Volume 92, Issue 7

Recent results obtained in studying mono- and bimetallic catalysts for selective hydrogenation of unsaturated carbonyl compounds, even unsaturated ones, acetylenic and nitro compounds as well as CO and bio-available alcohols oxidation are reviewed from the standpoint of the strong interaction between the metal nanoparticles, on the one hand, and two metals in the composition of bimetallic nanoparticles, on the other hand. Such interactions were demonstrated to result in partial positive or negative charging of metal nanoparticles, which, in turn, changes their adsorption and catalytic properties, especially with respect to the reactions involving hydrogen. Among the systems studied, Au–Pt, Au–Pd, Au–Cu, Au–Fe, Pt–WO x , Fe–Pd, Fe–Pt, Fe–Cu nanoparticles prepared by the redox procedure are considered to be most perspective in diverse catalytic applications because of the proper combination of the particle size and the electronic state of the metals.

The International Year of The Periodic Table of Chemical Elements revealed that the Table remains both a deeply fundamental paradigm for various branches of chemistry and a universal practical tool for predictable design of new materials. Silver is a notable “nanoelement” particularly known by its plasmonic properties. A key advantage of this metal is an easily achievable morphological variety of nanostructured materials. This element represents a research branch of precise engineering of shapes and sizes of nanoparticle ensembles and smart hierarchic nanostructures. In the review, unique features of silver are discussed with respect to the development of novel analytical methods for forthcoming applications of surface-enhanced Raman spectroscopy (SERS) in ecology, biology and medicine.

One of the essential themes in modern catalysis is that of bridging the gap between its homogeneous and heterogeneous counterparts to combine their individual advantages and overcome shortcomings. One more incentive can now be added to the list, namely the ability of transition metal complexes to provide strong nuclear magnetic resonance (NMR) signal enhancement upon their use in homogeneous hydrogenations of unsaturated compounds with parahydrogen in solution. The addition of both H atoms of a parahydrogen molecule to the same substrate, a prerequisite for such effects, is implemented naturally with metal complexes that operate via the formation of a dihydride intermediate, but not with most heterogeneous catalysts. Despite that, it has been demonstrated in recent years that various types of heterogeneous catalysts are able to perform the required pairwise H 2 addition at least to some extent. This has opened a major gateway for developing highly sensitive and informative tools for mechanistic studies of heterogeneous hydrogenations and other processes involving H 2 . Besides, production of catalyst-free fluids with NMR signals enhanced by 3-4 orders of magnitude is essential for modern applications of magnetic resonance imaging (MRI), including biomedical research and practice. The ongoing efforts to design heterogeneous catalysts which can implement the homogeneous (pairwise) hydrogenation mechanism are reported.

2-Amino-2-deoxy-pyranosyl units are important structural components of cell-wall polymers in prokaryotes, fungi and mammals. With respect to the need for development of novel and efficient vaccines and tools for serodiagnosis of infectious diseases, of particular interest are the oligosaccharide cell-wall antigens of pathogenic bacteria and fungi, which comprise 2-amino-2-deoxy-D-glucopyranose and 2-amino-2-deoxy-D-galactopyranose units as α- or β-anomers. Synthesis of N-acylated α-GlcN and α-GalN containing oligosaccharides is a special challenge due to the presence of a participating group at C2 which favors the formation of β- rather than α-glycoside bond. Herein we overview the efficient two-step approach for preparation of 1,2- cis -glycosides of 2-amino-2-deoxy-D-glucopyranose and 2-amino-2-deoxy-D-galactopyranose, which was recently developed in our laboratory. In the first step, an efficient and straightforward azidophenylselenylation procedure of glycals gives phenyl 2-azido-2-deoxy-1-selenoglycosides as versatile glycosyl donors. In the second step, these donors can be efficiently transformed into α- or β-glycosides depending on the choice of the solvent. In acetonitrile, total β-stereocontrol was achieved, and the use of diethyl ether as a solvent favouring α-stereoselectivity of glycosylations with phenyl 2-azido-2-deoxy-1-selenoglycosides. Besides, it was shown, that low reactivity and nucleophilicity of glycosyl acceptors which are glycosylated with phenyl 2-azido-2-deoxy-1-selenogalactosides facilitated the formation of α-GalN derivatives. To date, homogenous azidophenylselenylation of glycals and glycosylation with phenyl 2-azido-2-deoxy-1-seleno-α-D-glycopyranosides can be regarded as most useful tool for introduction of 2-amino-2-deoxy-D-glycopyranoside residues into complex synthetic oligosaccharides.

