Improved models for the phase behaviour of hydrogen fluoride: chain and ring aggregates in the SAFT approach and the AEOS model

Hydrogen fluoride presents one of the strongest hydrogen bonds known. Ring aggregates exist both in the vapour and liquid phases at low temperatures resulting in an anomalously high low-temperature vapour pressure. The effect of ring-like aggregates on the vapour—liquid phase equilibria of associating fluids is studied within the framework of the statistical associating fluid theory (SAFT) and in the chemical model of Lencka and Anderko (AEOS). The SAFT approach incorporates separate contributions to describe chain formation, association (hydrogen bonding), and long range dispersion forces. The treatment of the association interactions stems from the thermodynamic perturbation theory of Wertheim. At the first level of approximation the contribution of ring-like aggregates is neglected and only chain- and treelike structures are treated. In this work an earlier extension of the approach to incorporate ring aggregates is used to model the phase behaviour of hydrogen fluoride. The chemical model of Lencka and Anderko for associating fluids is also considered together with a modification that takes into account the formation of ring aggregates. Vapour pressures and coexistence densities are examined together with heats of vapourization, and the calculations are compared with experimental data.     

Electron spin resonance studies of 199HgH, 201HgH, 199HgD and 201HgD isolated in neon and argon matrices at 4K: an electronic structure investigation

Various isotopomers of the mercury hydride radical (HgH) have been generated in a microwave discharge and trapped in neon and argon matrices at 4 K for electron spin resonance (ESR) investigations. Both the dipolar (A_dip) and isotropic (A_iso) components of the nuclear hyperfine interactions have been directly measured for ¹⁹⁹Hg, ²⁰¹Hg, H and D. Electronic structure information for HgH in its X²Σ ground state obtained from the hyperfine data is compared with theoretical results from several different computational methods. The hyperfine interactions in HgH are unusually large with A_iso(¹⁹⁹Hg) = 6859(3), A_dip(¹⁹⁹Hg) = 446(3), A_iso(H) = 730(2) and A_dip(H) = 0(2) MHz. A standard analysis of the hyperfine interactions demonstrates the need for a more in-depth theoretical treatment of HgH that should include relativistic effects. An interesting shift in spin density is observed when deuterium replaces hydrogen in HgH. The decreased spin density on deuterium, which was demonstrated in earlier studies, can now be more fully investigated since these new measurements confirm an associated increase in spin density on mercury     

The Saffman-Taylor problem for an extremely shear-thinning fluid

We consider a steady flow driven by pushing a finger of gasinto a highly shear-thinning power-law fluid, with exponentn, in a Hele-Shaw channel. We formulate the problem in termsof the streamfunction , which satisfies the p-Laplacian equation (with ), and investigate travelling wave solutions in the large-n (extreme shear-thinning) limit.We take a Legendre transform of the free-boundary problem for, which reduces it to a linear problem on a fixed domain. The solution to this problem is foundby using matched asymptotic expansions and the resulting shapeof the finger deduced (being, to leading order, a semi-infinitestrip). The nonlinear problem for the streamfunction is alsotreated using matched asymptotic expansion in the physical plane.The finger-width selection problem is briefly discussed in termsof our results.     

Modelling,simulation, animation,and real-time control (MoSART) for a class of electromechanical systems: a system-theoretic approach

This paper describes an interactive modelling, simulation, animation, and real-time control (MoSART) environment for a class of ‘cart-pendulum’ electromechanical systems that may be used to enhance learning within differential equations and linear algebra classes. The environment is useful for conveying fundamental mathematical/systems concepts through computer-aided analysis, design, graphical visualization, and 3D animation. Referred to as Cart-Pendulum Control3D-Lab1Control3D-Lab-short for control 3D animation laboratory. The author to whom correspondence should be addressed., the environment is based on Microsoft Windows/Visual C++/Direct-3D and MATLAB/Simulink2MATLAB and Simulant are trademarks of The Masterworks, Inc.. Pull-down menus provide access to systems/models/control laws, exogenous signals, parameters, animation models and visual indicators, a suite of (easy-to-modify) Simulant diagrams containing models and control laws, MATLAB m-files for detailed analysis and design, and detailed documentation for each of the above. Three blocks enable animation, joystick inputs, and real-time animation within Simulant. Examples are presented to illustrate the utility of the environment as a valuable tool for analysing/visualizing the above class of electromechanical systems and for enhancing mathematics instruction.     

