• 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 март 2019 г.

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D. S. Bolotin, V. Korzhikov-Vlakh, E. Sinitsyna, S. N. Yunusova, V. V. Suslonov, A. Shetnev, A. Osipyan, M. Krasavin, V. Yu. Kukushkin, Biocompatible zinc(II) 8-(dihydroimidazolyl)quinoline complex and its catalytic application for synthesis of poly(L,L-lactide), J. Catal., 372 (2019) 362–369; DOI: 10.1016/j.jcat.2019.03.002.

Abstract

A 1:1 reaction of 8-(dihydroimidazolyl)quinoline (abbreviated as L) with MCl2·2H2O (M = CoII, NiII, CuII, ZnII) conducted in EtOAc (for ZnII and CuII) or MeOH (NiII and CoII) at 50 °C for 10 min provided the respective air- and shelf-stable [MCl2L] complexes (94–96%). The catalytic activity of these well-defined species was evaluated in L-lactide ring-opening polymerization (ROP) that was conducted in the presence of 2-hydroxyethylmethacrylate (HEMA) as a nucleophilic initiator. The biocompatible zinc(II) complex was found to be more catalytically active in ROP compared to the other three complexes as well as SnOct2, a common reference catalyst. The zinc(II)-catalyzed ROP also gives the macromolecular product with the lowest polydispersity index (1.2). The applicability of the HEMA-terminated PLA, prepared in the presence of the [ZnCl2L] complex, was demonstrated when PLA was converted into amphiphilic copolymer PLA-PEG via the thiol-ene click reaction. The PLA-PEG copolymer was shown to form nanospheres (calculated mean diameter 95 ± 10 nm) characterized by low particle size distribution. This – along with anticipated lower toxicity of [ZnCl2L] traces in the polymer – makes these nanospheres potentially applicable as vehicles for intravenous drug delivery.


Lijun Fu, Qunting Qu, Rudolf Holze, Veniamin V. Kondratiev and Yuping Wu, Composites of metal oxides and intrinsically conducting polymers as supercapacitor electrodes: The best of both worlds? J. Mater. Chem. A, 2019. DOI:10.1039/C8TA10587A.

Abstract

Composite materials combining intrinsically conducting polymers and metal oxides suggested as electrode materials in supercapacitors are reviewed with attention to achieved stability and specific functions and effects both components contribute to performance of the materials.


Mikhail V.Dobrynin, Carla Pretorius, Dumisani V.Kama, Andreas Roodt, Vadim P.Boyarskiy, Regina M.Islamova, Rhodium(I)-catalysed cross-linking of polysiloxanes conducted at room temperature, J. Catal., V. 372, 2019, 193-200. DOI: 10.1016/j.jcat.2019.03.004.

Abstract

Acetylacetonate and 4-arylimino-2-pentanonate carbonyl complexes of rhodium(I) [Rh(RC(O)C(R')C(O)R“)(CO)2] (1: R = Me, R' = H, R'' = Me; 2: R = Me, R' = Cl, R'' = Me; 3: R = Me, R' = H, R'' = CO2Me; 4: R = Ph, R' = H, R'' = Me; 5: R = Ph, R' = H, R'' = Ph) and [Rh(MeC(NR''')CHC(O)Me)(CO)2] (6: R''' = Ph; 7: R''' = 2,6-Me2C6H3) were examined as hydrosilylation cross-linking catalysts at RT for the reaction of poly(dimethylsiloxane-co-ethylhydrosiloxane) copolymer with vinyl terminated poly(dimethylsiloxane) or vinyl terminated poly(dimethylsiloxane-co-styrene) copolymer. All complexes allow cross-linking of vinyl- and hydride-containing polysiloxanes and copolymers at RT without inhibitor addition. Complexes 1–7possess catalytic activity comparable to the industrially used complex of Pt0 and divinyltetramethyldisiloxane (Karstedt’s catalyst). 1 is the most active among the studied rhodium complexes at 1.0 × 10−4 mol⋅L−1 and 1.0 × 10−5 mol⋅L−1. Silicone rubbers obtained with the rhodium catalysts compared to Karstedt’s catalyst possess no visible defects (bubbles or cracks), and differed by improved elastic properties (the elongation at break increased from 160 to 255%) The activity and improved silicone rubber properties using 1 renders it one of the suitable alternatives to Karstedt’s catalyst.