Pavel O. Krasnov

Nanotube-derived carbon foam for hydrogen sorption

A new kind of carbon foam, which is based on the welding of single-walled carbon nanotubes, is built in a computer simulation. Its precisely defined architecture and all atomic positions allow one to perform detailed theoretical analysis of the properties. Such foam is as light as 19 of steel, while its stiffness is similar and nearly isotropic, and it represents a strong three-dimensional material with various possible applications. Furthermore, its nanoporous structure is accessible to molecular hydrogen and the potential surface analysis indicates that it should be an excellent hydrogen storage medium. Importantly, such foam is a feasible structure that can be produced based on the known tube/fullerene welding techniques.

Theoretical study of the influence of vacancies on the electronic structure of a hexagonal boron nitride monolayer

The influence of boron and nitrogen vacancies and divacancies on the electronic structure of a hexagonal boron nitride h-BN monolayer is studied. In the presence of vacancies in the structure, the introduced states appear in the forbidden band. The position of an introduced state with respect to the upper occupied level and the lower vacant level depends on deformation. Calculations show that, depending on the defect type and the magnitude of the applied deformation, the introduced state can be both localized and not localized on atoms surrounding the defect. When the state is localized in the system, the inhomogeneous distribution of the spin density is observed, resulting in the appearance of the magnetic moment in the system.

A complex of ceftriaxone with Pb(II): synthesis, characterization, and antibacterial activity study

A Pb(II) complex with ceftriaxone (H2Ceftria) antibiotic was synthesized by reaction of ceftriaxone disodium salt (hemi)heptahydrate with lead nitrate in water–ethanol medium. The complex was characterized on the basis of complexometric titration, spectrophotometric and thermogravimetric analyses, capillary electrophoresis, IR, Raman and UV–vis spectroscopies, and density functional theory calculations. Pb(II) is five-coordinate with distorted square pyramidal geometry. The coordination of Ceftria2− to Pb(II) occurs through N and O of the triazine, lactam carbonyl, carboxylate, and amine groups. The antibacterial activity study showed that Klebsiella pneumoniae is resistant to [Pb(Ceftria)]·3H2O. The antibacterial activity of [Pb(Ceftria)]·3H2O against Staphylococcus aureus is reduced compared with ceftriaxone. In contrast, the antibacterial activity of [Pb(Ceftria)]·3H2O against Escherichia coli is 28% higher than that of ceftriaxone antibiotic. Graphical Abstract

Possibility of a 2D SiC Monolayer Formation on Mg(0001) and MgO(111) Substrates

The geometrical characteristics of a 2D SiC monolayer on Mg(0001) and MgO(111) plates regarded as potential materials for growing two-dimensional silicon carbide were studied. The most favorable positions of the atoms of 2D SiC on the substrates were determined. In the 2D SiC/Mg(0001) system, unlike in 2D SiC/MgO(111), the deviation of the carbon atom from the silicon carbide monolayer was insignificant (0.08 Å). Consequently, magnesium can be used as a substrate for growing two-dimensional silicon carbide. The use of MgO(111) is not recommended because of a significant distortion of the 2D SiC surface.

Peculiarities of the decoration of carbon nanotubes with transition metal atoms

Carbon nanotubes decorated with transition metal, in particular, scandium, titanium, and vanadium, atoms offer promise for use in various applied science fields. We report the results of quantum-chemical calculations of the structure of the metallic layer of atoms of these metals coating the surface of (9, 0) and (10, 0) carbon nanotubes. It was shown that uniform one-layer coating by scandium and titanium could form on nanotubes with diameters no less than the diameter of (10, 0) nanotubes. Vanadium atoms could not uniformly cover nanotubes irrespective of their diameters.

