Diffusion-controlled distribution of solute in Sn-1% Bi specimens solidified by the submerged heater method

Two 1.35 kg, 5.8 cm diameter Sn-1% Bi specimens were solidified using the submerged heater method (SHM). The distribution of solute was found to be uniform axially, indicating that diffusion-controlled steady-state segregation, though to be unattainable on earth because of the gravity induced interference, was achieved.     

The error bounds of Gauss-Kronrod quadrature formulae for weight functions of Bernstein-Szegő type

We consider the Gauss-Kronrod quadrature formulae for the Bernstein-Szeg? weight functions consisting of any one of the four Chebyshev weights divided by the polynomial \(\rho (t)=1-\frac {4\gamma }{(1+\gamma )^{2}}\,t^{2},\quad t\in (-1,1),\ -1<\gamma \le 0\). For analytic functions, the remainder term of this quadrature formula can be represented as a contour integral with a complex kernel. We study the kernel, on elliptic contours with foci at the points ? 1 and sum of semi-axes ρ > 1, for the given quadrature formula. Starting from the explicit expression of the kernel, we determine the locations on the ellipses where maximum modulus of the kernel is attained. So we derive effective error bounds for this quadrature formula. An alternative approach, which has initiated this research, has been proposed by S. Notaris (Numer. Math. 103, 99–127, 2006).     

Decomposition of Complex Fluorescence Spectra Containing Components with Close Emission Maxima Positions and Similar Quantum Yields. Application to Fluorescence Spectra of Proteins

Despite of widely application of multivariate analysis in chemometrics, problem of resolving closely positioned components in the fluorescence spectra remained unsolved, thus limiting the usage of fluorescence spectroscopy in analytical purpose. In this paper we have described a novel procedure, adapted especially for the analysis of complex fluorescence spectra with multiple, closely positioned components’ maxima. The method was first tested on the simulated spectra and then applied on the spectra of proteins whose fluorophores have similar properties of both the excitation and the emission spectra. In this paper, simple but efficient modification of the method was applied. Instead of analyzing full size emission matrix (12 spectra), 9 spectra wide windows were analyzed, and 4 factors (greatest possible number of factors with physical meaning both for actin and simulated spectra) were extracted in each pass. Obtained factor scores were grouped by using the K-means algorithm. Groups of factor scores obtained from K-means algorithm were passed through the one more factor analysis (FA) in order to find one factor that represents each group. Our approach provides resolution of extremely closed spectral components, which is a vital data for protein conformation analysis based on fluorescence spectroscopy.     

A comparative analysis of a heat pump application with grey wastewater source for domestic hot water preparation in hotels

Journal of Thermal Analysis and Calorimetry - System for domestic hot water (DHW) preparation generally represents a considerable portion of the energy and water consumption in hotels worldwide. As...     

Configurational Isomerism in Polyoxovanadates

A water‐soluble derivative of the polyoxovanadate {V₁₅E₆O₄₂} (E=semimetal) archetype enables the study of cluster shell rearrangements driven by supramolecular interactions. A reaction unique to E=Sb, induced exclusively by ligand metathesis in peripheral [Ni(ethylenediamine)₃]²⁺ counterions, results in the formation of the metastable α₁* configurational isomer of the {V₁₄Sb₈O₄₂} cluster type. Contrary to all other polyoxovanadate shell architectures, this isomer comprises an inward‐oriented vanadyl group and is ca. 50 and 12 kJ mol^?1 higher in energy than the previously isolated α and β isomers, respectively. We discuss this unexpected reaction in light of supramolecular Sb?O???V and Sb?O???Sb contacts manifested in {V₁₄Sb₈O₄₂}₂ dimers detected in the solid state. ESI MS experiments confirm the stability of these dimers also in solution and in the gas phase. DFT calculations indicate that other, as of yet elusive isomers of {V₁₄Sb₈}, might be accessible as well.     

Interpretative optimization and artificial neural network modeling of the gas chromatographic separation of polycyclic aromatic hydrocarbons

An interpretative strategy (factorial design experimentation+total resolution analysis+chromatogram simulation) was employed to optimize the separation of 16 polycyclic aromatic hydrocarbons (PAHs) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-c,d)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene) in temperature-programmed gas chromatography (GC). Also, the retention behavior of PAHs in the same GC system was studied by a feed-forward artificial neural network (ANN). GC separation was investigated as a function of one (linear temperature ramp) or two (linear temperature ramp+the final hold temperature) variables. The applied interpretative approach resulted in rather good agreement between the measured and the predicted retention times for PAHs in both one and two variable modeling. The ANN model, strongly affected by the number of input experiments, was shown to be less effective for one variable used, but quite successful when two input variables were used. All PAHs, including difficult to separate peak pairs (benzo(k)fluoranthene/benzo(b)fluoranthene and indeno(1,2,3-c,d)pyrene/dibenzo(a,h)anthracene), were separated in a standard (5% phenyl-95% dimethylpolysiloxane) capillary column at an optimum temperature ramp of 8.0 degrees C/min and final hold temperature in the range of 260-320 degrees C.     

Orbital views of the electron transport in molecular devices

Extended pi-conjugated molecules are interesting materials that have been studied theoretically and experimentally with applications to conducting nanowire, memory, and diode in mind. Chemical understanding of electron transport properties in molecular junctions, in which two electrodes have weak contact with a pi-conjugated molecule, is presented in terms of the orbital concept. The phase and amplitude of the HOMO and LUMO of pi-conjugated molecules determine essential properties of the electron transport in them. The derived rule allows us to predict single molecules' essential transport properties, which significantly depend on the type of connection between a molecule and electrodes. Qualitative predictions based on frontier orbital analysis about the site-dependent electron transport in naphthalene, phenanthrene, and anthracene are compared with density functional theory calculations for the molecular junctions of their dithiolate derivatives, in which two gold electrodes have strong contact with a molecule through two Au-S bonds.