Analysis of PCBs in Biotic Matrices by Two-Dimensional GC-ECD

Abstract

The suitability of three GC-ECD systems for the separation of a model mixture containing various congeners of PCBs together with persistent chlorinated aromatics (pesticides and their metabolites, industrial chemicals) was tested. Analyses were performed on two parallel capillaries, the stationary phase of one of them was always in routine practice very common 5% phenyl-methylpolysiloxane, the second one was either 50% phenylmethylpolysiloxane or 7% phenyl-7% cyanopropyl-methylpolysiloxane. The number of unresolved (coeluted) analytes was significantly reduced in these systems and thus unbiased quantitation of PCBs and other components used for regulation was possible. The utilization of this type of multidimensional chromatography for rapid and reliable analysis of real samples (fish oil, human fat) was documented.     

Effect of gap and flow orientation on two-phase flow in an oil-wet gap: Relative permeability curves and flow structures

Naturally fractured reservoirs contain about 25–30% of the world supply of oil. In these reservoirs, fractures are the dominant flow path. Therefore, a good understanding of transfer parameters such as relative permeability as well as flow regimes occurring in a fracture plays an important role in developing and improving oil production from such complex systems. However, in contrast with gas–liquid flow in a single fracture, the flow of heavy oil and water has received less attention. In this research, a Hele-Shaw apparatus was built to study the flow of water in presence of heavy oil and display different flow patterns under different flow rates and analyze the effect of fracture orientations on relative permeability curves as well as flow regimes. The phase flow rates versus phase saturation results were converted to experimental relative permeability curves. The results of the experiments demonstrate that, depending on fracture and flow orientation, there could be a significant interference between the phases flowing through the fracture. The results also reveal that both phases can flow in both continuous and discontinuous forms. The relative permeability curves show that the oil–water relative permeability not only depends on fluid saturations and flow patterns but also fracture orientation.     

Poisson–Boltzmann for oppositely charged bodies: an explicit derivation

The interaction between two parallel charged plates in ionic solution is a general starting point for studying colloidal complexes. An intuitive expression of the pressure exerted on the plates is usually proposed, which includes an electrostatic plus an osmotic contribution. We present here an explicit and self-consistent derivation of this formula in the only framework of the Poisson–Boltzmann (PB) theory. We also show that, depending on external constraints, the correct thermodynamic potential can differ from the usual PB free energy. For asymmetric, oppositely charged plates, the resulting expression predicts a non-trivial equilibrium position with the plates separated by a finite distance. The depth of this energy minimum is decisive for the stability of the complex. It is therefore crucial to obtain its explicit dependence on the charge densities of the plates and on the ion concentration. Analytic expressions for the position and depth of the energy minimum were derived in 1975 by Ohshima [Colloid Polym. Sci. 253, 150 (1975)] but, surprisingly, these important results seem to have been overlooked. We retrieve these expressions in a simpler formalism, more familiar to the physics community, and give a physical interpretation of the observed behavior.     

The extended Hulburt–Hirschfelder‐long‐range oscillator model for direct‐potential‐fit analysis

In the present work, an extended Hulburt–Hirschfelder oscillator model is proposed as a means of simplifying potential energy functions for direct‐potential‐fit analyses. The new potential energy function is joined smoothly to the long‐range inverse‐power dispersion energy expression. The new model is employed in direct‐potential‐fits using spectroscopic line positions that involve the ground electronic states of the principal isotopologues of hydrogen iodide and carbon monoxide, and the ground and first singlet‐sigma excited states of hydrogen fluoride and hydrogen chloride. The present methodology is found to lead to compact, flexible, and robust representations for the potential energy that compare favorably with the results of past work where more complicated models were employed.     

Lattice Boltzmann simulation of two-sided lid-driven flow in a staggered cavity

In this article, the lattice Boltzmann method is employed in order to explore incompressible fluid flow inside a two-sided lid-driven staggered cavity. Results of the lattice Boltzmann simulation for antiparallel motion of lids are compared with the data from existing literature. For parallel motion of lids, the characteristics of flow pattern for a variety of Re numbers (50–3200) are presented. An asymmetric steady-state flow pattern for parallel motion of lids is obtained.     

Synthesis,structural characterization and in vitro cytotoxic activity of novel polymeric triorganotin(IV) complexes of urocanic acid

Two novel triorganotin carboxylate complexes of the biologically active urocanic acid have been synthesized and characterized. Elemental analysis, melting point, spectroscopic techniques – IR, ¹H, ¹³C and ¹¹⁹Sn NMR – mass spectrometry and X‐ray diffraction studies have been used for structural characterization. Crystal structures of the tin(IV) derivatives show that urocanic acid acts as a bridging bidentate ligand through its imidazole nitrogen atom and its carboxylic group, producing a polymeric one‐dimensional chain. The molecular structures of the complexes, catena‐poly‐tri(n‐butyl)tin(IV) 3‐(3H‐imidazol‐4‐yl)prop‐2‐enoate (1) and catena‐poly‐triphenyltin(IV) 3‐(3H‐imidazol‐4‐yl)prop‐2‐enoate (2), present a distorted trigonal–bipyramidal configuration. This is further confirmed by ¹¹⁹Sn NMR in the solid state. The tin(IV) derivatives form double‐stranded ribbons via N―H^…O―H bonds. Nevertheless, the compounds are essentially monomeric in solution, with a tetrahedral configuration as observed by ¹¹⁹Sn NMR in solution. The cytotoxic activity of the titled compounds has been tested against six human cell lines and the corresponding IC₅₀ values are reported. Both tin(IV) compounds have a high to very high in vitro cytotoxic activity against the tumor cell lines K562, HCT‐15 and MCF‐7. Compound 1 is 86 times more active than cisplatin in the HTC‐15 cell line. Copyright © 2012 John Wiley & Sons, Ltd.     

The maximum number of columns in supersaturated designs with

Cheng and Tang [Biometrika, 88 (2001), pp. 1169–1174] derived an upper bound on the maximum number of columns that can be accommodated in a two‐symbol supersaturated design (SSD) for a given number of rows () and a maximum in absolute value correlation between any two columns (). In particular, they proved that for (mod ) and . However, the only known SSD satisfying this upper bound is when . By utilizing a computer search, we prove that for , and . These results are obtained by proving the nonexistence of certain resolvable incomplete blocks designs. The combinatorial properties of the RIBDs are used to reduce the search space. Our results improve the lower bound for SSDs with rows and columns, for , and . Finally, we show that a skew‐type Hadamard matrix of order can be used to construct an SSD with rows and columns that proves . Hence, we establish for and for all (mod ) such that . Our result also implies that when is a prime power and (mod ). We conjecture that for all and (mod ), where is the maximum number of equiangular lines in with pairwise angle .     

On the variety of triangles for a hyper-Kähler fourfold constructed by Debarre and Voisin

We study the similarities between the Fano varieties of lines on a cubic fourfold, a hyper-Kähler fourfold studied by Beauville and Donagi, and the hyper-Kähler fourfold constructed by Debarre and Voisin in [3]. We exhibit an analog of the notion of “triangle” for these varieties and prove that the 6-dimensional variety of “triangles” is a Lagrangian subvariety in the cube of the constructed hyper-Kähler fourfold.