The effect of metal cations on the nature of the first electronic transition of liquid water as studied by attenuated total reflection far-ultraviolet spectroscopy

The first electronic transition (?←X?) of liquid water was studied from the perspective of the hydration of cations by analyzing the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of the Group I, II, and XIII metal nitrate electrolyte solutions. The ?←X? transition energies of 1 M electrolyte solutions are higher (Li(+): 8.024 eV and Cs(+): 8.013 eV) than that of pure water (8.010 eV) and linearly correlate with the Gibbs energies of hydration of the cations. The increases in the ?←X? transition energies are mostly attributable to the hydrogen bond formation energies of water molecules in the ground state induced by the presence of the cations. The deviation from the linear relation was observed for the high charge density cations, H(+), Li(+), and Be(2+), which reflects that the electronic energies in the excited states are also perturbed. Quantum chemical calculations show that the ?←X? transition energies of the water-cation complexes depend on the hydration structures of the cations. The calculated ?←X? transition energies of the water molecules hydrating high charge density cations spread more widely than those of the low charge density cations. The calculated transition energy spreads of the water-cation complexes directly correlate with the widths of the ?←X? transition bands measured by ATR-FUV spectroscopy.     

On a synchronization queue with two finite buffers

In this paper, we consider a synchronization queue (or synchronization node) consisting of two buffers with finite capacities. One stream of tokens arriving at the system forms a Poisson process and the other forms a PH-renewal process. The tokens are held in the buffers until one is available from each flow, and then a group-token is instantaneously released as a synchronized departure. We show that the output stream of a synchronization queue is a Markov renewal process, and that the time between consecutive departures has a phase type distribution. Thus, we obtain the throughput of this synchronization queue and the loss probabilities of each type of tokens. Moreover, we consider an extended synchronization model with two Poisson streams where a departing group-token consists of several tokens in each buffer. This revised version was published online in June 2006 with corrections to the Cover Date.     

Whitening as a Tool for Estimating Mutual Information in Spatiotemporal Data Sets

We address the issue of inferring the connectivity structure of spatially extended dynamical systems by estimation of mutual information between pairs of sites. The well-known problems resulting from correlations within and between the time series are addressed by explicit temporal and spatial modelling steps which aim at approximately removing all spatial and temporal correlations, i.e. at whitening the data, such that it is replaced by spatiotemporal innovations; this approach provides a link to the maximum-likelihood method and, for appropriately chosen models, removes the problem of estimating probability distributions of unknown, possibly complicated shape. A parsimonious multivariate autoregressive model based on nearest-neighbour interactions is employed. Mutual information can be reinterpreted in the framework of dynamical model comparison (i.e. likelihood ratio testing), since it is shown to be equivalent to the difference of the log-likelihoods of coupled and uncoupled models for a pair of sites, and a parametric estimator of mutual information can be derived. We also discuss, within the framework of model comparison, the relationship between the coefficient of linear correlation and mutual information. The practical application of this methodology is demonstrated for simulated multivariate time series generated by a stochastic coupled-map lattice. The parsimonious modelling approach is compared to general multivariate autoregressive modelling and to Independent Component Analysis (ICA).     

New method for preparing saturated and unsaturated aliphatic polyurethanes

Saturated and unsaturated aliphatic polyurethane were obtained from three different routes. In route 1, 1,4-dichloro-2-butene, sodium cyanate, and methanol were reacted to give dimethyl 2-butene-1,4-dicarbamate. This is hydrogenated easily to give dimethyl butane-1,4-dicarbamate. Ester exchange reaction of this compound with glycol gave saturated aliphatic polyurethane. In another procedure, route 2, 1,4-dichloro-2-butene, sodium cyanate and excess glycol were reacted to give bis(ω-hydroxyalkyl)-2-butene-1,4-dicarbamate. This was hydrogenated to give bis(ω-hydroxyalkyl)-butane-1,4-dicarbamate. A glycol elimination reaction gave poly(polymethylene tetramethyl-enedicarbamate). By route 3, 1,4-dichloro-2-butene, sodium cyanate, and glycol were reacted to give poly(polymethylene 2-butene-1,4-dicarbamate), a new unsaturated aliphatic polyurethane.     

Electroreductive intramolecular coupling of chiral alpha-imino esters: stereoselective synthesis of mixed ketals of cis-2,4-disubstituted azetidine-3-ones

The electroreduction of chiral aromatic alpha-imino esters prepared from (S)-alpha-amino acids, such as (S)-valine, (S)-leucine, and (S)-phenylalanine, in the presence of chlorotrimethylsilane and triethylamine afforded four-membered cyclized products, mixed ketals of cis-2,4-disubstituted azetidine-3-ones, stereospecifically (>99% de, 85-99% ee). The best result of the electroreductive cyclization was obtained using Bu(4)NClO(4) as a supporting electrolyte and a Pt cathode. The absolute stereochemistry of the obtained single stereoisomers was confirmed to be 2R,3R,4S by X-ray crystallography. Calculations for the transition states of the cyclization support the stereospecific formation of the (2R,3R,4S)-isomers.     

Frequencies of breathing vibrations of nearly spherical Ar clusters calculated by molecular dynamics

The breathing vibration of Ar _N cluster,N=13, 20, 25, 30 and 55, was investigated by use of the molecular dynamics method. The average distance \((\bar r)\) averaged over the positions of all Ar atoms with respect to the center of mass was calculated as a function of time and its frequency spectrum was derived by the Fourier transform analysis. The \(\bar r\) value was proved to be a good index of the breathing vibration in comparison with the exact breathing vibration of an Ar dense sphere. The vibrational frequency thus estimated,f _MD, was found to increase with the cluster sizen as expected.     

Optical modeling of nanocrystalline TiO2 films

The light transmittance, T, in nanocrystalline TiO2 films was studied as a function of the light wavelength, lambda, the nanocrystal radius, a, and the film thickness, d. Two types of TiO2 nanoparticles were employed: a commercial powder (P25) and synthesized particles from titanium isopropoxide (SP). The X-ray diffraction measurements revealed that both P25 and SP are mainly anatase and the average crystal sizes, 2a, of P25 and SP are 50.3 and 23.7 nm, respectively. Despite the visual difference between micron-order thin films of P25 and SP, the light hemispherical transmittance corrected with the surface specular reflectance has a clear dependence of ln(T) = -0.5beta lambda(-4)a(3)d, with beta = 1.5 x 10(3) from visible to near-infrared wavelengths. The dependence and beta value were successfully explained by the simplest model on the basis of the Rayleigh scattering theory. This indicates that the nanocrystalline TiO2 thin films are a typical medium where the simplest scattering model is a good approximation. However, the model was inapplicable to light scattering in relatively thick P25 films of 1.5-3.0 microm because of nonnegligible internal multiple scattering. For the moderate thickness films, ln(T) proportional to lambda(gamma), where gamma increases from -4 in proportion to the film thickness is an alternative approximation. With these light scattering models, the light absorption rate of the TiO2 crystal was successfully evaluated from experimental extinction rates.     

Iridoidglucoside aus Leucocarpus perfoliatus G. DON. 174. Mitteilung über organische Naturstoffe

Iridoidglucosides from Leucocarpus perfoliatus G. DON . The known iridoid glucoside boschnalosid (1) was isolated from Leucocarpus perfoliatus in addition to the hitherto unknown yuheinosid, for which structure 2 was deduced.