Marsil K. Kadirov

New Functional Cyclic Aminomethylphosphine Ligands for the Construction of Catalysts for Electrochemical Hydrogen Transformations

Eight-membered cyclic functional bisphosphines, namely 1,5-di-aryl-3,7-di(2-pyridyl)-1,5-diaza-3,7-diphosphacyclooctanes (aryl=2-pyridyl, m-tolyl, p-tolyl, diphenylmethyl, benzyl, (R)-(+)-(α-methyl)benzyl), with 2-pyridyl substituents on the phosphorus atoms have been synthesized by condensation of 2-pyridylphosphine, formaldehyde, and the corresponding primary amine. The structures of some of these bisphosphines have been investigated by X-ray crystallography. The bisphosphines readily form neutral P,P-chelate complexes [(κ(2)-P,P-L)MCl2], cationic bis-P,P-chelate complexes [(κ(2)-P,P-L)2 M](2+), or a five-coordinate complex [(κ(2)-P,P-L)2 NiBr]Br. The electrochemical behavior of two of the nickel complexes, and their catalytic activities in electrochemical hydrogen evolution and hydrogen oxidation, including the fuel-cell test, have been studied.

Novel bolaamphiphilic pyrimidinophane as building block for design of nanosized supramolecular systems with concentration-dependent structural behavior.

A new macrocyclic bolaamphiphile with thiocytosine fragments in the molecule (B1) has been synthesized and advanced as perspective platform for the design of soft supramolecular systems. Strong concentration-dependent structural behavior is observed in the water-DMF (20% vol) solution of B1 as revealed by methods of tensiometry, conductometry, dynamic light scattering, and atomic force microscopy. Two breakpoints are observed in the surface tension isotherms. The first one, around 0.002 M, is identified as a critical micelle concentration (cmc), whereas the second critical concentration of 0.01 M is a turning point between the two models of the association involved. Large aggregates of ca. 200 nm are mostly formed beyond the cmc, whereas small micelle-like aggregates exist above 0.01 M. The growth of aggregates between these critical points occurs, resulting in a gel-like behavior. An unusual decrease in the solution pH with concentration takes place, which is assumed to originate from the steric hindrance around the B1 head groups. Because of controllable structural behavior, B1 is assumed to be a candidate for the development of biomimetic catalysts, nanocontainers, drug and gene carriers, etc.

Mediated electrochemical synthesis of Pd0 nanoparticles in solution

Efficient electrosynthesis of palladium(0) nanoparticles is carried out in solution by mediated electrochemical reduction of a complex dianion [PdCl4]2– in the DMSO/0.1 M Bu4NCl medium. The mediator function was performed by methylviologen and tetraviologen calix[4]resorcines MVCA-Cn8+ with methyl (n = 1), n-pentyl (n = 5), and n-decyl (n = 10) substituents in resorcinol rings at the potentials of redox pairs MV2+/MV•+, MVCA-Cn8+/MVCA-Cn4•+. The resulting metal nanoparticles gradually aggregate to yield coarser particles. The smallest size (255 nm) have metal particles obtained in the presence of MVCA-C58+ for the rest mediators, metal particles of the micron size are formed. Sonication results in disintegration of aggregates to nanoparticles.

Structural, biocomplexation and gene delivery properties of hydroxyethylated gemini surfactants with varied spacer length.

Gemini surfactants with hexadecyl tails and hydroxyethylated head groups bridged with tetramethylene (G4), hexamethylene (G6) and dodecamethylene (G12) spacers were shown to self-assemble at the lower critical micelle concentration compared to their conventional m-s-m analogs. The lipoplex formation and the plasmid DNA transfer into different kinds of host cells were studied. In the case of eukaryotic cells, high transfection efficacy has been demonstrated for DNA-gemini complexes, which increased as follows: G6<G4<G12. Different activity series, i.e., G6>G4>G12 has been obtained in the case of transformation of bacterial cells with plasmid DNA-gemini complexes, mediated by electroporation technique. Solely G6 shows transformation efficacy exceeding the control result (uncomplexed DNA), while the inhibitory effect occurs for G4 and G12. Analysis of physico-chemical features of single surfactants and lipoplexes shows that compaction and condensation effects change as follows: G6<G4 ≤ G12, i.e., agree with the order of transfection efficacy, which is supported by membrane tropic properties of G12. On the other hand, gel retardation assay and docking study testify low electrostatic affinity in G12/DNA pair, thereby indicating that hydrophobic effect probably plays important role in the lipoplex formation. Two factors are assumed to be responsible for the inhibition effect of gemini in the case of transformation of bacterial cells. They are (i) an unfavorable influence of cationic surfactants on the electroporation procedure due to depressing the electrophoretic effect; and (ii) antibacterial activity of cationic surfactants that may cause the disruption of integrity of cell membranes.

