Cinchonidine adsorption on gold and gold-containing bimetallic platinum metal surfaces: an attenuated total reflection infrared and density functional theory study

Adsorption of cinchonidine on monometallic Au and bimetallic Pt-Au and Pd-Au thin model films prepared by physical vapor deposition has been investigated with attenuated total reflection infrared (ATR-IR) spectroscopy. On Au the alkaloid forms an adsorbed layer that shows higher stability against desorption than the corresponding adsorption on Pt. In this adsorption layer the intermolecular interactions dominate over metal-adsorbate interactions as indicated by the absence of the spectroscopic features attributed to strongly flat adsorbed species. This behavior is further supported by Density Functional Theory (DFT) calculations indicating that flat and tilted orientations of the quinoline ring have comparable adsorption energy on Au but lower (7-10 kcal/mol) compared to adsorption on Pt (ca. 40 kcal/mol). As a consequence, the creation of a metal surface with isolated chiral sites is prevented by formation of an adsorbed structure formed by intermolecularly bound cinchonidine molecules on Au. While the binding to Pt is due to the formation of sigma-bonds to surface atoms, such aggregates are bound to Au mainly by van der Waals forces. Given this different nature of bonding of cinchonidine to Au and Pt, addition of Au to Pt and Pd films could be used to probe the changes of fractional coverage of the different adsorbed species of cinchonidine on the platinum metals. It is demonstrated that the lowering of the domain size of the platinum group metal by Au can simulate the effect of particle size on the distribution of the surface conformations of the alkaloid on a metal surface.     

Electroreduction of aromatic oximes: diprotonation, adsorption, imine formation, and substituent effects

Aromatic oximes are reduced in aqueous solution in a four-electron process. The reducible species in the pH range 5-8 is a diprotonated form of the oxime. This species is generated in the course of electrolysis in the vicinity of the electrode surface from the adsorbed neutral form of the oxime. The reduction is initiated by a cleavage of the N-O bond. The diprotonation facilitates the reduction process by the preformation of OH2+ as a good leaving group and by a positive charge on the azomethine nitrogen. Diprotonation has been proven based on shapes of i = f(pH) plots, by observed shifts of half-wave potentials with pH and by comparison with the reduction of nitrones. Some observed deviations from theoretical i = f(pH) plots were attributed to the role of adsorption on the rate of protonation. Adsorption is also responsible for dips on some of the i-E curves. Adsorption plays a role at concentrations as low as 1 x 10(-5) M, when the electrode surface is still not fully covered. This indicates that catalyzed protonation occurs on islets of adsorbed materials. At pH 2-5 the studied oximes in the vicinity of the electrode are predominately present in a protonated form, which is less strongly adsorbed. In this pH range the protonation takes place in a homogeneous reaction layer of the electrode. It yields a monoprotonated form, which is reduced. The separation of two two-electron waves observed for some oximes in acidic media serves as an experimental proof of the formation of imines as reduction intermediates. This separation is caused by the differences in pKa values of protonated forms of oximes and imines. The effects of substituents in the para position on the benzene ring are characterized by correlation with the Hammett substituent constant sigmax. This has been proven at pH 1.5 for substituted benzaldehyde oximes and at pH 5.0 for substituted acetophenone oximes.     

Chiral recognition in surface explosion

The vast majority of chiral compounds crystallize into racemic crystals. It has been predicted and was experimentally established as a rule that chiral molecules on surfaces are more easily separated into homochiral domains due to confinement into a plane and lower entropic contributions. We investigated the formation and stability of two-dimensional tartrate crystals on a Cu(110) surface for the racemic mixture for the first time by means of temperature-programmed desorption (TPD), low-energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). At low coverage, a bitartrate species becomes separated into homochiral domains, while at high coverage a monotartrate species forms a racemic mixture. At the same coverage and lateral arrangement, the thermally induced autocatalytic decomposition reaction occurs for the monotartrate racemate at a lower temperature than for the pure enantiomers. The stereochemistry in this so-called "surface explosion" reaction is explained by a higher stability of the enantiopure lattice due to lateral hydrogen-bond formation. The higher stability of the enantiopure two-dimensional lattice is in contrast to the higher stability of racemic three-dimensional tartaric acid crystals but is consistent with the observation that homochirality is preferred in hydrogen-bonded self-assembled biomolecular structures.     

