Synthesis and optoelectronic properties of hexahydroxylated 10-O-R-substituted anthracenes via a new modification of the Friedel-Crafts reaction using O-protected ortho-acetal diarylmethanols

A new modification of the Friedel-Crafts type intramolecular cyclization involving O-protected ortho-acetal diarylmethanols as a new type of reactant, was carried out for the first time in a medium containing a large amount of water at room temperature and enabled synthesis of a series of electron-rich, hexahydroxylated 10-O-R-substituted anthracenes, where R is an alkyl (Me, nBu, n-C(16)H(33)) or arylalkyl group (CH(2)Ph, CH(2)-2-Napht, CH(2)C(6)H(4)CH(2)OAr) and also evaluation of their electronic and optoelectronic properties in solution, crystal, and solid thin film. In this transformation, a central 10-O-R-substituted benzene ring was formed, fused to rings originating from two independent aromatic aldehydes. The reaction proceeded via two identified mechanisms involving acetal and/or free aldehyde groups. The acid sensitive acetal and dibenzyl alkoxy functions have never been used together in the intramolecular Friedel-Crafts type cyclization. The new compounds revealed deep blue fluorescence and quantum yields in solution around 0.3. The electrical properties investigated for thin films obtained by vacuum deposition on glass were 10-O-R-substituent dependent and showed much faster transient current decay in the case of the 10-O-CH(2)Ph derivative than for the material with a 10-O-Me substituent (the lifetime of charge carriers was 25 times shorter in this case). The AFM images of thin films, Stokes shifts, and X-ray analysis of π-stacking interactions in crystals of the new materials have been also obtained.     

Selective Cycloaddition of Tetracyanoethene (TCNE) and 7,7,8,8‐Tetracyano‐p‐quinodimethane (TCNQ) to Afford meso‐Substituted Phenylethynyl Porphyrins

π‐Extended TCBD‐porphyrins that contained a 1,1,4,4‐tetracyanobuta‐1,3‐diene unit were prepared by a highly efficient [2+2] cycloaddition of tetracyanoethene (TCNE) or 7,7,8,8‐tetracyano‐p‐quinodimethane (TCNQ) with meso‐substituted trans‐A₂B₂‐porphyrins that contained two phenylethynyl groups, followed by a retro‐electrocyclization reaction. Depending on the electronic properties of the arylethynyl groups, the cycloaddition reaction took place exclusively on either one or two ethynyl moieties with high yield. The addition of TCNQ proceeded with complete regioselectivity. The resulting π‐expanded TCBD‐porphyrins had a hypsochromically shifted Soret band and showed unique, broad absorption in the visible region.     

Crystal structure, electronic properties and cytotoxic activity of palladium chloride complexes with monosubstituted pyridines

Palladium(II) complexes attract great attention due to their remarkable catalytic and biological activity. In the present study X-ray characterization, UV-Vis and Time-Dependent Density Functional Theory (TD-DFT) calculations for six PdCl(2)(XPy)(2) complexes (where: Py = pyridine; X = H, CH(3) or Cl) were applied in order to investigate substituent effects on their crystal structures and electronic properties and to combine the results with their catalytic and cytotoxic activity. The structures of complexes PdCl(2)(3-MePy)(2), PdCl(2)(4-MePy)(2) and PdCl(2)(2-ClPy)(2), have been described for the first time and we compared our results with available data for the whole series of six complexes. All compounds exhibit a square planar coordination geometry in which the palladium ion coordinates two nitrogen atoms of pyridine ligands and two chlorine atoms in trans positions. For complexes with ortho substituted XPy ligands a cis disposition of substituents takes place, whereas for other ligands: 3-MePy and 3-ClPy--the substituents are in trans positions. For XPy the energies of π-π* and n-π* transitions depend on the position and nature of the X substituent in the XPy ring. After complex formation a hipsochromic shift (24-34 nm) of π-π* and a bathochromic shift of n-π* bands are observed. The UV-Vis spectra of PdCl(2)(XPy)(2) confirm that square planar coordination geometry of complexes I-VI and two dπ-π* transitions are expected. With the help of the TD-DFT calculations we proved that dπ-π* transitions in solutions of PdCl(2)(XPy)(2) complexes result from MLCT (metal-to-ligand charge transfer) with contribution from chlorine atoms to palladium. We also studied substituent effects on cytotoxic properties of Pd(II) complexes against the human breast cancer cell line MCF7, the human prostate cancer cell line PC3, and the human T-cell lymphoblast-like cell line CCRF. The studied complexes were the most active against the CCRF cell line and less or even no cytotoxic effect was observed for PC3 cells. Complexes with MePy ligands showed increased cytotoxic activity compared to unsubstituted pyridine ligands.     

