Source: http://ananikovlab.ru/ru/publics?y=2018
Timestamp: 2019-04-24 13:51:43+00:00

Document:
Chernysheva D. V., Chus Yu. A., Klushin V. A., Lastovina T. A., Pudova L. S., Smirnova N. V., Kravchenko O. A., Chernyshev V. M., Ananikov V. P., ChemSusChem, 2018, 20, 3599-3608.
Biomass processing wastes (humins) are anticipated to become a large‐tonnage solid waste in the nearest future, owing to the accelerated development of renewable technologies based on utilization of carbohydrates. In this work, the utility of humins as a feedstock for the production of activated carbon by various methods (pyrolysis, physical and chemical activation, or combined approaches) was evaluated. The obtained activated carbons were tested as potential electrode materials for supercapacitor applications and demonstrated combined micro‐ and mesoporous structure with a good capacitance of 370 Fg−1 (at a current density of 0.5 Ag−1) and good cycling stability with a capacitance retention of 92% after 10,000 charge/discharge cycles (at 10 Ag−1 in 6 M aqueous KOH electrolyte). Applicability of the developed activated carbon for practical usage as a supercapacitor electrode material was demonstrated by its successful utilization in symmetric two‐electrode cells and powering electric devices. These findings provide a new approach to deal with the problem of sustainable wastes utilization and to advance challenging energy storage applications.
Eremin D. B., Boiko D. A., Borkovskaya E. V., Khrustalev V. N., Chernyshev V. M., Ananikov V. P., Catal. Sci. Technol., 2018, 8, 3073-3080.
Palladium complexes with fluorinated acetylacetonate chelating ligands were studied as catalysts for alkyne hydrothiolation. A ten-fold increase in the catalytic efficiency was achieved by using 0.1 mol% of Pd(hfpd)2 complex (hfpd = hexafluoroacetylacetonate) with a variety of thiol–yne coupling partners. The principal possibility of a hundred-fold increase in the efficiency of Pd-catalyzed Markovnikov-type RSH addition with 0.01 mol% of the catalyst was successfully achieved with the hfpd ligand for the first time. The hexafluoroacetylacetonate chelating ligand not only enhanced the affinity of palladium centers to the triple bond of acetylene, but also stabilized the catalytic system against formation of insoluble polymeric [Pd(SPh)2]n species, thus ensuring that the reaction operates homogeneously. Utilizing other diketonate ligands resulted in cocktail-type catalysis with variable and poorly predictable contributions of homogeneous and heterogeneous pathways.
Rodygin K. S., Werner I., Ananikov V. P., ChemSusChem, 2018, 11, 292–298.
Synthesizing chemicals and materials based on renewable sources is one of the main tasks of modern science. Carbohydrates represent excellent renewable natural raw materials, that are eco-friendly, inexpensive and biologically compatible. Herein, we developed a green vinylation procedure for carbohydrates using readily available calcium carbide. Various carbohydrates were utilized as starting materials resulting in mono-, di- and tetra-vinyl ethers in high to excellent yields (81-92 %). The synthesized bio-based vinyl ethers were utilized as monomers in free radical and cationic polymerizations. A unique combination of smooth surface and intrinsic microcompartments was achieved in the synthesized materials. Two types of bio-based materials were prepared involving microspheres and "Swiss cheese" polymers. Scanning electron microscopy with built-in ion beam cutting was applied to reveal the spatial hierarchical structures in three-dimensional space.
Kucherov F.A., Romashov L.V., Galkin K.I., Ananikov V.P., ACS Sustainable Chem. Eng., 2018, 6, 8064-8092.
Recent advances in the area of biomass-derived C6-furanic platform chemicals for sustainable biomass processing are analyzed focusing on chemical reactions important for development of practical applications and materials science. Among the chemical processes currently being studied, tuning the amount of oxygen-containing functional groups remains the most active research direction. Production of efficient fuels requires the removal of oxygen atoms (reduction reactions), whereas utilization of biomass-derived furanic derivatives in material science points out the importance of oxidation in order to form dicarboxylic derivatives. Stimulated by this driving force, oxidation and reduction of 5-(hydroxymethyl)furfural (HMF) are nowadays massively studied. Moreover, these fundamental transformations are often used as model reactions to test new catalysts, and HMF transformations guide the development of new catalytic systems. From the viewpoint of organic synthesis, highly diverse chemical reactivity is explored and a number of bioderived synthetic building blocks with different functional groups are now accessible. This Perspective covers the most recent literature (since Jan 2017) to highlight the emerging research trends.
