Detrifluoroacetylation of Ethyl 2-(Ethoxymethylene)- 4,4,4-Trifluoro-3-Oxobutanoate

This work was financially supported by the Council for grants of the President of Russian Federation (grant no. MK-1453.2019.3)

Polynuclear Metallic Architectures Based on Fluorinated Functionalized Diketonates

K.Y.S. is thankful to the Council for grants of the President of Russian Federation (grant no. 1453.2019.3)

Heterometallic Molecular Architectures Based on Fluorinated β-Diketone Ligands

This review summarizes the data on the synthesis of coordination compounds containing two or more different metal ions based on fluorinated β-diketonates. Heterometallic systems are of high interest in terms of their potential use in catalysis, medicine and diagnostics, as well as in the development of effective sensor devices and functional materials. Having a rich history in coordination chemistry, fluorinated β-diketones are well-known ligands generating a wide variety of heterometallic complexes. In this context, we focused on both the synthetic approaches to β-dicarbonyl ligands with additional coordination centers and their possible transformations in complexation reactions. The review describes bi- and polynuclear structures in which β-diketones are the key building blocks in the formation of a heterometallic framework, including the examples of both homo- and heteroleptic complexes. © 2022 by the authors.Russian Academy of Sciences, РАН, (AAAA-A19-119011290117-6)This work was carried out in the framework of the basic theme of the Russian Academy of Sciences (state registration № AAAA-A19-119011290117-6)

A Rare Example of Discrete Lanthanide–Lithium Tetrakis-β-Diketonates: Synthesis, Structures, and Luminescence Properties

Abstract: The reactions of functionalized lithium CF3-β-diketonate (LiL) with europium(III) and terbium(III) chlorides in acetonitrile afford heterobimetallic complexes with the general formula [LiL-nL4(H2O)](CH3CN) (Ln = Eu (IIIa) and Tb (IIIb)). It is found that Ln–Li tetrakis-β-diketonates can also be prepared by the crystallization from acetonitrile of the previously synthesized complexes [(LnL3)(LiL)(MeOH)] (I) and [(LnL3)(LiL)(H2O)] (II). For the first time, the single crystals of the compounds in a series of Ln–Li tetrakis-β-diketonates are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1973632 (IIIa) and 1973633 (IIIb)). The photoluminescence properties of the synthesized heterometallic complexes in the solid state are studied. © 2020, Pleiades Publishing, Ltd.This work was supported by the Russian Foundation for Basic Research (project no. 18-33-20124), Council for Grants of President of the Russian Federation (grant no. MK-1453.2019.3), and basic themes of the Russian Academy of Sciences (state registration nos. AAAA-A19-119011790132-7 and AAAA-A19-119012490006-1)

Polyfluoroalkylated 2,3-Butanedione-Based Lithium Diketonates as Promising Building Blocks in Coordination and Heterocyclic Chemistry

Financial support from the Russian Foundation for Basic Research (grant № 18-33-20124) is gratefully acknowledged

Expanding 1,2,4-triketone Toolbox for use as Aluorinated Building Blocks in the Synthesis of Pyrazoles, Pyridazinones and β-diketohydrazones

Fluorinated lithium β-diketonates bearing a methyl acetal group behave in the condensation reactions with hydrazines as trielectrophilic building blocks for the preparation of pyrazoles, pyridazinones and β-diketohydrazones. For the first time, solvent-induced regioisomeric and heterocyclic ring size-controlled formation was observed for 1,2,4-triketone analogues. Fluoroalkylated acetyl NH-pyrazoles or substituted 5-RF-pyrazoles were obtained from the acid-catalyzed cyclocondensation of lithium β-diketonates with (aryl)hydrazines in ethanol. In methanol solvent acetyl-containing 3-CF3-pyrazoles were isolated because of inverse nucleophilic attack of arylhydrazines. The use of aprotic acetonitrile in the condensation resulted in regioselective trifluorinated pyridazinones and fluorinated β-diketohydrazones formation via initial acetal fragment interaction with N,N-dinucleophile. © 2021 Elsevier B.V.This work carried out in the framework of the basic theme of the Russian Academy of Sciences (state registration № AAAA-A19-119011790132-7). Single-crystal X-ray diffraction analysis for 3g, 3f and 10a was performed using the equipment of the JRC PMR IGIC RAS. Single-crystal X-ray diffraction analysis for 5d, 7a, 9a and physicochemical studies were carried out using the equipments of the Center for Joint Use "Spectroscopy and Analysis of Organic Compounds" at the Postovsky Institute of Organic Synthesis UB RAS