PHOTODYNAMIC ACTION OF CHEMICALLY RELATED FLAVONES

Abstract— Flavone, polyhydroxyflavones (apigenin, fisetin, kaempferol, luteolin, myricetin, quercetin, resokaempferol and robinetin), polymethoxyflavones and acetylated and benzylated flavones were tested for photodynamic activity using Tetrahymena pyriformis T as the test organism. Among these compounds, polymethoxyflavones showed the highest order of activity, followed by flavone and then flavone derivatives with OH and OCH₃ groups. Resokaempferol was the only active polyhydroxyflavone, the remainder being inactive such as the benzyl-derivative. The methoxyl group in the 5–position and an increase in number of methoxyl groups from one to three in the phenolic portion of the flavonoid tended to decrease photodynamic activity. Tetrahymena killed photodynamically by polymethoxyflavones were morphologically altered by blister-like blebs. Polymethoxyflavones showed the lowest cytotoxicity and the greatest photodynamic activity among those flavonoids tested. The majority of the favonoids in this series have absorption spectra in the 320–370 nm region.     

INTERACTION OF DIBUCAINEHCl LOCAL ANESTHETICS WITH BACTERIORHODOPSIN IN PURPLE MEMBRANE: A SPECTROSCOPIC STUDY

Several spectroscopic techniques (absorption, emission, transient absorption and differential scanning calorimetry--DSC) were used to investigate the deprotonation of dibucaine.HCl in a hydrophobic environment, and the interaction sites and mechanisms of the local anesthetic dibucaine.HCl on bacteriorhodopsin (bR) in purple membrane. The important results are summarized as follows: (1) the visible absorption features of native (lambda max = 568 nm) and deionized (lambda max = 608 nm) bR are sensitive to the amount of dibucaine.HCl added; (2) the emission spectrum of dibucaine.HCl embedded in the retinal-free mutant bR is similar to that of dibucaine free base in Triton X-100 micellar solutions; (3) the phosphorescence emission of dibucaine at 77 K is completely quenched by bR and the fluorescence quenching rate for the incorporated dibucaine.HCl in bR was determined as kq = 4.09 x 10(13) M-1 s-1; (4) the incorporation of dibucaine.HCl in bR inhibits the slow component rate of formation of M412 and decreases the amount of M412 formation in the photochemical cycle of bR; and (5) the thermal stability of native bR was measured by DSC in the presence and absence of dibucaine and yielded an endothermic transition at 95.9 +/- 1.0 degrees C with 13.6 J/g (3.25 +/- 0.12 cal/g) of enthalpy changes. All observations suggest that the action site of the local anesthetic, dibucaine.HCl, is near or at the chromophore, i.e. the retinal Schiff base of bR. The anesthetic action on bR purple membrane is probably via a specific site binding, but not a conformational mechanism.     

HUMIC MACROMOLECULES IN NATURAL WATERS

Abstract

Humic substances are the major organic constituents of soils and sediments. They also occur in small concentrations in natural surface waters and groundwaters. They form through the breakdown of plant and animal tissues by chemical and biological processes that tend to produce complex chemical structures that are more stable than the original material from which they were derived. One of the more important characteristics of humic substances is their ability to form water-soluble and water-insoluble complexes with metal ions and hydrous oxides and to interact with clay minerals and various organic compounds such as alkanes, fatty acids, and toxic organic substances such as pesticides.