Khazipov O.V., Shevchenko M.A., Chernenko A.Yu., Astakhov A.V., Pasyukov D.V., Eremin D.B., Zubavichus Y.V., Khrustalev V.N., Chernyshev V.M., Ananikov V.P., Organometallics, 2018, 37, 1483-1492.
The behavior of ubiquitously used nickel, palladium, and platinum complexes containing N-heterocyclic carbene ligands was studied in solution in the presence of aliphatic amines. Transformation of M(NHC)X 2L complexes readily occurred according to the following reactions: (i) release of the NHC ligand in the form of azolium salt and formation of metal clusters or nanoparticles and (ii) isomerization of mono-NHC complexes M(NHC)X2L to bis-NHC derivatives M(NHC)2X2. Facile cleavage of the M–NHC bond was observed and provided the possibility for fast release of catalytically active NHC-free metal species. Bis-NHC metal complexes M(NHC)2X2were found to be significantly more stable and represented a molecular reservoir of catalytically active species. Slow decomposition of the bis-NHC complexes by removal of the NHC ligands (also in the form of azolium salts) occurred, generating metal clusters or nanoparticles. The observed combination of dual fast- and slow-release channels is an intrinsic latent opportunity of M/NHC complexes, which balances the activity and durability of a catalytic system. The fast release of catalytically active species from M(NHC)X2L complexes can rapidly initiate catalytic transformation, while the slow release of catalytically active species from M(NHC)2X2 complexes can compensate for degradation of catalytically active species and help to maintain a reliable amount of catalyst. The study clearly shows an outstanding potential of dynamic catalytic systems, where the key roles are played by the lability of the M–NHC framework rather than its stability.
Yakukhnov S. A., Pentsak E. O., Galkin K. I., Mironenko R. M., Drozdov V. A., Likholobov V. A., Ananikov V. P., ChemCatChem, 2018, 10, 1869-1873.
A facile direct deposition approach for the preparation of recyclable Pd/C catalysts simply by stirring a solution of Pd 2dba3 with a suitable carbon material was evaluated. An extraordinary rapid catalyst preparation procedure (< 5 min) under mild conditions and its excellent performance in cross-coupling and hydrogenation reactions were demonstrated. The key point for catalyst design was to directly deposit Pd(0) centers onto highly accessible surface area and to avoid ill-defined Pd(II)/Pd(0) states.
Gordeev E.G., Eremin D.B., Chernyshev V.M., Ananikov V.P., Organometallics, 2018, 37, 787-796.
Oxidative addition of organic halides (R–X) to (NHC)Pd 0L complexes is involved in numerous metal-catalyzed reactions, and this step is expected to afford (NHC)PdII(R)(X)L intermediate complexes. However, these complexes may undergo further transformation via R–NHC coupling, which removes the NHC ligands from the metal and results in the generation of "bare" NHC-free metal species. The comparative theoretical study carried out in the present work revealed that the kinetic and thermodynamic stability of the (NHC)PdII(R)(X)L oxidative addition intermediates depends strongly on the nature of the organic group R. The predicted reactivity in the R–NHC coupling process decreases in the following order: R = Vinyl > Ethynyl > Ph > Me. Accordingly, for R = Me, a classical (NHC)PdII(R)(X)L intermediate can be expected as a product of the oxidative addition step, whereas for R = Ph, the outcome of the oxidative addition may already contain the NHC-free palladium complex. For R = Ethynyl, comparable amounts of both complexes should be formed, while for R = Vinyl, the NHC-free palladium complex can be the major product of the oxidative addition process. Unusual thermodynamic and kinetic instability of the (NHC)Pd(vinyl)(X)L complex and the tendency to vinyl–NHC coupling predicted by the computational modeling has been confirmed by experimental measurements with online mass spectrometric reaction monitoring. Thus, the outcome of the oxidative addition strongly depends on the type of organic group R and the R–NHC coupling process greatly influences the activity and stability of metal catalysts.
Galushko A. S., Gordeev E. G., Ananikov V. P., Langmuir, 2018, 34, 15739-15748.
A thermally induced cascade process leading to the formation of stable micro- and nanometer-size phosphoric droplets was developed starting from a molecular precursor. Microwave-induced pyrolysis of 1,2,3,4,5-pentaphenylphosphole oxide proceeded through a series of subsequent transformations involving formation of phosphorus-doped graphene oxide layers, seeding of carbon surface with phosphorus centers, and assembling of stable droplets. A complex nanostructured organization of the material was established in a remarkably short time of 3 min, and the process was performed in a thermally induced manner using microwave irradiation. High stability of the liquid phosphoric structures on the surface of doped graphene oxide over a few-month period was demonstrated, as well as under challenging conditions in organic solvents (chloroform, methylene chloride, or toluene media) and even under sonication. Detailed examination of this material by electron microscopy and a number of analytical methods showed its unique organization at the nanoscale, whereas computational modeling revealed unusually strong binding of phosphorus oxide P 4O10 to the graphene surface. The study demonstrates a fascinating opportunity to access a complex nanostructured multicomponent material from a single and easily available molecular precursor.
