliev  Maria O. Skripka  Mikhail V. Miroshnikov  Andrey N. Kochetkov  Nataliya V. Eliseeva  Yuliya V. Lifanova  Tatyana A. Kuzmenko  Lyudmila N. Divaeva  Anatolii S. Morkovnik 《Molecules (Basel, Switzerland)》2021,26(19)

A number of novel 2,3,4,5-tetrahydro[1,3]diazepino[1,2-a]benzimidazole derivatives 2 were obtained by alkylation mainly in the 1H-tautomeric form of 2,3,4,5-tetrahydro[1,3]diazepino[1,2-a]benzimidazole or its 8,9-dimethyl-substituted analog 4-chlorobenzyl bromide, 4-chloroacetic acid fluoroanilide, and 4-tert-butylphenacyl bromide in neutral medium. Compounds 3 were cyclized and synthesized earlier with 11-phenacyl-substituted diazepino[1,2-a]benzimidazoles upon heating in conc. HBr. The chemical structures of the compounds were clarified by using the ¹H Nuclear Magnetic Resonance Spectroscopy (¹H-NMR) technique. Anxiolytic properties were evaluated using the elevated plus maze (EPM) and open field (OF) tests. The analgesic effect of compounds was estimated with the tail flick (TF) and hot plate (HP) methods. Besides, possible the influence of the test compounds on motor activities of the animals was examined by the Grid, Wire, and Rotarod tests. Compounds 2d and 3b were the most active due to their prominent analgesic and anxiolytic potentials, respectively. The results of the performed in silico analysis showed that the high anxiolytic activity of compound 3b is explained by the combination of a pronounced interaction mainly with the benzodiazepine site of the GABA_A receptor with a prominent interaction with both the specific and allosteric sites of the 5-HT_2A receptor.  相似文献   

    

Olga Bakulina  Anna Inyutina  Dmitry Dar&#x;in  Mikhail Krasavin 《Molecules (Basel, Switzerland)》2021,26(21)

This review summarizes recent developments in multicomponent reactions of diazo compounds. The role of diazo reagent and the type of interaction between components was analyzed to structure the discussion. In contrast to previous reviews on related topics mostly focused on metal catalyzed transformations, a substantial amount of organocatalytic or catalyst-free methodologies is covered in this work.  相似文献   

    

Andrey N. Komogortsev  Valeriya G. Melekhina  Boris V. Lichitsky  Mikhail E. Minyaev 《Journal of heterocyclic chemistry》2021,58(3):864-872

A convenient method for the synthesis of novel imidazole-2-thione derivatives containing allomaltol fragment was elaborated. This approach includes one-pot multicomponent reaction of allomaltol, arylglyoxals, primary amines followed by addition of alkyl or aryl isothiocyanates. It was shown that the key intermediates of the studied process are substituted α-aminoketones and the corresponding imidazolidine-2-thione. The advantages of this synthesis are mild reaction conditions, atom economy, and easy workup procedure, which can avoid chromatographic purifications. The structures of an intermediate imidazolidine-2-thione and one of the final imidazole-2-thiones were determined by X-ray diffraction.  相似文献   

    

Viktor Pogorilyy  Anna Plyutinskaya  Nikita Suvorov  Ekaterina Diachkova  Yuriy Vasil&#x;ev  Andrei Pankratov  Andrey Mironov  Mikhail Grin 《Molecules (Basel, Switzerland)》2021,26(23)

In this work, we obtained the first selenium-containing chlorin with a chalcogen atom in exlocycle E. It was shown that the spectral properties were preserved in the target compound and the stability increased at two different pH values, in comparison with the starting purpurin-18. The derivatives have sufficiently high fluorescence and singlet oxygen quantum yields. The photoinduced cytotoxicity of sulfur- and selenium-anhydrides of chlorin p₆ studied for the first time in vitro on the S37 cell line was found to be two times higher that of purpurin-18 and purpurinimide studied previously. Moreover, the dark cytotoxicity increased four-fold in comparison with the latter compounds. Apparently, the increase in the dark cytotoxicity is due to the interaction of the pigments studied with sulfur- and selenium-containing endogenous intracellular compounds. Intracellular distributions of thioanhydride and selenoanhydride chlorin p₆ in S37 cells were shown in cytoplasm by diffusion distribution. The intracellular concentration of the sulfur derivative turned out to be higher and, as a consequence, its photoinduced cytotoxicity was higher as well.  相似文献   

