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Trapping the Short-Chain Odd Carbon Number Olefins Using Nickel(Ⅱ)-Catalyzed Tandem Ethylene Oligomerization and Friedel-Crafts Alkylation of Toluene

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Chinese Journal of Chemistry 2023年第21期41卷 2855-2865页

作者： Sergey V.Zubkevich Vladislav A.Tuskaev Svetlana Ch.Gagieva Alexander A.Pavlov Victor N.Khrustalev Fei Wang Li Pan Yuesheng Li Daniele Saracheno Anton A.Vikhrov Dmitry N.Zarubin boris.m.bulychev Department of Chemistry Lomonosov Moscow State UniversityLeninskie Gory 1Moscow119991 Russian Federation materials Research and Technology Department Luxembourg Institute of Science and Technology5Avenue des Hauts-FourneauxL-4362 Esch-sur-AlzetteLuxembourg A N Nesmeyanov Institute of Organoelement Compounds Russian Academy of SciencesVavilova st.28Moscow119991 Russian Federation BmSTU Center of National Technological Initiative“Digital material Science:New material and Substances” Bauman MoscowState Technical University2nd Baumanskaya st.5MoscowRussian Federation Peoples’Friendship University of Russia(RUDN University) Miklukho-Maklay St.6Moscow117198 Russian Federation Zelinsky Institute of Organic Chemistry Russian Academy of SciencesLeninsky Prospekt 47Moscow119991 Russian Federation Institute of Advanced Polymer materials School of Materials Science and EngineeringTianjin UniversityTianjin300350 China

Nickel(Ⅱ)complexes with pyrazole-based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel-Crafts alkylation of *** have prepared ten new nickel(Ⅱ)dibromide complexes with various substituted bis(azolyl)*** have been characterized using^(1)H NmR,IR,high resolution mass spectrometry and elemental *** structures of three complexes have been unambiguously established using X-ray *** was found that these complexes in the presence of Et2AlCl or Et_(3)Al_(2)Cl_(3)are active both in ethylene oligomerization and Friedel-Crafts alkylation processes(activity up to 3720 kgoligomer·mol[Ni]^(−1)·h^(−1)).The use of Et_(3)Al_(2)Cl_(3)results in a higher share of alkylated products(up to 60%).moreover,catalytic systems activated with Et_(3)Al_(2)Cl_(3)produced small amounts of odd carbon number olefins(up to 0.8%).The Friedel-Crafts alkylation was used as a trap for previously undetected short-chain odd carbon number olefins(C_(3)and C_(5)).

关键词： Ethylene oligomerization Friedel-Crafts alkylation Nickel(Ⅱ)complexes N-ligands Odd carbon number olefins

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Surface-enhanced Raman scattering inside Au@Ag core/shell nanorods

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Nano Research 2016年第8期9卷 2303-2318页

作者： boris Khlebtsov Institute of Biochemistry and Physiology of Plants and microorganisms Russian Academy of Sciences Saratov 410049 Russia Saratov National Research State University Saratov 410012 Russia

The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications. However, direct synthesis of such nanostructures with controllable shape, size, and plasmonic properties remains extremely challenging. Here we report on the preparation of uniform Au@Ag core/sheU nanorods with controllable Ag shells of 1 to 25 nm in thickness. 1,4-Aminothiophenol （4-ATP） molecules, used as the Raman reporters, were located between the Au core and the Ag shell. Successful embedding of reporter molecules inside the core/shell nanoparticles was confirmed by the absence of selective oxidation of the amino groups, as measured by Raman spectroscopy. The dependence of Raman intensity on the location of the reporter molecules in the inside and outside of the nanorods was studied. The molecules in the interior showed strong and uniform Raman intensity, at least an order of magnitude higher than that of the molecules on the nanoparticle surface. In contrast to the usual surface-functionalized Raman tags, aggregation and clustering of nanoparticles with embedded molecules decreased the surface-enhanced Raman scattering （SERS） signal. The findings from this study provide the basis for a novel detection technique of low analyte concentration utilizing the high SERS response of molecules inside the core/shell metal nanostructures. As an example, we show robust SERS detection of thiram fungicide as low as 10-9 m in solutions.

关键词： surface-enhanced Ramanscattering (SERS) Au@Ag nanorods nanocuboids multipole plasmons

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Binuclear and Hexanuclear Ti(Ⅳ) Complexes Supported by [OOOO]^(4–)-type Ligand for Preparing Disentangled UHmWPE

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Chinese Journal of Polymer Science 2019年第5期37卷 471-477页

作者： Vladislav A.Tuskaev Svetlana Ch.Gagieva Dmitry A.Kurmaev Viktor G.Vasil'ev Nikolay A.Kolosov Sergey V.Zubkevich Elena S.mikhaylik Evgenii K.Golubev Galina G.Nikiforova Pavel A.Zhizhko Olga A.Serenko boris.m.bulychev Department of Chemistry M.V.Lomonosov Moscow State University A.N.Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Enikolopov Institute of Synthetic Polymer materials Russian Academy of Sciences

Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]^(4–)-type ligand were active in ethylene polymerization in the presence of Et2 AlCl/Bu2 mg binary co-catalyst, giving high molecular weight polyethylene. The binuclear complex showed significantly higher catalytic activity and thermal stability in comparison to mononuclear analogue. Ultra high molecular weight polyethylene(UHmWPE) samples were processed by a solid-state uniaxial deformation into high-strength(up to 2.5 GPa) and highmodulus(over 100 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.