Electrochemical mediated synthesis of silver nanoparticles in solution

Methyl viologen MV2+ and tetraviologen calix[4]resorcinol MVCA-C58+ with n-pentyl substituents in the resorcinol rings at potentials of MV2+/MV•+ and MVCA-C58+ /MVCA-C54•+ redox couples proved to be effective mediators of the electrochemical reduction of Ag+ ions in DMF/0.1 M Bu4NPF6. The potentiostatic nondiaphragm electrolysis at controlled mediator reduction potentials at room temperature using an Ag anode as an in situ supplier of Ag+ led to the formation of metallic silver nanoparticles in solution. The only resulting effect of electrolysis was the quantitative transfer of the metal anode into the metal nanoparticles in solution. In the case of MV2+, the nanoparticles aggregated into larger particles. MVCA-CC58+ serves not only as a mediator, but also, to some extent, as a stabilizer of silver nanoparticles and can be recorded by a set of experimental methods.

Electrochemical evaluation of a number of nickel complexes with P,N-heterocyclic ligands as catalysts for hydrogen oxidation/release

The efficiency of a series of nickel complexes of P,N-cyclic ligands (potential catalysts in hydrogen fuel cells) in the electrocatalytic reduction of H+ to hydrogen and the oxidation of H2 in the coordination shell/cavity of the catalyst in DMF (acetonitrile with variable nickel: ligand ratio (1: 1, 1: 2) and different counterions (X=Cl− and BF4−)) was tested, and the most favorable conditions and structures were determined. The relation between the activity of the catalysts and the values of the electrochemical gap was found.

Electron spin and electron nuclear double resonances of the stable 1-(4-nitrophenyl)-3-phenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl free radical

The 1H and 14N hyperfine structure constants for the stable 1-(4-nitrophenyl)-3-phenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl free radical obtained by the oxidation of 1-(4-nitrophenyl)-3-phenyl-1,4-dihydro-1,2,4-benzotriazine or N-phenylbenzamide 4-nitrophenylhydrazone were determined by the ESR and 1H electron nuclear double resonance methods.

“Clickable” thiacalix[4]arene derivatives bearing polymerizable 1,3-butadiyne fragments: synthesis and incorporation into polydiacetylene vesicles

p-tert-Butylthiacalix[4]arene derivatives in 1,3-alternate stereoisomeric form bearing polymerisable 1,3-butadiyne fragments on the one side and amino/carboxylic groups on another were synthesized using stepwise functionalisation. Calixarene 7 embedded in polydiacetylene nanoparticles showed a selective colorimetric response toward lanthanide ions.

Langmuir monolayers and thin films of amphifilic thiacalix[4]arenes. Properties and matrix for the immobilization of cytochrome c.

Formation and properties of Langmuir films of thiacalix[4]arene (TCA) derivatives containing N-donor groups on the lower rim (Y═O(CH2)3CN; OCH2CN; NH2; OCH2ArCN-p) in 1,3-alternate conformation on aqueous subphase and solid substrates have been studied. Only tetra-cyanopropoxy-p-tert-butylthiacalix[4]arene 1 forms a typical monomolecular layer with perpendicular orientation of the macrocycle relative to the water-air interface that is able to immobilize cytochrome c in the entire range of the surface pressure. Obtained monolayers were transferred by Langmuir-Schaefer technique onto quartz, indium-tin oxide (ITO), and silicon. It was demonstrated that protein activity is retained after immobilization on the substrate.

Cyclic voltammetry of nitronyl- and iminonitroxyls detected by electron spin resonance

The combined cyclic voltammetry method (cyclic voltammetry detected by electron spin resonance, CVA-DESR CVA) was applied to study the electrochemical reactions of nitronyl- and iminonitroxyls (NN and IN) and to estimate the diffusion and absorption characteristics of their products. The ESR method yielded the hyperfine structure constants, including 13C. Even if exposed to lower temperature, all the studied NN were shown to spontaneously lose oxygen and to convert gradually into the relevant IN. For each specific NN, the combined CVA-DESR CVA experiments found the reduction potential value at which it can be virtually completely converted into the relevant IN.