Electrochemical recognition of synthetic heparin mimetic at liquid/liquid microinterfaces

Electrochemically controlled molecular recognition of a synthetic heparin mimetic, Arixtra, at nitrobenzene/water microinterfaces was investigated to obtain a greater understanding of interfacial recognition and sensing of heparin and its analogues with biomedical importance. In contrast to unfractionated heparin, this synthetic pentasaccharide that mimics the unique Antithrombin III binding domain of heparin possesses well-defined structure and ionic charge to enable quantitative interpretation of cyclic voltammetric/chronoamperometric responses based on the interfacial recognition at micropipet electrodes. Arixtra is electrochemically extracted from the water phase into the bulk nitrobenzene phase containing highly lipophilic ionophores, methyltridodecylammonium or dimethyldioctadecylammonium. Numerical analysis of the kinetically controlled cyclic voltammograms demonstrates for the first time that formal potentials and standard rate constants of polyion transfer at liquid/liquid interfaces are ionophore dependent. Moreover, octadecylammonium and octadecylguanidinium are introduced as new, simple ionophores to model recognition sites of heparin-binding proteins at liquid/liquid interfaces. In comparison to octadecyltrimethylammonium, the best ionophore for heparin recognition at liquid/liquid interfaces reported so far, these new ionophores dramatically facilitate Arixtra adsorption at the interfaces. With a saline solution at physiological pH, an Arixtra molecule is selectively and cooperatively bound to 5 molecules of the guanidinium ionophore, suggesting hydrogen-bond-directed interactions of each guanidinium with a few of 10 negatively charged sulfo or carboxyl groups of Arixtra at the interfaces.     

Influence of the angle of attack on the transition from a laminar to a turbulent boundary layer in the case of supersonic flow past sharp circular cones

Some results are given of an experimental investigation into the influence of the angle of attack on the transition in the symmetry plane of a sharp cone at Mach number M = 6.1. These results and available experimental data are used to establish the dependence of the transition Reynolds number on the angle of attack on the flow division line of sharp circular cones.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 160–163, July–August, 1982.     

Results of an experimental and numerical study of the aerodynamic heating of the undersurface of delta wings with sharp leading edges at mach numbers M∞=6.1 and 8

The heat transfer between a supersonic flow and the undersurface of delta wings with leading-edge sweep angles x=65 and 70° is investigated in a shock tunnel at angles of attack 15°. The supersonic inviscid flow over these wings in regimes in which the bow shock is attached to the sharp leading edges is calculated numerically. The compressible boundary layer problem is solved for the calculated inviscid flow fields in the laminar, transition and turbulent flow zones. The calculations and experimental values of the heat flux on the surface of the wings are compared. The calculations are in satisfactory agreement with the experimental data in the laminar and transition zones, but diverge significantly (by up to 20%) in the turbulent zone.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 183–188, July–August, 1991.The authors wish to thank A. A. Golubinskii for assisting with the solution of the problem of supersonic inviscid gas flow over a wing.     

Electrochemical heparin sensing at liquid/liquid interfaces and polymeric membranes

The monitoring of heparin and its derivatives in blood samples is important for the safe usage of these anticoagulants and antithrombotics in many medical procedures. Such an analytical task is, however, highly challenging due to their low therapeutic levels in the complex blood matrix, and it still relies on classical, indirect, clot-based assays. Here we review recent progress in the direct electrochemical sensing of heparin and its analogs at liquid/liquid interfaces and polymeric membranes. This progress has been made by utilizing the principle of electrochemical ion transfer at the interface between two immiscible electrolyte solutions (ITIES) to voltammetrically drive the interfacial transfer of polyanionic heparin and monitoring the resulting ionic current as a direct measure of heparin concentration. The sensitivity, selectivity, and reproducibility of the ion-transfer voltammetry of heparin are dramatically enhanced compared to those of traditional potentiometry. This voltammetric principle was successfully applied for the detection of heparin in undiluted blood samples, and was used to develop highly sensitive ion-selective electrodes based on thin polymeric membranes that are intended for analytical applications beyond heparin detection. The mechanism of heparin recognition and transfer at liquid/liquid interfaces was assessed quantitatively via sophisticated micropipet techniques, which aided the development of a powerful ionophore that can extract large heparin molecules into nonpolar organic media. Moreover, the reversible potentiometric detection of a lethal heparin-like contaminant in commercial heparin preparations was achieved through the use of a PVC membrane doped with methyltridodecylammonium chloride, which enables charge density dependent polyanion selectivity.     

Synergism of hydrogenating capacity in the Ni-Pd/Al2O3 system

In liquid-phase hydrogenation of ethyl acetoacetate on bimetallic Ni-Pd catalysts supported on Al₂O₃, the reaction rate increases sharply and passes through a maximum with an increase in the concentration of Pd. The change in the rate of hydrogenation with a change in the composition of the catalysts is not due to a change in the dispersion of the metallic phase in them or enrichment of their surface with one of the metals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 11–13, January, 1990.     

Enhanced dispersion of CdSe/MEH-CN-PPV hybrid nanocomposites by in situ polymerization using AEM as photopolymerizable precursor

Colloidal quantum dots (CQDs) can easily become aggregated when blended in a polymer matrix. Although several techniques have been reported to prepare dispersed CQDs in a polymer matrix, the novel approach of this work is to obtain well-dispersed CQD–polymer nanocomposites through the in situ photopolymerization of a third source, thereby broadening the material selection available for such nanocomposites. Therefore, dispersed CQD–polymer nanocomposites were prepared by the photopolymerization of 2-aminoethyl methacrylate hydrochloride (AEM) precursor in a blend of trioctyl phosphine oxide-capped CdSe CQDs and poly(2-methoxy-5-(2′-ethylhexyloxy)-α,α′dicyano-p-xylylidene-alt-2,5-dihexyoxy-p-xylylidene) (MEH-CN-PPV). The photopolymerization of AEM was developed for this work in order to prevent possible decomposition of CQDs induced by introducing metallic catalysts or heat and to eliminate the need for further functionalization of CQDs or polymers. The morphology of the photopolymerized CdSe CQD/MEH-CN-PPV/AEM was corroborated by direct observation of the quantum dot dispersion in the resultant sphere-shaped structures via transmission electron microscopy. Photoluminescence quenching and shorter photoluminescence decay lifetime of the MEH-CN-PPV in the photopolymerized nanocomposite were observed, indicating that the photopolymerized CdSe CQD/MEH-CN-PPV/AEM nanocomposite has an enhanced energy transfer efficiency in comparison to typical aggregated CdSe quantum dot/MEH-CN-PPV nanocomposites as a result of better dispersion.