关键词： Binuclear catalysts Titanium Ethylene Ziegler-Natta polymerization UHmWPE

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Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands

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Chinese Journal of Polymer Science 2024年第1期42卷 52-62,I0007页

作者： Vladislav A.Tuskaev Kasim F.magomedov Svetlana Ch.Gagieva Dmitry A.Kurmaev Yulia V.Nelyubina Evgenii K.Golubev maria D.Evseeva Viktor G.Vasil'ev Galina G.Nikiforova mikhail I.Buzin Vyacheslav S.Bogdanov boris.m.bulychev Department of Chemistry M.V.Lomonosov Moscow State UniversityMoscow 119992Russian Federation A.N.Nesmeyanov Institute of Organoelement Compounds Russian Academy of SciencesMoscow119991Russian Federation Enikolopov Institute of Synthetic Polymer materials Russian Academy of SciencesMoscow 117393Russian Federation

A series of Ti(Ⅳ) dichloride and dialkoxide com plexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been *** molecular structures of complexes 1 and 4 were established by single-crystal X-ray diffraction *** complexes adopt a distorted octahedral coordination structure around the titanium atom and two oxygen atoms are situated in trans position while two nitrogen atoms and two outgoing ligands(Cl or iPrO) are situated in cis *** of activators(mmAO-12 and combinations Et_nAICl_(3-n)+Bu_(2)mg) and outgoing ligand(Cl or iPrO) nature on the catalytic activity and properties of the resulting polymers was *** Ti complexes,despite the nature of the outgoing ligands(Cl or iPrO) in the presence of Al/mg activators,was found to display a high ethylene polymerization activity in the range 1600-3830 kg_(polymer)·mol_(Ti)^(-1)·h^(-1)·atm^(-1) with a viscosity average molecular weight(m_v) value in the range 1.1×10~6-7.1×10~6 Dalton(Da).The resulting UHmWPE can be processed by a solventless method into high-strength and high-modulus oriented *** rheological characteristics of a polymer melt have been *** absence of a cross-over point did not allow to compare the values of the molecular weight distribution of polymers obtained on fluorinated and non-fluorinated pre-catalysts,however,the estimation of the entanglement density is in good agreement with the mechanical characteristics of oriented film *** activation with methylalumoxane,the activity of the com plexes decreased very significantly;however,a polymer with a molecular weight of about 12 million Da was *** the process of ethylene/octene-1 copolymerization,fluorine-containing precatalysts showed a clear advantage over non-fluorinated analogues both in activity and in comonomer content.

关键词： FI catalysts Titanium(IV) (Co)polymerization Al/mg co-catalyst Ultra-high molecular weight polyethylene

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Capacitance,charge dynamics,and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes

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Progress in Natural Science:materials International 2015年第6期25卷 631-641页

作者： boris Dyatkin Eugene mamontov Kevin m.Cook Yury Gogotsi Department of materials Science & Engineering and A.J.Drexel Nanomaterials Institute Drexel University Spallation Neutron Source Oak Ridge National Laboratory materials Engineering Division Naval Air Systems Command

This study analyzed the dynamics of ionic liquid electrolyte inside of defunctionalized,hydrogenated,and aminated pores of carbide-derived carbon supercapacitor *** approach tailors surface functionalities and tunes nanoporous structures to decouple the influence of pore wall composition on capacitance,ionic resistance,and long-term ***-elastic neutron scattering probes the self-diffusion properties and electrode-ion interactions of electrolyte molecules confined in functionalized ***-temperature ionic liquid interactions in confined pores are strongest when the hydrogen-containing groups are present on the *** property translates into higher capacitance and greater ion transport through pores during electrochemical *** hydrogenated pores,aminated pores do not favorably interact with ionic liquid ions and,subsequently,are outperformed by defunctionalized surfaces.

关键词： Supercapacitor Carbide-derived carbon Neutron scattering Energy storage Porous materials Surface chemistry

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mechanism of the Initial Stage of Thermal Decomposition of Nitroguanidine

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火炸药学报 2023年第1期46卷 31-40页

作者： boris E.Krisyuk Danila A.markin Timofey m.Sypko Viktor V.Zakharov Nikita V.Chukanov boris L.Korsunskiy Federal Research Center of Problems of Chemical Physics and medicinal Chemistry Russian Academy of Sciences142432prosp.Academician Semenov1ChernogolovkaMoscow RegionRussia Plekhanov Russian University of Economics Department of Chemistry and Physics36 Stremyanny laneMoscow 117997Russia Lomonosov moscow State University Faculty of Fundamental Physical and Chemical engineeringGSP-11 Leninskie Goryp.51Moscow 119991Russia N.N.Semenov Federal Research Center for Chemical Physics Russian Academy of Science 4 Kosygina StreetBuilding 1Moscow 119991Russia

