Competitive Complexation by Ligand and Solvent: Polarographic Characterization of ATRP Catalyst Polyamine–Copper Complexes in Acetonitrile + Water Mixed Solvents

In the Atom Transfer Radical Polymerization (ATRP) technique, the suggested polymerization scheme is pivoted by a metal complex acting as a redox catalyst able to coordinate with the incipient radicals. The development of an a priori criterion of choice of the best (complex + solvent) combination is one of the current topics in this field. In this context we performed polarographic investigations on copper complexes with multidentate amino ligands (TMEDA and Me₆TREN, plus acetonitrile as a reference) in water and in water + acetonitrile mixed solvents. In the latter case we took into account the competition between the co-solvent acetonitrile [a weaker ligand, but concentrated, selectively stabilizing Cu(I)], and the polyamine [a stronger ligand, but diluted, preferentially stabilizing Cu(II)], achieving further stabilization of the complexed copper, with a narrow potential range of stability as Cu(I), which is modulated through the acetonitrile/polyamine ratio. An interpretative scheme is presented.     

Detection of prion protein using a capillary electrophoresis-based competitive immunoassay with laser-induced fluorescence detection and cyclodextrin-aided separation

The development of capillary electrophoresis (CE)-based competitive immunoassay for prion protein (PrP) using carboxymethyl beta-cyclodextrin (CM-beta-CD) as a buffer additive is described here. The assay was based on the competitive binding of PrP and a fluorescein-labeled peptide from the prion protein with a limiting amount of specific antibody. The amount of both free and fluorescein-labeled peptide bound to antibody (immunocomplex) were determined by CE with laser-induced fluorescence detection. In the presence of PrP, the peak height ratio of the immunocomplex and the free peptide was altered compared to the control. These changes were directly proportional to the amount of PrP present. The fluorescently labeled peptide spanning amino acid positions 140-158 of the PrP and its corresponding monoclonal antibody is reported here. The reaction times of the antibody with either the peptide or the recombinant PrP was less than 1 min and is a large improvement over the 16-18 h required to achieve equilibrium for polyclonal antibodies. CM-beta-CD was explored as a buffer additive to suppress analyte adsorption and enhance separation selectivity in the CE analysis. A fast (1.1 min), selective (resolution 4.7), and reproducible (relative standard deviations of migration time for free and bound fluorescein isothiocyanate (FITC)-peptide 0.56% and 0.64%, respectively) separation was obtained with 0.6% CM-beta-CD in 25 mM N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid (TAPS) at pH 8.8. The concentration detection limit of the assay for recombinant PrP was determined to be 80 ng/mL (or mass detection limit 1 pg). When blood samples from scrapie-infected sheep and from normal sheep were tested, the results of the blood assay were consistent with scrapie status of the sheep as determined post mortem by Western blot analysis. Development of this assay will lead to a potentially robust, rapid, and specific preclinical diagnosis for transmissible spongiform encephalopathies (TSEs) in animals and humans.     

Capillary gas chromatography based on a capsule-insertion technique. 1. General aspects and comparison with split-injection systems

A capsule-insertion system tailored to the needs of capillary gas chromatography is described. It provides the basis for a truly quantitative and improved qualitative approach to open tubular capillary GLC. The advantages of the system lie in its simplicity of handling and in the possibility of using relatively low injection temperatures, thus reducing the risks to thermally unstable samples. The observed high efficiencies characterizing this capillary GLC capsule technique allow full advantage to be taken of the operating capacity of the superior capillary columns to give a performance competitive with the best known split-injection systems.     

Substituent effects on the amination of racemic allyl carbonates using commercially available chiral rhodium catalysts

In the presence of commercially available chiral rhodium catalysts, a competitive benzylamination of racemic allyl carbonates, substituted with p-X-Ph groups, shows that the reaction proceeds faster with substituents (X) that are more electron-withdrawing. Mechanistic implications of these results are discussed.     

A note on “Location of hubs in a competitive environment”

This note suggests modifications to two models for locating hubs in a competitive environment introduced by Marianov et al. [European Journal of Operational Research 114 (1999) 363–371]. They make it possible to provide optimal solutions much faster. It is also shown that the implementation of the heuristic proposed by Marianov et al. contains a flaw. Yet the heuristic itself is correct.     