Perfluoroalkyl Chain Length Effect on Crystal Packing and [LnO8] Coordination Geometry in Lanthanide-Lithium β-Diketonates: Luminescence and Single-Ion Magnet Behavior

Functionalized perfluoroalkyl lithium β-diketonates (LiL) react with lanthanide(III) salts (Ln = Eu, Gd, Tb, Dy) in methanol to give heterobimetallic Ln-Li complexes of general formula [(LnL3)(LiL)(MeOH)]. The length of fluoroalkyl substituent in ligand was found to affect the crystal packing of complexes. Photoluminescent and magnetic properties of heterobimetallic β-diketonates in the solid state are reported. The effect of the geometry of the [LnO8] coordination environment of heterometallic β-diketonates on the luminescent properties (quantum yields, phosphorescence lifetimes for Eu, Tb, Dy complexes) and single-ion magnet behavior (Ueff for Dy complexes) is revealed. © 2023 by the authors.Russian Academy of Sciences, РАН: AAAA-A19-119011790132-7This work carried out in the framework of the basic theme of the Russian Academy of Sciences (state registration № AAAA-A19-119011790132-7)

Murine Pancreatic Adenocarcinoma Reduces Ikaros Expression and Disrupts T Cell Homeostasis

Background Maintenance of T cell immune homeostasis is critical for adequate anti-tumor immunity. The transcription factor Ikaros is essential for lymphocyte development including T cells. Alterations in Ikaros expression occur in blood malignancies in humans and mice. In this study, we investigated the role of Ikaros in regulating T cell immune balance in pancreatic cancer mouse models. Methodology and Principal Findings Using our Panc02 tumor-bearing (TB) mouse model, western blot analysis revealed a reduction in Ikaros proteins while qRT-PCR showed no differences in Ikaros mRNA levels in TB splenocytes compared to control. Treatment of naïve splenocytes with the proteasomal inhibitor, MG132, stabilized Ikaros expression and prevented Ikaros downregulation by Panc02 cells, in vitro. Western blot analyses showed a reduction in protein phosphatase 1 (PP1) and protein kinase CK2 expression in TB splenocytes while CK2 activity was increased. Immunofluorescence microscopy revealed altered punctate staining of Ikaros in TB splenocytes. Flow cytometry revealed a significant decrease in effector CD4+ and CD8+ T cell percentages but increased CD4+CD25+ regulatory T cells in TB splenocytes. Similar alterations in T cell percentages, as well as reduced Ikaros and CK2 but not PP1 expression, were observed in a transgenic, triple mutant (TrM) pancreatic cancer model. Ikaros expression was also reduced in enriched TB CD3+ T cells. MG132 treatment of naïve CD3+ T cells stabilized Ikaros expression in the presence of Panc02 cells. Western blots showed reduced PP1 and CK2 expression in TB CD3+ T cells. Conclusions/Significance The results of this study suggest that the pancreatic tumor microenvironment may cause proteasomal degradation of Ikaros, possibly via dysregulation of PP1 and CK2 expression and activity, respectively. This loss of Ikaros expression may contribute to an imbalance in T cell percentages. Ikaros may potentially be a therapeutic target to restore T cell homeostasis in pancreatic cancer hosts, which may be critical for effective anti-tumor immunity

Динамика газовыделений больных тяжелой бронхиальной астмой на фоне базисной противовоспалительной терапии

Because of the shortcomings of existing methods of assessment of asthma severity, the method of laser opto-acoustic spectroscopy was considered using for this purpose. Findings results show the availability of this method for diagnostics of clinical course severe asthma.В связи с недостатками существующих методов оценки состояния тяжести бронхиальной астмы рассмотрены возможности использования для этой цели метода лазерной оптико-акустической спектроскопии. Полученные результаты показывают перспективность данного метода для диагностики течения тяжелой бронхиальной астмы