A theoretical and experimental study of the thermal decomposition of nitroguanidine(NQ) has been carried out. Various thermolysis channels were studied by quantum chemistry methods at the CCSD(or DLPNO-CCSD) level using the aug-cc-pVDZ basis set. It is shown that the lowest activation enthalpies(170-180kJ/mol) are characteristic of the reactions of NO2abstraction from the initial NQ and the reaction channel with the transfer of oxygen from the nitro group to carbon in the limiting stage. Additionally, the thermolysis of NQ was studied experimentally in a nonisothermal mode with heating rates from 1 to 10K/min. In these experiments, the weight loss of the sample, thermal effects, and mass spectra of the products were recorded. An analysis of the experimental data confirmed the results of a theoretical study of the mechanism of thermal decomposition of NQ. The main thermolysis products are N2O, HNCO, NH3, and NO2, which fully corresponds to quantum chemical calculations.

关键词： primary thermolysis steps quantum-chemical calculation mass spectrometry DSC TG

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Post-Late Paleozoic Collisional Framework of Southern Great Altai

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Acta Geologica Sinica(English Edition) 2012年第5期86卷 1093-1104页

作者： boris m. CHIKOV Sergei V. ZINOVIEV Еugene V. DEYEV Institute of Geology Siberian Branch of Russian Academy of Sciences Novosibirsk 630090 Russia

We outline the post-Late Paleozoic （latest Permian to Cenozoic） collisional framework of the southern Great Altai （Central Asia） produced by the convergence between the Tuva-mongolia and Junggar continental terranes （microplates）. The collisional structures in the region classified on the basis of their geometry and deformation style, dynamic metamorphism, and compositions of tectonites are of three main types：（1） mosaic terranes made up of large weakly deformed Paleozoic blocks separated by younger shear zones; （2） contractional deformation systems involving structures formed in post-Late Paleozoic time, parallel faults oriented along collisional deformation systems, and relict lenses of Paleozoic orogenic complexes; and （3） isolated zones of dynamic metamorphism composed mostly of collisional tectonites different in composition and alteration grade.

关键词： continental collision post-Late Paleozoic events tectonic framework dynamic metamorphism Altai Central Asia

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Interface-induced warping in hybrid two-dimensional materials

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Nano Research 2015年第6期8卷 2015-2023页

作者： John m. Aired Zhuhua Zhang Zhili Hu boris I. Yakobson Department of material Science and Nanoengineering Rice University Houston Texas 77005 USA

Two-dimensional hybrid materials consisting of heterogeneous domains have been of great interest. Using empirical molecular dynamical simulation, we show that the morphology of such hybrid 2D materials can extend into the third dimension via strong warping intrinsic to the interfaces between the domains. The interface warping stems from the compressive stress in the domain with a larger lattice constant and even penetrates into the stretched domain. Based on classic plate theory, we analytically quantify the amplitude, wave length and penetration depth of the interface warping as functions of the lattice mismatch, achieving good agreement with the simulations. moreover, we propose that periodically placing pentagon-heptagon dislocations along the interface can eliminate the warping in the 2D material and such defective interface can be more favorable than the warped one over a critical domain size, which is consistent with recent experimental observations. Our results suggest that the interface warping in 2D hybrid materials should be considered in further exploring their promising properties.

关键词： graphene interface rippling mechanical property hybrid 2D materials

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Integrating geographical information in the Linked Digital Earth

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International Journal of Digital Earth 2014年第7期7卷 554-575页

作者： Luis m.Vilches-Blazquez boris Villazon-Terrazas Oscar Corcho Asuncion Gomez-Perez Ontology Engineering Group Departamento de Inteligencia ArtificialFacultad de InformaticaUniversidad Politecnica de MadridMadridSpain

many progresses have been made since the Digital Earth notion was envisioned thirteen years ***,the mechanism for integrating geographic informa-tion into the Digital Earth is still quite *** this context,we have developed a process to generate,integrate and publish geospatial Linked Data from several Spanish National *** data-sets are related to four Infrastructure for Spatial Information in the European Community(INSPIRE)themes,specifically with Administrative units,Hydrography,Statistical units,and *** main goal is to combine different sources(heterogeneous,multidisciplinary,multitemporal,multiresolution,and multilingual)using Linked Data *** goal allows the overcoming of current problems of information integration and driving geographical information toward the next decade scenario,that is,‘Linked Digital Earth’.

关键词： geographical information integration Digital Earth Linked Data

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A case of severe refractive changes induced by Galyfilcon A silicone hydrogel contact lenses

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International Journal of Ophthalmology(English edition) 2016年第1期9卷 175-177页

作者： boris Severinsky New England College of Optometry Boston 02115 USA

Dear Sir, I＇m boris Severinsky from the New England College of Optometry, Boston, USA. I write you to present an interesting case of extreme refractive and corneal topography changes induced by daily wearing of Acuv... 详细信息

关键词： A case of severe refractive changes induced by Galyfilcon A silicone hydrogel contact lenses case Vision Figure

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