Some minimal bimolecular mass-action systems with limit cycles

We discuss three examples of bimolecular mass-action systems with three species, due to Feinberg, Berner, Heinrich, and Wilhelm. Each system has a unique positive equilibrium which is unstable for certain rate constants and then exhibits stable limit cycles, but no chaotic behaviour. For some rate constants in the Feinberg–Berner system, a stable equilibrium, an unstabe limit cycle, and a stable limit cycle coexist. All three networks are minimal in some sense.By way of homogenising these three examples, we construct bimolecular mass-conserving mass-action systems with four species that admit a stable limit cycle. The homogenised Feinberg–Berner system and the homogenised Wilhelm–Heinrich system admit the coexistence of a stable equilibrium, an unstable limit cycle, and a stable limit cycle.     

Competitive exclusion in a nonlocal reaction–diffusion–advection model of phytoplankton populations

We continue our study on the global dynamics of a nonlocal reaction–diffusion–advection system modeling the population dynamics of two competing phytoplankton species in a eutrophic environment, where both populations depend solely on light for their metabolism. In our previous work, we proved that system (1.1) is a strongly monotone dynamical system with respect to a non-standard cone related to the cumulative distribution functions, and further determined the global dynamics when the species have either identical diffusion rate or identical advection rate. In this paper, we study the trade-off of diffusion and advection and their joint influence on the outcome of competition. Two critical curves for the local stability of two semi-trivial equilibria are analyzed, and some new competitive exclusion results are obtained. Our main tools, besides the theory of monotone dynamical system, include some new monotonicity results for the principal eigenvalues of elliptic operators in one-dimensional domains.     

在线计算中的几个未解问题(英文)

讨论组合优化中的一个迅速发展的领域──在线计算，选出几个典型的未解问题进行方法介绍．     

Sequence Specific Electrochemical DNA Detection Based on Solution‐Phase Competitive Hybridization

We report a novel electrochemical method for detecting sequence‐specific DNA based on competitive hybridization that occurs in a homogeneous solution phase instead of on a solution‐electrode interface as in previously reported competition‐based electrochemical DNA detection schemes. The method utilizes the competition between the target DNA (t‐DNA) and a ferrocene‐labeled peptide nucleic acid probe (Fc‐PNA) to hybridize with a probe DNA (p‐DNA) in solution. The neutral PNA backbone and the electrostatic repulsion between the negatively‐charged DNA backbone and the negatively‐charged electrode surface are then exploited to determine the result of the competition through measurement of the electrochemical signal of Fc. Upon the introduction of the t‐DNA, the stronger hybridization affinity between the t‐DNA and p‐DNA releases the Fc‐PNA from the Fc‐PNA/p‐DNA hybrid, allowing it to freely diffuse to the negatively charged electrode to produce a significantly enhanced electrochemical signal of Fc. Therefore, the presence of the t‐DNA is indicated by the appearance or enhancement of the electrochemical signal, rendering a signal‐on DNA detection, which is less susceptible to false positive and can produce more reliable results than signal‐off detection methods. All the competitive hybridizations occur in a homogeneous solution phase, resulting in very high hybridization efficiency and therefore extremely short assay time. This simple and fast signal‐on solution‐competition‐based electrochemical DNA detection strategy has promising potential to find application in fields such as nucleic acid‐based point‐of‐care testing.     

Competitive Transfer Hydrogenation of Unsaturated Alcohol-Alkene-Diene Systems

The paper describes hydrogenation of unsaturated alcohols, alkenes and dienes in individual and binary systems of substrates by use of catalytic hydrogen transfer from ammonium formate in methanol on a palladium catalyst. A significant structural effect of hydrogenated alcohols upon their reactivity and adsorptivity was observed. Following comparison to the data acquired from typical hydrogenation by use of molecular hydrogen, it was inferred that the components of the CTH system increase the selectivity of competitive transfer hydrogenation to a significant extent in systems of unsaturated alcohol — unsaturated hydrocarbon with regard to the relative increase of reactivity of unsaturated alcohols. This occurs primarily due to affecting the relative adsorptivity.