Photoinduced superoxide radical anion and singlet oxygen generation in the presence of novel selenadiazoloquinolones (an EPR Study)

Novel 7‐substituted 6‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐h]quinoline ( SeQ(1–6) ) and 8‐substituted 9‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐f ]quinoline derivatives ( SeQN(1–5) ) with R₇, R₈ = H, COOC₂H₅, COOCH₃, COOH, COCH₃ or CN were synthesized and their spectral characteristics were obtained by UV/Vis spectroscopy. Ultraviolet A photoexcitation of the selenadiazoloquinolones in dimethylsulfoxide or acetonitrile resulted in the formation of paramagnetic species coupled with molecular oxygen activation generating the superoxide radical anion or singlet oxygen, evidenced by electron paramagnetic resonance spectroscopy. The cytotoxic/photocytotoxic impact of selenadiazoloquinolones on murine and human cancer cell lines was demonstrated using the derivative SeQ5 (with R₇ = COCH₃).     

Cation-anion interactions involving hydrogen bonds: Syntheses and crystal structures study of hexafluorotitanate(IV) salts with pyridine and methyl substituted pyridines

Fluorotitanates (LH)₂[TiF₆]·nH₂O (1: R = pyridine, n = 1, 2: R = 2-picoline, n = 2, 3: R = 2,6-lutidine, n = 0, 4: R = 2,4,6-collidine, n = 0) and (LH)[TiF₅(H₂O)] (3a: L = 2,6-lutidine) have been synthesized by the reaction of pyridine or corresponding methyl substituted pyridines and titanium dioxide dissolved in hydrofluoric acid. The crystal structures of ionic compounds 1, 2, 3, 3a and 4 have been determined by single-crystal X-ray diffraction analysis. The hydrogen bonding led to the formation of discrete (LH)₂[TiF₆] units (4), chains (1-3), and layers (3a). The additional π-π interactions present in 1, 2, and 4 results in chain structures of 1 and 4 and in a layer structure of 2. The [TiF₆]²⁻ and [TiF₅(H₂O)]⁻ anions were observed by ¹⁹F NMR spectroscopy in aqueous solutions of 1, 2, 3, 3a and 4.     

Size-dependent electrocatalytic activity of gold nanoparticles on HOPG and highly boron-doped diamond surfaces

Gold nanoparticles were prepared by electrochemical deposition on highly oriented pyrolytic graphite (HOPG) and boron-doped, epitaxial 100-oriented diamond layers. Using a potentiostatic double pulse technique, the average particle size was varied in the range from 5 nm to 30 nm in the case of HOPG as a support and between < 1 nm and 15 nm on diamond surfaces, while keeping the particle density constant. The distribution of particle sizes was very narrow, with standard deviations of around 20% on HOPG and around 30% on diamond. The electrocatalytic activity towards hydrogen evolution and oxygen reduction of these carbon supported gold nanoparticles in dependence of the particle sizes was investigated using cyclic voltammetry. For oxygen reduction the current density normalized to the gold surface (specific current density) increased for decreasing particle size. In contrast, the specific current density of hydrogen evolution showed no dependence on particle size. For both reactions, no effect of the different carbon supports on electrocatalytic activity was observed.     

Optimal anisotropic three-phase conducting composites: Plane problem

The paper establishes tight lower bound for effective conductivity tensor K₁ of two-dimensional three-phase conducting anisotropic composites and defines optimal microstructures. It is assumed that three materials are mixed with fixed volume fractions and that the conductivity of one of the materials is infinite. The bound expands the Hashin–Shtrikman and translation bounds to multiphase structures, it is derived using a combination of translation method and additional inequalities on the fields in the materials; similar technique was used by Nesi, 1995, Cherkaev, 2009 for isotropic multiphase composites. This paper expands the bounds to the anisotropic composites with effective conductivity tensor K₁. The lower bound of conductivity (G-closure) is a piece-wise analytic function of eigenvalues of K₁, that depends only on conductivities of components and their volume fractions. Also, we find optimal microstructures that realize the bounds, developing the technique suggested earlier by Albin et al., 2007a, Cherkaev, 2009. The optimal microstructures are laminates of some rank for all regions. The found structures match the bounds in all but one region of parameters; we discuss the reason for the gap and numerically estimate it.     

Principal Compliance and Robust Optimal Design

The paper addresses a problem of robust optimal design of elastic structures when the loading is unknown and only an integral constraint for the loading is given. We propose to minimize the principal compliance of the domain equal to the maximum of the stored energy over all admissible loadings. The principal compliance is the maximal compliance under the extreme, worst possible loading. The robust optimal design is formulated as a min-max problem for the energy stored in the structure. The maximum of the energy is chosen over the constrained class of loadings, while the minimum is taken over the design parameters. It is shown that the problem for the extreme loading can be reduced to an elasticity problem with mixed nonlinear boundary conditions; the last problem may have multiple solutions. The optimization with respect to the designed structure takes into account the possible multiplicity of extreme loadings and divides resources (reinforced material) to equally resist all of them. Continuous change of the loading constraint causes bifurcation of the solution of the optimization problem. It is shown that an invariance of the constraints under a symmetry transformation leads to a symmetry of the optimal design. Examples of optimal design are investigated; symmetries and bifurcations of the solutions are revealed.     

Some remarks on the two-body-problem in geometrodynamics

The interest in the two body problem in geometrodynamics and its present status are discussed. Special consideration is given to time-symmetric initial data. An equation relating the “bare mass energy,” the potential energy and the “vibrational energy” at the initial moment is proposed. The significance of coordinate conditions in dynamical equations is discussed next. Conditions implying maximal slicings of spacetime and harmonic coordinates in those slices are considered in detail, as they seem to be well suited for numerical calculations and for interpretation of the results of such calculations.     

Syntheses of some azolopyridopyrimidines

Syntheses of isomeric azolopyridopyrimidines are described. As starting material the corresponding pyridopyrimidines were used. It could be established that in many cases a transformation of a functional group with the purpose to form an annelated five-membered ring proceeded with ring opening at the pyrimidine part. Subsequent ring closure with one carbon synthons gave then the desired tricyclic heterocycles.