A new series of homobivalent Dimebon analogs, bis-γ-carbolines with alkylene, phenylenedialkylene, and triazole-containing spacers, was synthesized. Doubling the γ-carboline pharmacophore increased inhibitory potency against acetylcholinesterase (AChE) compared with Dimebon, while keeping Dimebon’s anti-butyrylcholinesterase activity; therefore, leading to inversion of selectivity. Molecular docking revealed the reasons for the increased anti-AChE activity and ability to block AChE-induced aggregation of β-amyloid for bis-γ-carbolines, which became double-site inhibitors of AChE. Conjugates with ditriazole-containing spacers were the most active antioxidants in both the ABTS-test and prevention of lipid peroxidation in brain homogenates without inhibiting the mitochondrial permeability transition (MPT). Conjugates with alkylene ( 4a–d ), phenylenedialkylene ( 4e ), and monotriazole ( 8 ) spacers were less active as antioxidants but prevented induction of the MPT and increased the calcium retention capacity of mitochondria. Lead compound 4e showed neuroprotective potential in a cellular calcium overload model of neurodegeneration. Computational studies showed that all the bis-γ-carbolines were expected to have high values for intestinal absorption and very good blood-brain barrier permeability along with good drug-likeness. Overall, the results showed that new homobivalent Dimebon analogs exhibit an expanded spectrum of biological activity and improved pharmacological properties, making them promising candidates for further research and optimization as multitarget agents for Alzheimer’s disease treatment.

While metal-organic frameworks based on aromatic carboxylates are very numerous and well investigated, the chemistry of their fully fluorinated analogues is at the very beginning. This minireview aims at summarizing all metal complexes with octafluorobiphenyl-4,4′-dicarboxylate (oFBPDC 2− ) anion and in particular, porous coordination polymers, their syntheses, crystal structures and functional properties highlighting the importance of further investigation of such systems.

Heterometallic carboxylate complexes are of paramount interest in pure and applied coordination chemistry. Despite that plurality of such type compounds have been published to date, synthetic aspects of their chemistry often remain in the shadow of intriguing physical properties manifesting by these species. Present review summarizes reliable data on direct synthesis of low nuclearity molecular compounds as well as coordination polymers on their base with carboxylate-bridged {M 2 Mg} (M = Co 2+ , Ni 2+ , Cd 2+ ), {M 2 Li 2 } (M = Co 2+ , Ni 2+ , Zn 2+ , VO 2+ ), {M 2 Ln 2 } and {M 2 Ln} (M = Cu 2+ , Zn 2+ , Co 2+ ) metal cores. Structural features and stabilization factors are considered and principal outcomes are confirmed by quantum-chemical calculations. Particular attention is paid to consideration of ligand-exchange reactions that allow controllable modification of heterometallic metal core under mild conditions giving diverse molecular complexes with modified ligand environment or Metal-Organic Frameworks with permanent porosity.

A kinetic model of the heavy oil feedstock hydroconversion performed in continuous flow reactor in the presence of in-situ synthesized dispersed nanosize catalyst Molybdenum disulfide (MoS 2 ) has been proposed. The kinetic parameters of heavy oil feedstock with different properties have been determined for the two process versions: with coke formation and without appreciable coke formation. It has been stated that hydroconversion in the presence of in-situ synthesized dispersed MoS 2 (C(Mo) = 0.05% wt. (per feed)) corresponds to a first-order reaction for all studied feedstock samples. The rate and activation energy constants have been determined. It has been shown that the conditions of polycondensation products (coke) formation result in increasing process rate and decreasing activation energy.

The regularities of changing chemical composition and size of a ultra-small multicomponent gas bubble growing in a viscous solution have been analyzed. The full-scale effects of solution viscosity and bubble curvature at non-stationary diffusion of arbitrary number of dissolved gases with any value of gas supersaturations and solubilities in the surrounding liquid solution have been taken into account. The nonuniform concentration profiles of gas species in supersaturated solution around the growing bubble with changing composition have been found as a function of time and distance from the bubble center. Equations describing transition to stationary concentrations of gases in the bubble with increasing radius have been obtained. Analytic asymptotic solutions of these equations for a ternary system have been presented.