Seitkalieva M. M., Kashin A. S., Egorova K. S., Ananikov V. P., ACS Sustainable Chem. Eng., 2018, 6, 719–726.
Storage and handling of toxic wastes is a top-priority challenge for sustainable development and public health. In recent years, the risk of irreversible environmental pollution has been increasing gradually, necessitating the development of new concepts in this highly demanding area. Here, we report a flexible approach to address the problem using tunable ionic liquids as a carrier and storage medium for chemicals. Encapsulation in microscale tunable media surrounded by an inert ionic liquid facilitates the efficient capture of chemicals. The adaptive character of the designed microscale compartments opens new possibilities for the waste management of chemicals of a diverse nature. Real-time field-emission scanning electron microscopy was used to visualize the formation of microscale compartments upon the sequestration of chemicals in ionic liquids. Ionic liquids captured the chemicals better than traditional organic solvents or water; moreover, the chemicals subsequently could be effectively extracted for destruction or utilization. Our work presents a new model for the sustainable management of chemical wastes; the concept was evaluated for a number of multiton chemicals currently affecting our environment.
Seitkalieva M. M., Kashin A. S., Egorova K. S., Ananikov V. P., Sep. Purif. Technol., 2018, 196, 318-326.
For the first time, extraction process in ionic liquids was visualized by direct electron microscopy observation. Microscopy images revealed the micro-heterogeneous nature of the studied extraction systems. Depending on the nature of ionic liquids and studied compounds, four main micro-scale areas were observed: a) uniform homogeneous phase; b) microcompartments in the liquid phase; c) solid microinclusions on the phase boundary; and d) solid microinclusions inside the separated microphases. The microscopic monitoring showed stepwise sequence of the extraction process, and the retention ability of the ionic liquid–water system decreased in the following order: homogeneous phase > microcompartments > solid microinclusions.
Egorova K. S., Ananikov V. P., J. Mol. Liq., 2018, 272, 271-300.
Voronin V.V., Ledovskaya M.S., Bogachenkov A.S., Rodygin K.S., Ananikov V.P., Molecules, 2018, 23, 2442.
Recent progress in the leading synthetic applications of acetylene is discussed from the prospect of rapid development and novel opportunities. A diversity of reactions involving the acetylene molecule to carry out vinylation processes, cross-coupling reactions, synthesis of substituted alkynes, preparation of heterocycles and the construction of a number of functionalized molecules with different levels of molecular complexity were recently studied. Of particular importance is the utilization of acetylene in the synthesis of pharmaceutical substances and drugs. The increasing interest in acetylene and its involvement in organic transformations highlights a fascinating renaissance of this simplest alkyne molecule.
Voronin V.V., Ledovskaya M.S., Gordeev E.G., Rodygin K.S., Ananikov V.P., J. Org. Chem., 2018, 83, 3819–3828.
Ledovskaya M., Rodygin K.S., Ananikov V.P., Org. Chem. Front., 2018, 5, 226–231.
In this work, a novel synthetic methodology for the one-pot preparation of isoxazoles directly from the reaction of calcium carbide with aldoximes is reported. Calcium carbide acts as a safe and inexpensive acetylene source and, in addition, as a source of the Ca(OH)2 base to enable the generation of nitrile oxide. Various 3-substituted isoxazoles were synthesized from the corresponding aldoximes in good yields (up to 95%) and a series of new deuterated 4,5-dideuteroisoxazoles were prepared.
Rodygin K.S., Bogachenkov A.S., Ananikov V.P., Molecules, 2018, 23, 648.
We developed a simple and efficient strategy to access N-vinyl secondary amines of various naturally occurring materials using readily available solid acetylene reagents (calcium carbide, KF, and KOH). Pyrrole, pyrazole, indoles, carbazoles, and diarylamines were successfully vinylated in good yields. Cross-linked and linear polymers were synthesized from N-vinyl carbazoles through free radical and cationic polymerization. Post-modification of olanzapine (an antipsychotic drug substance) was successfully performed.
Gordeev E. G., Galushko A. S., Ananikov V. P., PLoS ONE, 2018, 13, e0198370.

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