Influence of polarity of solvents on the spectral properties of bichromophoric coumarins

Absorption and fluorescence spectra of bichromophoric coumarins were investigated in different solvents and in polymer matrices. These bichromophoric coumarins were composed of a coumarin dimethylamino-substituted at position 7 or unsubstituted coumarin and phthalimide or a 1,8-naphthylimide linked with an iminomethyl bridge to the position 3 or 8 of the coumarin ring. Absorption spectra of 7-dimethylamino derivatives in position 3 of coumarin were quite similar, exhibiting broad bands around 430-440 nm like the parent compound 7-dimethylaminocoumarin-3-carbaldehyde. For coumarin derivatives substituted in position 8, the absorption maximum was shifted to shorter wavelength as for derivatives without position 7 dimethylamino substitution. The most intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin in polar solvent, while intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)iminomethyl]-coumarin in non polar solvent (chloroform), comparable with the fluorescence of 7-amino-4-methylcoumarin. Spectral measurements of bichromophoric coumarins in polymer matrices revealed that the maxima lies in between those for chloroform and methanol yielding more intense fluorescence then in solutions. Completely different solvent effects were observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)imino-methyl]coumarin and 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin. With addition of polar methanol the intensity of fluorescence decreases, yielding a Stern-Volmer-like constant of 0.54 dm3 mol?1 for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxo-benz[de]isoquinolinyl)iminomethyl]coumarin and an even higher one of 1.08 dm3·mol?1 for 7-dimethylaminocoumarin-3-carbaldehyde compared to the rather low one of 0.024 dm3 mol?1 for 7-amino-4-methylcoumarin. Contrary to this, addition of methanol under identical conditions brings about an increase in fluorescence intensity of 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin (about 60-fold). The reasons for these different solvent effects are discussed.     

The Last Fortress of Tin's Tyranny – Protodenitration of Nitroalkanes

Protodenitration, a direct reduction of nitroalkanes to corresponding alkanes, already spans two centuries and is enabled by various reagents. This mini-review provides a historical development of the fundamental transformation and highlights the governing position of the Ono-Tanner reaction employing tributyltin hydride. Due to the unchallenged dominance of the toxic tributyltin hydride and environmentally unpopular solvents sharply contrasting with modern ecological trends, the current situation was dubbed “the last fortress of tin's tyranny.”     

The attractor of the scalar reaction diffusion equation is a smooth graph

For the scalar reaction diffusion equation with Dirichlet boundary conditions, it is proved that its maximal compact attractor is the graph of a C¹ function from a subset with nonempty interior of a subspace of the state space the dimension of which is equal to the maximal Morse index of the equilibria of the equation.     

Some exact results for the spin-1/2 Falicov-Kimball model in the strong coupling limit

The spin-1/2 Falicov-Kimball model for electronically driven valence and metal-insulator transitions is studied analytically using strong-coupling perturbation theory. It is shown that in the limit of the infinite interaction strength between localized and itinerant electrons the Falicov-Kimball model undergoes two types of discontinuous valence transitions: the insulator-metal transitions from an integer-valence ground state (n _f = 1) into an inhomogeneous intermediate-valence ground state (0 < n _f < 1) and the insulator-metal transitions from n _f = 1 to n _f = 0. In addition, we discuss the role of the electron-phonon interaction on the mechanism of valence transitions and we present possible extensions of the exact one dimensional results to higher dimensions.     

Molecular characterization and first report of Cryptosporidium genotypes in human population in the Slovak Republic

In our study, we examined 91 fecal samples from five different groups of people containing HIV patients, hemodialysis patients, kidney transplant recipients, immunocompetent humans without clinical signs, and humans with suspected cryptosporidiosis. The purpose of our study was to determine species and genotype composition of representatives of Cryptosporidium spp. using PCR analysis of small subunit ribosomal RNA gene and 60‐kDa glycoprotein gene and examine their phylogenetic relationship. In HIV‐positive/AIDS‐infected group of patients and in hemodialysis patients, no presence of Cryptosporidium species was detected. In two kidney transplant recipients, we detected species/genotypes Cryptosporidium parvum IIaA13G1T1R1 (KT355488) and Cryptosporidium hominis IaA11G2R8 (KT355489) and in two immunocompetent patients with clinical symptoms, we identified Cryptosporidium muris and C. hominis IbA10G2T1 (KT355490). In the group of healthy immunocompetent individuals without clinical signs, we identified species/genotype C. hominis IbA11G2 (KT355491) in one sample.     

On a Model of a Currency Exchange Rate – Local Stability and Periodic Solutions

A delay differential equation is presented which models how the behavior of traders influences the short time price movements of an asset. Sensitivity to price changes is measured by a parameter a. There is a single equilibrium solution, which is non-hyperbolic for all a>0. We prove that for a< 1 the equilibrium is asymptotically stable, and that for a>1 a 2-dimensional global center-unstable manifold connects the equilibrium to a periodic orbit. Its birth at a=1 is not of Hopf type and seems part of a Takens–Bogdanov scenario.     

Determination of eddy transport coefficients in thermo-lattice Boltzmann modeling of two-dimensional turbulence

Thermal Lattice Boltzmann (TLBE) techniques are used to consider the time evolution of free-decaying two dimensional (2D) turbulence induced by a double velocity shear layer. In particular, we consider the effect of this turbulence at a Reynolds number of 2555 on a strong temperature gradient. Since all structures are resolved on the 1024×1024 grid, the Smagorinsky model is employed to compute directly the eddy viscosity and eddy diffusivity. These transport coefficients play an integral part in large eddy simulations at very high Reynolds numbers where a direct simulation cannot resolve all excited scales. TLBE codes have the virtue of being readily extended to 3D, can readily handle nonperiodic geometries, and are ideally suited for multi-parallel computer architectures.This work was supported by a joint US-Czech DoE Grant #93066. Computations were performed under the auspices of the SPP (Special Parallel Processing) on the C90 at NERSC.     

Vibrational relaxation of the bending mode of HDO in liquid D2O

The vibrational relaxation of the bending mode of HDO in liquid D2O has been studied using time-resolved mid-infrared pump-probe spectroscopy. At short delays, the transient spectrum clearly shows the v = 1 --> 2 induced absorption and v = 1 --> 0 bleaching and stimulated emission, whereas at long delays, the transient spectrum is dominated by the spectral changes caused by the temperature increase in the sample after vibrational relaxation. From the decay of the v = 1 --> 2 induced absorption, we obtain an estimate of 390 +/- 50 fs for the vibrational lifetime, in surprisingly good agreement with recent theoretical predictions. In the v = 0 --> 1 frequency region, the decay of the absorption change involves a second, slower component, which suggests that after vibrational relaxation the system is not yet in thermal equilibrium.     

Graph with given achromatic number

An irreducible (point-determining) graph is one in which distinct vertices have distinct neighbourhoods. Every graph X can be reduced to an irreducible graph X¹ by identifying all vertices with the same neighbourhood; the colourability properties of X¹ carry over to X. Hence irreducible graphs are instrumental in the study of achromatic number. We prove that there are only finitely many irreducible graphs with a given achromatic number, and describe all graphs with achromatic number less than four. We deduce certain bounds on the achromatic number X in terms of the number of vertices of X¹. In the course of the proofs we calculate the achromatic numbers of paths and cycles. Generalizations of the main theorem to homomorphisms other than colourings are discussed.