Construction of a new Hg(2+)-selective liquid-state electrode

The construction and basic characteristics of a new liquid-state Hg(2+)-selective membrane electrode are discussed. The membrane consists of the PAN chelate of Hg(II), dissolved in CHCl(3). The linear response range of the electrode is 10(-1) -10(-5)M Hg(2+) with a slope of 28.5 mV/decade of concentration. The response time of the electrode in dilute solutions is less than 3 min, and in concentrated solutions it is only a few sec. The electrode has been used in precipitation or complexation titrations in which Hg(2+) is involved (e.g., in the determination of some organic compounds in drug synthesis).     

Iterative computation of noncooperative equilibria in nonzero-sum differential games with weakly coupled players

We study the Nash equilibria of a class of two-person nonlinear, deterministic differential games where the players are weakly coupled through the state equation and their objective functionals. The weak coupling is characterized in terms of a small perturbation parameter . With =0, the problem decomposes into two independent standard optimal control problems, while for 0, even though it is possible to derive the necessary and sufficient conditions to be satisfied by a Nash equilibrium solution, it is not always possible to construct such a solution. In this paper, we develop an iterative scheme to obtain an approximate Nash solution when lies in a small interval around zero. Further, after requiring strong time consistency and/or robustness of the Nash equilibrium solution when at least one of the players uses dynamic information, we address the issues of existence and uniqueness of these solutions for the cases when both players use the same information, either closed loop or open loop, and when one player uses open-loop information and the other player uses closed-loop information. We also show that, even though the original problem is nonlinear, the higher (than zero) order terms in the Nash equilibria can be obtained as solutions to LQ optimal control problems or static quadratic optimization problems.This research was supported in part by the US Department of Energy under Grant DE-FG-02-88-ER-13939.Paper presented at the 29th IEEE Conference on Decision and Control, Honolulu, Hawaii, 1990.     

The Scaled Hermite–Weber Basis Still Highly Competitive

The effectiveness of the usual harmonic oscillator basis is demonstrated on a wide class of Schrödinger Hamiltonians with various spectral properties. More specifically, it is shown numerically that an appropriately scaled Hermite–Weber basis yields extremely accurate results not only for the energy eigenvalues which differ slighly from the harmonic oscillator levels, but also for the states which reflect a purely anharmonic character.     

Radical scavenging activity and antioxidant capacity of bay leaf extracts

Bay leaves (BL) (Laurus nobilis L., Family: Lauraceae) are traditionally used orally to treat the symptoms of gastrointestinal problems, such as epigastric bloating, impaired digestion, eructation, and flatulence. In this study, lyophilized extracts (both water and ethanol) of BL were studied for their antioxidant properties. The antioxidant activity, reducing power, free radical scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging and metal chelating activities were evaluated to determine the total antioxidant capacity of both BL extracts. Both extracts exhibited strong total antioxidant activity in linoleic acid emulsion. Concentrations of 20, 40, and 60 μg ml^?1 showed 84.9, 95.7, 96.8, and 94.2, 97.7, and 98.6% inhibition of lipid peroxidation of linoleic acid emulsion, for water and ethanol extracts, respectively. On the other hand, 60 μg ml^?1 of the standard antioxidants butylated hydroxyianisole (BHA), butylated hydroxytoluene (BHT), and α-tocopherol exhibited 96.6, 99.1, and 76.9% inhibition of lipid peroxidation in linoleic acid emulsion, respectively. In addition, the both BL extracts had effective reducing power, DPPH? free radical scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging and metal chelating activities at 20, 40, and 60 μg ml^?1. The total amount of phenolic compounds in each BL extract was determined as gallic acid equivalents.     

Prompt gamma neutron activation analysis of boron with a 241Am-Be neutron source

A prompt gamma neutron activation analysis (PGAA) setup installed at ANRTC has been used to analyze boron. It consists of a 22.6% REGe detector and a 740 GBq ²⁴¹Am-Be neutron source moderated with water and paraffin. At the sample irradiation position, the thermal neutron fluence rate measured was 2.36·10⁴ n·m^–2· s^–1 and the corresponding Cd-ratio was 22 for gold monitor. The absolute detection efficiency in the range of 120–1500 keV was determined using ¹⁵²Eu standard solution. The sensitivity and detection limit for standard boric acid samples has been determined. The boron content in boric acid prepared from Turkish borate ores is measured to be 15.91±0.46% wt.     