Calculation of the energy of binding of titanium and scandium complexes to the surface of carbon nanotubes

Complexes of zigzag-type carbon nanotubes (CNTs) with transition metal atoms, scandium and titanium, were studied. It was demonstrated that the energy of binding of both atoms with a carbon surface decreases whereas the rate of diffusion along the surface increases with increasing nanotube diameter. The rate constant of migration of scandium atoms over a CNT surface are several orders of magnitude higher than that for titanium atoms, because the CNT surface—Sc atom binding energy is substantially lower.

Effect of fluorosubstitution on the structure of single crystals, thin films and spectral properties of palladium phthalocyanines

Abstract In this work, the crystalline structure of single crystals grown by vacuum sublimation of unsubstituted palladium phthalocyanines (PdPc), its tetrafluorinated (PdPcF 4 ) and hexadecafluorinated (PdPcF 16 ) derivatives have been investigated using X-ray diffraction measurements. Two crystalline phases have been identified for PdPc; the molecules in both phases crystallize in stacks with herringbone arrangement in the monoclinic space groups ( C 2/ c for α-PdPc; P2 1 /n for γ-PdPc). Both PdPcF 4 and PdPcF 16 crystallize in the triclinic P-1 space group, forming stacks of molecules in columnar arrangement with molecules in adjacent columns aligned parallel to one another. X-ray diffraction measurements have also been used to elucidate the structural features and molecular orientation of thin films of PdPc, PdPcF 4 and PdPcF 16 , grown by organic molecular beam deposition at different substrate temperatures. The effect of fluorosubstitution on UV-visible optical absorption and vibrational spectra of palladium phthalocyanine derivatives is also discussed.

Hypothesis of Hemoprotein Sensor Confirmed by Ab initio Quantum-Chemical Method

The nature of the chemical bond of complexes of iron and cobalt porphyrinates with ligands is studied by the quantum-chemical method in the Hartree–Fock self-consistent field approximation using the 3-21G basis set. The addition of oxygen molecule to the MP and MPIm complexes (M = Fe, Co; Im is imidazole) is established to be more favorable than water addition. However, imidazole, which is the second ligand in the MPImO2 and MPImH2O complexes (M = Fe, Co), increases the M–O2 and M–H2O binding energies for iron, but decreases them for cobalt. The Co atom is bound with the porphyrin ring more strongly than the iron atom due to the larger total overlap of the atomic orbitals. The calculations of the binding energy in the complexes demonstrate similar changes in the structures of the spatial conformation of the deoxy form (FeP + H2O) of iron porphyrinate and the oxy form (CoP + O2) of cobalt porphyrinate. This is an argument in favor of the hypothesis of hemoprotein sensor of partial oxygen stress in tissues.

Static polarization of the supramolecular dyads of fullerene C60 with porphyrin derivatives

The nonlinear optical properties of four supramolecular dyads consisting of fullerene C60 non-covalently bonded to porphyrin, porphyrazine, tetrabenzoporphyrin and phthalocyanine were investigated by calculating their electronic polarizability and first- and second-order hyperpolarizabilities using the finite field method and the density functional theory with the Grimme dispersion correction. Large first- and second-order hyperpolarizabilities result in nonlinear dependence of the polarization of dyads on the strength of external electric field. The increase in the size of the π-conjugated electron system of the porphyrin analogs leads to the increase of the polarizability and first- and second-order hyperpolarizabilities of the dyads. The absence of the covalent bonds between the components of the dyads prevents the field-induced electron transfer from porphyrin analogs to fullerene. The main reason for the nonlinear behavior of the polarization of dyads is the mutual polarization of fullerene and porphyrin analogs amplified by the external electric field.

Theoretical investigation of the structure and properties of the VN(111) monolayer on the MgO(111) surface

The VN(111) monolayer on the MgO(111) surface has been simulated and optimized in terms of the density functional theory (DFT) calculations. The most favorable arrangement of vanadium nitride on the surface of the magnesium oxide plate has been found. The band structure and densities of states for the VN(111) monolayer have been calculated. It has been concluded based on the densities of states for the VN monolayer on the MgO surface that this structure exhibits properties of a diluted magnetic semiconductor.