    

Sofia A. Zakharenkova  Marina I. Lebedeva  Alexandra N. Lebedeva  Irina A. Doroshenko  Ksenya Yu Vlasova  Anastasiya A. Bartoshevich  Vladimir M. Senyavin  Sergey S. Abramchuk  George G. Krivtsov  Alexander A. Ezhov  Tatyana A. Podrugina  Natalia L. Klyachko  Mikhail K. Beklemishev 《Molecules (Basel, Switzerland)》2021,26(24)

Imaging-guided delivery is developed for hydrophobic drugs, and to a much lesser extent, hydrophilic ones. In this work we have designed a novel strategy for real-time monitoring of hydrophilic drug delivery. Traditionally, the drug and the dye are covalently attached to a nanocarrier or are electrostatically adsorbed. Recently, we found an efficient way to bind the drug by ion-paring with an appropriate counter-ion to form the aggregate that embeds a hydrophobic dye with a considerable fluorescence enhancement. We synthesized a series of carbocyanine dyes of hydrophobicity sufficient for solubilization in hydrophobic ion pairs, which restores their emission in the near-infrared (NIR) region upon the formation of the ternary aggregates. To avoid using toxic surfactants, we applied an amphiphilic polymer-oligomer poly(hexamethylene guanidine) (PHMG) as a counter-ion. Сeftriaxone was used as a model hydrophilic drug ensuring the highest fluorescent signal. The so-formed drug–counter-ion–dye aggregates were encapsulated into a cross-linked maleated chitosan carrier. Confocal laser scanning microscopy (CLSM) studies have demonstrated internalization of the encapsulated model drug by breast adenocarcinoma cells at 40 min after treatment. These results suggest the potential application of hydrophobic ion pairs containing an NIR dye in imaging-guided delivery of hydrophilic compounds.  相似文献   

    

Olga E. Andreeva  Yuri Y. Shchegolev  Alexander M. Scherbakov  Ekaterina I. Mikhaevich  Danila V. Sorokin  Margarita V. Gudkova  Irina V. Bure  Ekaterina B. Kuznetsova  Dmitry S. Mikhaylenko  Marina V. Nemtsova  Dmitry V. Bagrov  Mikhail A. Krasil&#x;nikov 《Molecules (Basel, Switzerland)》2021,26(9)

  相似文献   

    

Anton Budeev  Grigory Kantin  Dmitry Dar&#x;in  Mikhail Krasavin 《Molecules (Basel, Switzerland)》2021,26(9)

Diazocarbonyl compounds have found numerous applications in many areas of chemistry. Among the most developed fields of diazo chemistry is the preparation of azoles from diazo compounds. This approach represents a useful alternative to more conventional methods of the synthesis of azoles. A comprehensive review on the preparation of various azoles (oxazoles, thiazoles, imidazoles, pyrazoles, triazoles, and tetrazoles) from diazocarbonyl and related compounds is presented for the first time along with discussion of advantages and disadvantages of «diazo» approaches to azoles.  相似文献   

    

Victoria E. Gontcharenko  Mikhail A. Kiskin  Vladimir D. Dolzhenko  Vladislav M. Korshunov  Ilya V. Taydakov  Yury A. Belousov 《Molecules (Basel, Switzerland)》2021,26(9)