Facile Synthesis and Characterization of 5-[(3-Methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole and Its Potentiometric Sensor Application in a Polyvinyl Chloride Membrane for the Determination of Copper(II)

A novel Schiff base designated as 5-[(3-methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole was synthesized and characterized. A polyvinyl chloride-membrane potentiometric copper(II)-selective sensor was prepared by using the synthesized 5-[(3-methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole compound. The prepared polyvinyl chloride-membrane copper(II)-selective sensor exhibited very good selectivity and sensitive potentiometric response towards copper(II) ions compared to a wide variety of other cations. The sensor had a fast response time of <5?s, and showed a linear Nerstian behavior to copper(II) ions over a wide concentration range from 1.0?×?10^?5 to 1.0?×?10^?1 mol L^?1 with a slope of 29.2?±?0.7 and correlation coefficient of 0.9998. The prepared polyvinyl chloride-membrane copper(II)-selective sensor was used for 14 weeks without any significant change in its potentiometric response. The potentiometric response of the developed sensor was highly repeatable. Additionally, the developed sensor was used as an indicator electrode for the potentiometric titration of copper(II) ion with ethylenediaminetetraacetic acid. The sensor was also successfully applied to the direct determination of copper(II) ions in tap water, river water, and dam water samples.     

Kinetic of decomposition of some complexes under non-isothermal conditions

Kinetics of thermal decomposition of three structurally similar complexes Co₂Cu(C₂O₄)₃ (R-diam)₂, where R is ethyl, 1,2-propyl or 1,3-propyl, was studied under non-isothermal conditions and nitrogen dynamic atmosphere at heating rates of 5, 7, 10, 12 and 15 K min⁻¹. For data processing the Flynn-Wall-Ozawa and a modified non-parametric kinetic methods were used. By both methods the activation energy are in the range of 97–102 kJ mol⁻¹. The formal kinetic is r=kα(1−α)². Also a compensation effect between lnA and E was evidenced. The kinetic analysis lead to the conclusion of an identic decomposition mechanism by a single step process.     

High-performance liquid chromatographic separation of polyolefin antioxidants and light-stabilisers

Summary A scheme was devised for the identification of 22 common antioxidants and light-stabilisers in polyolefins. The separation of these stabilisers was performed by isocratic reversed phase high-performance liquid chromatography on a RP-18 column. Three different separation conditions have been used: the mobile phase composition was 100% acetonitrile (MeCN), 90/10 meCN/H₂O and 80/20 MeCN/H₂O. The UV₂₅₄/UV₂₈₀ ratio and the elution time of each stabiliser were determined for these three mobile phase compositions. The values of UV₂₅₄/UV₂₈₀ ratios may be used together with the retention time values for the identification of unknown stabilisers in polyolefin samples.     

The burial of solvent-accessible surface area is a predictor of polypeptide folding and misfolding as a function of chain elongation

The hydrophobic effect is a major driving force in all chemical and biological events involving chain collapse in aqueous solution. Here, we show that the burial of nonpolar solvent-accessible surface area (NSASA) is a powerful criterion to predict the folding and misfolding behavior of small single-domain proteins as a function of chain elongation. This bears fundamental implications for co- and post-translational protein folding in the cell and for understanding the interplay between noncovalent interactions and formation of native-like structure and topology. Comparison between the fraction of NSASA in fully unfolded and folded elongating chains shows that efficient burial of nonpolar surface area is preferentially achieved only when the polypeptide chain is almost complete. This effect has no preferential vectorial character in that it is present upon elongation from both the N and C termini. For incomplete chains that do not have the ability to fold and bury nonpolar surface intramolecularly, the overall hydrophobic nature of the polypeptide chain (expressed as FBA, i.e., fractional buried surface area per residue) dictates the tendency toward misfolding and self-association. N-terminal chains characterized by FBA exceeding 0.73 are likely to misfold and aggregate, if unable to fold intramolecularly.     

Synthesis of chiral crown ethers and complexation with chiral protonated amine compounds: X-ray crystal and nuclear magnetic resonance studies of perchlorate salt of chiral benzo-monoaza-15-crown-5 and chiral monoaza-15-crown-5

The X-ray crystal structure of IX, perchlorate salt of R-(?-2-ethyl-N-benzyl-4,7,19,13-tetraoxa-8,9-benzo-1-azacyclopentadec-8-ene has been determined. In the molecule, the protonated nitrogen atom participates in two N-H?O hydrogen bonds. The unusually high proton affinity of aza crown ether leads to the formation of diastreomer instead of complex formation with chiral R-(+)-1-phenyl ethyl ammonium perchlorate and S-(?)-1-phenyl ethyl ammonium perchlorate. The complex ability of host ethers was evaluated in terms of structural modification.