Results of studies on the analytical capabilities of gold nanoparticles in the methods of optical molecular absorption spectroscopy are reported. Peculiar effects of the nature of nanoparticle stabilizer, its charge, morphology of nanoparticles, form in which they are present in the system (in a colloidal solution or as a part of a nanocomposite with polyurethane foam) upon the determination of organic compounds (thiols, cationic compounds, catecholamines) and inorganic anions are considered. The determination is based on aggregation of nanoparticles or change in the state of their surface and morphology as a result of silver coating, leading to significant spectral and color changes, which can be monitored both by optical molecular absorption spectroscopy and visually. The ways to increase sensitivity and to control selectivity of the analysis using gold nanoparticles and their nanocomposites are outlined.

Ion exchange membranes are widely used in chemical power sources, including fuel cells, redox batteries, reverse electrodialysis devices and lithium-ion batteries. The general requirements for them are high ionic conductivity and selectivity of transport processes. Heterogeneous membranes are much cheaper but less selective due to the secondary porosity with large pore size. The composition of grafted membranes is almost identical to heterogeneous ones. But they are more selective due to the lack of secondary porosity. The conductivity of ion exchange membranes can be improved by their modification via nanoparticle incorporation. Hybrid membranes exhibit suppressed transport of co-ions and fuel gases. Highly selective composite membranes can be synthesized by incorporating nanoparticles with modified surface. Furthermore, the increase in the conductivity of hybrid membranes at low humidity is a significant advantage for fuel cell application. Proton-conducting membranes in the lithium form intercalated with aprotic solvents can be used in lithium-ion batteries and make them more safe. In this review, we summarize recent progress in the synthesis, and modification and transport properties of ion exchange membranes, their transport properties, methods of preparation and modification. Their application in fuel cells, reverse electrodialysis devices and lithium-ion batteries is also reviewed.

Successful using of cage metal complexes (clathrochelates) and the functional hybrid materials based on them as promising electro- and (pre)catalysts for hydrogen and syngas production is highlighted in this microreview. The designed polyaromatic-terminated iron, cobalt and ruthenium clathrochelates, adsorbed on carbon materials, were found to be the efficient electrocatalysts of the hydrogen evolution reaction (HER), including those in polymer electrolyte membrane (PEM) water electrolysers. The clathrochelate-electrocatalayzed performances of HER 2H + /H 2 in these semi-industrial electrolysers are encouraging being similar to those for the best known to date molecular catalysts and for the promising non-platinum solid-state HER electrocatalysts as well. Electrocatalytic activity of the above clathrochelates was found to be affected by the number of the terminal polyaromatic group(s) per a clathrochelate molecule and the lowest Tafel slopes were obtained with hexaphenanthrene macrobicyclic complexes. The use of suitable carbon materials of a high surface area, as the substrates for their efficient immobilization, allowed to substantially increase an electrocatalytic activity of the corresponding clathrochelate-containing carbon paper-based cathodes. In the case of the reaction of dry reforming of methane (DRM) into syngas of a stoichiometry CO/H 2 1:1, the designed metal(II) clathrochelates with terminal polar groups are only the precursors (precatalysts) of single atom catalysts, where each of their catalytically active single sites is included in a matrix of its former encapsulating ligand. Choice of their designed ligands allowed an efficient immobilization of the corresponding cage metal complexes on the surface of a given highly porous ceramic material as a substrate and caused increasing of a surface concentration of the catalytically active centers (and, therefore, that of the catalytic activity of hybrid materials modified with these clathrochelates). Thus designed cage metal complexes and hybrid materials based on them operate under the principals of “green chemistry” and can be considered as efficient alternatives to some classical inorganic and molecular (pre)catalysts of these industrial processes.

Medicinal plants have an enormous potential for producing bioactive compounds of great benefit to mankind. There is a great scope for new drug candidates based on traditional medicinal plants throughout the world. The number of drugs derived from medicinal plants that are recently introduced into clinical use is increasing. Besides, numerous of standardized herbal extracts were also approved as phytomedicines by the health authorities to be used in phytotherapy. The drug discovery program from nature in our laboratory involves several steps from plant collection, extraction, HTS of the extracts by using in vitro enzyme inhibitory tests, bioassay-guided fractionation through the isolation and structure elucidation of bioactive compounds. Continuing our researches in the field of anticholinesterase activity, neuroprotective potential of Iris pseudacorus L. have presented in this article.