Application of a retention database to the identification of individual polychlorinated biphenyl congeners in Aroclors mixture using selected polychlorinated biphenyls as a reference series

The database of the relative retention times (RRTs) of polychlorinated biphenyls (PCBs) reported in literature was used to calculate the retention indices (RIs) of all 209 PCB congeners on temperature programmed capillary column Rtx-5. Calculation of retention indices was based on reference series of seven congeners (PCB IUPAC Nos. 18, 52, 101, 143, 185, 203 and 206) that exhibit linear relative retention time behaviour as a function of chlorine number. The calculated indices were compared to those determined in our laboratory as well as to those obtained by other authors. The proposed indices system was applied for identification individual congeners in mixture of Aroclors 1242:1254:1260, using only reference series of PCBs.     

Simultaneous determination of uranium(IV) and thorium(IV) ions with Arsenazo III by partial least squares method

A multivariate calibration method, Partial Least Squares Type 1 (PLS-1), is proposed for simultaneous spectrophotometric determination of uranium and thorium ions as their complexes with arsenazo III in hydrochloric acid medium. Several data characteristics are taking into account in order to minimize the optimum number of factors required for the construction of calibration model, while using various statistical criterions of selection. Finally, the evaluated calibration model is satisfactorily applied to determination of these ions in samples that resemble sulfuric acid leach solution obtained from a uranium ore.     

Pure phase correlation with improved discrimination capability

Pure phase correlation with improved discrimination capability is proposed. The improvement is achieved by designing a region of support based on the discrimination capability (DC). We propose four approaches for designing this region; some of them consider the input scene in the design, while others are input scene invariant. The performances of these approaches are compared by numerical simulation. The DC is improved significantly for the multi-object scenes even when using an input scene invariant region of support design.     

Molecular weight dependent charge carrier mobility in poly(3,3' '-dioctyl-2,2':5',2' '-terthiophene)

Poly(3,3' '-dioctyl-2,2':5',2' '-terthiophene), a polymer recently used for the fabrication of organic field effect transistors, has been fractionated into five fractions distinctly differing in their molecular weights (Mn), with the goal of determining the influence of the degree of polymerization (DPn) on its principal physicochemical parameters. It has been demonstrated that within the Mn range studied (from 1.5 kDa to 10.5 kDa by SEC), corresponding to DPn from 10 to 38, the polymer band gap steadily decreases with growing molecular weight, which is clearly manifested by an increasing bathochromic shift of the band originating from the pi-pi* transition. The same trend is observed for the HOMO level, determined from the onset of the p-doping in cyclic voltammetry, which shifts from -5.10 eV to -4.90 eV for the lowest and the highest molecular weight fractions, respectively. The most pronounced influence of DPn has been found for the charge carriers' mobility-one of the most important parameters of field effect transistors (FETs) fabricated from this polymer. A fourfold increase in DPn results in an increase of the carriers' mobility by more than 3 orders of magnitude. Comparison of these results with those obtained for fractionated regioregular poly(3-hexylthiophene) shows a strikingly similar behavior of both polymers with respect to the molecular weight.     

Interaction between rhodanine and silver species on a nanocolloidal surface and in the solid state

This paper discusses and compares molecular interactions of rhodanine (Rd), the heterocyclic compound containing N, S, and O atoms, with two forms of silver species, i.e. Ag(I) ions and silver nanocolloidal particles. Vibrational spectroscopic and powder crystallography studies on coordination of Ag(I) ions in the solid state, supported by density functional theory, clearly indicate complexation through the nitrogen (the deprotonated imino group) and exocyclic sulfur atoms. Molecules of the complex are arranged in a one‐dimensional infinite polymeric chain structure that intertwines to give a helix motif. On the other hand, adsorption geometry of Rd on the silver surface was determined by using surface‐enhancement Raman scattering (SERS) spectroscopy. Observed differences between the SERS and the normal Raman spectra of Rd suggest that Rd adsorbs on the silver species after the rearrangement of the keto‐thione form into the enol‐thiol tautomer in acidic and neutral solutions. This leads to adsorption on this silver species through the thiolate ion. On the other hand, the alkaline pH forces first N‐deprotonation of Rd, and, in consequence, the obtained anion of the keto‐thione form interacts with the silver surface as a result of the presence of lone pairs of nitrogen and sulfur atoms, similar to the case discussed for the solid state. Copyright © 2009 John Wiley & Sons, Ltd.     

Heat kernel characterisation of Besov-Lipschitz spaces on metric measure spaces

We give a heat-kernel characterisation of the Besov-Lipschitz spaces Lip (α, p, q)(X) on domains which support a Markovian kernel with appropriate exponential bounds. This extends former results of Grigor’yan et al. (Trans Am Math Soc 355:2065–2095, 2008), Hu and Zähle (Studia Math 170:259–281, 2005), Pietruska-Pa?uba (Stoch Stoch Rep 67:267–285, 1999; 70:153–164, 2000), which were valid for ${\alpha = \frac{d_w}{2}, p = 2, q = \infty}$ , where d _w is the walk dimension of the space X.     

Execution of active reduction of vibrations by means of kinematic excitations

The major objective of this study is to show how to carry out the process of structural and parametrical synthesis that is understood as a method intended to seek for the structure and parameters of a discrete model of the system with active suppression of vibrations. Active components are implemented as mechanical components with kinematic excitations. The other objective is to analyze how the active subsystem interacts with the overall investigated structure. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Helical twisting power of antiferroelectric chiral terphenyls in different matrices

To determine the influence of chemical structure on the Helical Twisting Power (HTP), we tested four optically active dopants having a terphenyl rigid core and the same chiral centre but differing in the length of nonchiral terminal chain and the substitution of benzene rings with fluorine atoms. The compounds were added to different achiral liquid crystalline matrices: nematic and smectic C. It was found that HTP as well as its temperature variation depends on the kind of used matrices. It gives a conclusion that information about HTP obtained in one matrix cannot be uncritically transferred to another one.