XAFS investigations of nitrided NbN–SiO2 sol–gel derived films

This work presents the results of the structural analysis of xNbN–(100-x)SiO₂ (x = 100, 80, 60 mol%) thin films by X-ray absorption spectroscopy (XAS). To prepare the films, thermal nitridation of sol–gel derived coatings have been performed. The resulting films have a granular structure with NbN grains distributed in the SiO₂ matrix. The size of the grains depends on the NbN/SiO₂ molar ratio. A detailed X-ray absorption fine structure (XAFS) data analysis shows that in all the samples both nitrogen and oxygen atoms are present as nearest neighbours of Nb. The intra-granular phase is an ordered NbN phase, whereas the shells around the grains are formed mainly by an oxide phase and, possibly, by other niobium nitride phases (probably with low nitrogen content). Two possible origins of the inter-granular oxide phase were considered: incomplete nitridation of Nb₂O₅ and addition of SiO₂. Both of them are connected with the sample preparation method. The obtained XAS results allowed us to correlate the thickness and stoichiometry of the films under study with the electronic structure of the Nb ions and with the local geometric structure in their environment.     

Variational methods for the fractional Sturm–Liouville problem

This article is devoted to the regular fractional Sturm–Liouville eigenvalue problem. By applying the methods of fractional variational analysis, we prove the existence of a countable set of orthogonal solutions and corresponding eigenvalues. Moreover, we formulate two results showing that the lowest eigenvalue is the minimum value for a certain variational functional.     

Study of the cosmic rays transport problems using second order parabolic type partial differential equation

It has been exactly 100 years since Hess’s historical discovery: an extraterrestrial origin of cosmic rays [1]. Galactic cosmic rays (GCR) being charged particles, penetrate the heliosphere and are modulated by the solar magnetic field. The propagation of cosmic rays is described by Parker’s transport equation [2], which is a second order parabolic type partial differential equation. It is time dependent 4-variables (with r, θ, φ, R, meaning: distance from the Sun, heliolatitudes, heliolongitudes and particles’ rigidity, respectively) equation which is a well known tool for studying problems connected with solar modulation of cosmic rays. Transport equation contains all fundamental processes taking place in the heliosphere: convection, diffusion, energy changes of the GCR particles owing to the interaction with solar wind’s inhomogeneities, drift due to the gradient and curvature of the regular interplanetary magnetic field and on the heliospheric current sheet.     

Stochastic resonance for information flows on hierarchical networks

A simple model of information flows represented by package delivery on networks with hierarchical structures is considered. The packages should be transferred from one network node to another and the delivery process is influenced by two types of noise. The first type of noise is related to a partially false knowledge of network topology (topological noise), i.e. membership of nodes in communities in a shipping algorithm include a number of errors corresponding to a random rewiring of a fraction of network links. The second type of noise (dynamical noise) is related to a diffusive part in packet dynamics, i.e. package paths do not follow from completely deterministic rules. In the case of a pure topological noise and in the case of combination of both types of noises, we observe a resonance-like phenomenon for communication efficiency. The system performance measured as a fraction of packages that are delivered in a certain time period or as an inverse of time of a package delivery is maximal for intermediate levels of noise. This effect resembles the phenomenon of stochastic resonance that exists in many complex systems where a noise can enhance the information transfer.     

Morphology of struvite crystals as an evidence of bacteria mediated growth

Influence of Proteus mirabilis on the growth, morphology and size of struvite crystals in artificial urine has been studied. The growth in the presence of Proteus mirabilis shows formation of struvite crystals of more regular habits compared with that in the absence of bacteria. This implies that in the presence of Proteus mirabilis, struvite crystals grow with relative growth rates within smaller range of variability compared to the absence of bacteria. The results show that bacteria affect size and struvite morphology while the habit remains almost unchanged. It is suggested that the changes in struvite crystal morphology are induced by the presence of Proteus mirabilis. Microorganism's negatively charged residues interact electrostatically with positive ions which outcrop given surfaces and lead to an enhanced expression of these surfaces. This means that microorganisms actively mediate in growth processes. Therefore, the investigations provide evidence for the importance of biological regulation in crystallization process.