Three novel lanthanide complexes with the ligand 4,4-difluoro-1-(1,5-dimethyl-1H-pyrazol-4-yl)butane-1,3-dione (HL), namely [LnL₃(H₂O)₂], Ln = Eu, Gd and Tb, were synthesized, and, according to single-crystal X-ray diffraction, are isostructural. The photoluminescent properties of these compounds, as well as of three series of mixed metal complexes [Eu_xTb_1-xL₃(H₂O)₂] (Eu_xTb_1-xL₃), [EuxGd_1-xL₃(H₂O)₂] (Eu_xGd_1-xL₃), and [Gd_xTb_1-xL₃(H₂O)₂] (Gd_xTb_1-xL₃), were studied. The Eu_xTb_1-xL₃ complexes exhibit the simultaneous emission of both Eu³⁺ and Tb³⁺ ions, and the luminescence color rapidly changes from green to red upon introducing even a small fraction of Eu³⁺. A detailed analysis of the luminescence decay made it possible to determine the observed radiative lifetimes of Tb³⁺ and Eu³⁺ and estimate the rate of excitation energy transfer between these ions. For this task, a simple approximation function was proposed. The values of the energy transfer rates determined independently from the luminescence decays of terbium(III) and europium(III) ions show a good correlation.  相似文献   

    

Alexander S. Zyubin  Tatyana S. Zyubina  Olga I. Istakova  Nataliia V. Talagaeva  Ekaterina V. Zolotukhina  Mikhail A. Vorotyntsev  Dmitry V. Konev 《中国化学会会志》2023,70(3):637-647

Quantum chemical approach has been applied for modeling the change in the conformation of the polypyrrole (PPy) chain both in its neutral and positively charged (doped) states due to its interaction with incorporated counterions. Polymer has been modeled by oligopyrrole molecule of 9–15 monomer units. It is shown that it is energetically favorable to reorient the pyrrole rings closest to the anion from trans to cis position. This reorientation leads to the formation of meanders which include 3–5 pyrrole rings per loop. Reduction in the loop size decreases the energy of interaction with the ion while an increase in the loop size reduces the number of attached ionic species accompanied by a slight change in their interaction energy with the PPy chain. The observed effect of polymer chain structuring in the presence of anions is proposed as a possible reason explaining the experimentally recorded broadening of the electroactivity potential region and the conductive state of the polypyrrole film on the electrode surface as a result of multiple repetitions of charge/discharge cycles of the polymer chain. Vibrational spectra of oligopyrrole complexes have been calculated, and prospects for experimental detection of predicted conformational states by IR spectroscopy are assessed.  相似文献   

    

Evgeniia E. Ondar  Dr. Mikhail V. Polynski  Prof. Dr. Valentine P. Ananikov 《Chemphyschem》2023,24(11):e202200940

Water-soluble Pt complexes are the key components in medicinal chemistry and catalysis. The well-known cisplatin family of anticancer drugs and industrial hydrosylilation catalysts are two leading examples. On the molecular level, the activity mechanisms of such complexes mostly involve changes in the Pt coordination sphere. Using ¹⁹⁵Pt NMR spectroscopy for operando monitoring would be a valuable tool for uncovering the activity mechanisms; however, reliable approaches for the rapid correlation of Pt complex structure with ¹⁹⁵Pt chemical shifts are very challenging and not available for everyday research practice. While NMR shielding is a response property, molecular 3D structure determines NMR spectra, as widely known, which allows us to build up 3D structure to ¹⁹⁵Pt chemical shift correlations. Accordingly, we present a new workflow for the determination of lowest-energy configurational/conformational isomers based on the GFN2-xTB semiempirical method and prediction of corresponding chemical shifts with a Machine Learning (ML) model tuned for Pt complexes. The workflow was designed for the prediction of ¹⁹⁵Pt chemical shifts of water-soluble Pt(II) and Pt(IV) anionic, neutral, and cationic complexes with halide, NO₂⁻, (di)amino, and (di)carboxylate ligands with chemical shift values ranging from −6293 to 7090 ppm. The model offered an accuracy (normalized root-mean-square deviation/RMSD) of 1.08 %/145.02 ppm on the held-out test set.  相似文献