• Mohammad Kassem, Maria Bokova, Andrey S. Tverjanovich, Daniele Fontanari, David Le Coq, Anton Sokolov, Pascal Masselin, Shinji Kohara, Takeshi Usuki, Alex C. Hannon, Chris J. Benmore and Eugene Bychkov*, Bent HgI2 Molecules in the Melt and Sulfide Glasses: Implications for Nonlinear Optics, Chem. Mater. 2019. DOI: 10.1021/acs.chemmater.9b00860

    Nonlinear optical (NLO) crystals are widely used in advanced photonic technologies for second harmonic and difference frequency generation (SHG and DFG, respectively), producing coherent light at frequencies where existing lasers are unavailable. Isotropic glasses do not exhibit SHG or DFG, except temporarily induced anisotropy under external stimuli. However, recent reports on glasses with chiral structural motifs show promising permanent NLO properties. We propose an alternative solution: hybrid molecular/network glasses with noncentrosymmetric HgI2 monomers. Mercury(II) iodide consists of linear HgI2 triatomic molecules in the vapor phase and in the yellow orthorhombic polymorph stable above 400 K. At lower temperatures, the tetragonal red form is composed of corner-sharing HgI4/2 tetrahedra forming a layered extended framework...

  • Dan Wang, Lihui Xiao, Peixia Yang,* Zhengrui Xu, Xiangyu Lu, Lei Du,* Oleg Levin, Liping Ge, Xiaona Pan, Jinqiu Zhang and Maozhong An, Dual-nitrogen-source engineered Fe–Nx moieties as a booster for oxygen electroreduction, J. Mater. Chem. A, 2019, 7, 11007-11015. DOI: 10.1039/C9TA01953G

    Metal–air batteries, particularly Zn–air batteries, have triggered considerable enthusiasm of communities due to their high theoretical power density. Developing highly active, cost-effective and alternative non-precious metal catalysts for the oxygen reduction reaction (ORR) is pivotal for popularizing zinc–air batteries. The rational design and synthesis of this type of catalyst are therefore critical, but it is still challenging to control the well-defined active sites as expected. Herein, we report a dual-nitrogen-source mediated route for synergistically controlling the formation of active Fe–Nx moieties that are embedded in the carbon matrix...

  • Maartje J.Levels, Cynthia M.Fehres, Lisa G.M. van Baarsen, Nathalie O.P. van Uden, Kristine Germar, Tom G.O'Toole, Iris C.J.Blijdorp, Johanna F.Semmelink, Marieke E.Doorenspleet, Arjen Q.Bakker, Mikhail Krasavin, Alexey Tomilin, Sophie Brouard, Hergen Spits, Dominique L.P.Baeten, Nataliya G.Yeremenko, BOB.1 controls memory B-cell fate in the germinal center reaction, J. Autoimmun. 2019. DOI: 10.1016/j.jaut.2019.04.011

    During T cell-dependent (TD) germinal center (GC) responses, naïve B cells are instructed to differentiate towards GC B cells (GCBC), high-affinity long-lived plasma cells (LLPC) or memory B cells (Bmem). Alterations in the B cell-fate choice could contribute to immune dysregulation leading to the loss of self-tolerance and the initiation of autoimmune disease. Here we show that mRNA levels of the transcription regulator BOB.1 are increased in the lymph node compartment of patients with rheumatoid arthritis (RA), a prototypical autoimmune disease caused by the loss of immunological tolerance. Investigating to what extent levels of BOB.1 impact B cells during TD immune responses we found that BOB.1 has a crucial role in determining the B cell-fate decision. High BOB.1 levels promote the generation of cells with phenotypic and functional characteristics of Bmem. Mechanistically, overexpression of BOB.1 drives ABF1 and suppresses BCL6, favouring Bmem over LLPC or recycling GCBC. Low levels of BOB.1 are sufficient for LLPC but not for Bmem differentiation...

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Репрезентативные публикации за февраль 2019 г.


Ekaterina Oleneva, Julia Savosina, Marina Agafonova-Moroz, Alexander Lumpov, Vasily Babain, Igor Jahatspanian, Andrey Legin, Dmitry Kirsanov, Potentiometric multisensor system for tetra- and hexavalent actinide quantification in complex rare earth metal mixtures related to spent nuclear fuel reprocessing, Sensors and Actuators B: Chemical, 2019, 288, 155-162. DOI: 10.1016/j.snb.2019.02.113


A potentiometric multisensor system, composed of 12 cross-sensitive sensors, is proposed for uranium and thorium quantification in multi-component mixtures simulating PUREX process tailing solutions. Various ligands with high extraction capacity to lanthanides and actinides were used as active compounds in plasticized polymeric sensor membranes. The sensitivity of the individual sensors to tetra- and hexavalent actinides (UO22+ and Th4+) in aqueous nitric acid solutions with pH = 2 has been studied for the first time. The sensors with pronounced sensitivity to actinides were comprised into the multisensor system that was applied for UO2+2and Th4+ quantitative determination in presence of each other and lanthanides cations (La3+, Pr3+, Sm3+, Gd3+, Yb3+). The nitric acid quantification in the set of mixtures with UO2+2 and La3+ was also performed using the same system. Projection on latent structures (PLS) algorithm was used for multivariate regression models calculation. The results of PLS models validation with independent test set show the possibility of UO2+2 and Th4+ quantification with mean relative error (MRE) equal to 17% and 14% correspondingly, and HNO3 quantification with MRE = 7%. This accuracy is appropriate for real-time technological control of PUREX process.

Gomathy Chakkaradhari, Toni Eskelinen, Cecilia Degbe, Andrey Belyaev, Alexey S. Melnikov, Elena V. Grachova, Sergey P. Tunik, Pipsa Hirva, and Igor O. Koshevoy, Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence, Inorg. Chem., 2019. DOI: 10.1021/acs.inorgchem.8b03166


The series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(μ2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag23-SCN)(t-SCN)(P4)]2 (11) and [Ag23-SCN)(P4)]22+ (12). Complexes 711 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 1317 with the weakly coordinating SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 517 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (λem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

Kristina S. Kisel, Alexei S. Melnikov, Elena V. Grachova, Antti J. Karttunen, Antonio Doménech-Carbó, Kirill Yu. Monakhov, Valentin G. Semenov, Sergey P. Tunik, and Igor O. Koshevoy, Supramolecular Construction of Cyanide-Bridged ReI Diimine Multichromophores, Inorg. Chem., 2019, 58 (3), pp 1988–2000. DOI: 10.1021/acs.inorgchem.8b02974


The reactions of labile [Re(diimine)(CO)3(H2O)]+ precursors (diimine = 2,2′-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO)3}2CN)]+ (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO)2(PPh3)}2CN]+ (3), while the employment of a neutral metalloligand [Au(PPh3)(CN)] affords heterobimetallic complex [{Re(phen)(CO)3}NCAu(PPh3)]+ (4). Furthermore, the utilization of [Au(CN)2], [Pt(CN)4]2–, and [Fe(CN)6]4–/3– cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO)3NC}xM]m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 18 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this process can be substantially modified by the properties of the ancillary ligands that allows to attain near-IR emission for 3em = 737 nm in CH2Cl2). The Re–FeII/III complexes 9 and 10 are not luminescent but exhibit low energy absorptions, reaching 846 nm (10) due to ReI → FeIIItransition.