Hydrogen atom abstraction reactions of charged polyaromatic sigma-radicals related to the active intermediates of the enediyne antitumor drugs

Polar effects are demonstrated to play an important role in controlling the reactivity of polyaromatic sigma-radicals that are structurally related to the active intermediates of the enediyne anticancer type antibiotics. This was accomplished by measuring the rate constants of hydrogen atom abstraction for novel, charged dehydroquinolines, dehydroisoquinolines, dehydrobenzenes, and dehydronaphthalenes in the gas phase by using Fourier-transform ion cyclotron resonance mass spectrometry. The reactivity trends observed for these radicals upon hydrogen atom abstraction from tetrahydrofuran and 2-methyltetrahydrofuran, simple models of deoxyribose, do not reflect differences in reaction exothermicities, radical sizes, exact location of the radical site in the ring system, or heteroatom-radical site distances. However, the reactivity trends match the trend in the calculated electron affinities of the radicals. The radicals' different electrophilicities result in variations in the reaction barrier due to different extents of polarization of the transition state. Generally, the reaction efficiencies are the greatest when the formally charged heteroatom is contained within the same ring system as the radical site. In this case, polar effects have the greatest influence on radical reactivity. Hence, insertion of a basic heteroatom (which gets protonated in biological systems) into specific locations in the polyaromatic ring system of the sigma-biradicals, which ultimately cause cleavage of DNA exposed to the enediyne antitumor drugs, should allow tuning of the reactivity of these radicals.     

Kinetic‐Spectrophotometric Determination of Metronidazole Benzoate in Surfactant Medium

A kinetic method for the accurate and sensitive determination of metronidazole benzoate (MB) has been described. The method is based on the oxidation of MB with KMnO₄ in alkaline medium in the presence of sodium dodecyl sulphate (SDS). At a fixed time of 10 min, the formed magnate ion is spectrophotometrically measured at 610 nm. The determination of MB by the fixed‐concentration and rate constant method is feasible with the calibration equation obtained, but the fixed‐time method proves to be more applicable. The proposed method was successfully used for the quantitative determination of MB in suspended oral syrup after the separation of MB with a simple separation method. Beer's law was obeyed from 0.55 mgL^?1 to 33 mgL^?1 and the RSD% value for syrup was 3.44. The results obtained agreed with those obtained by the BP method.     

Double frictional receding contact problem for an orthotropic layer loaded by normal and tangential forces

With the increasing research in the field of contact mechanics, different types of contact models have been investigated by many researchers by employing various complex material models. To ascertain the orthotropy effect and modeling parameters on a receding contact model, the double frictional receding contact problem for an orthotropic bilayer loaded by a cylindrical punch is taken into account in this study. Assuming plane strain sliding conditions, the governing equations are found analytically using Fourier integral transformation technique. Then, the resulting singular integral equations are solved numerically using an iterative method. The weight function describing the asymptotic behavior of the stresses are investigated in detail and powers of the stress singularities are provided. To control the trustworthiness and correctness of the analytical formulation and to compare the resulting stress distributions and contact boundaries, a numerically efficient finite element method was employed using augmented Lagrange contact algorithm. The aim of this paper is to investigate the orthotropy effect, modeling parameters and coefficients of friction on the surface and interface stresses, surface and interface contact boundaries, powers of stress singularities, weight function and to provide highly parametric benchmark results for tribological community in designing wear resistant systems.

     

Design and operation of an evanescent optical fiber sensor

Design and operation of an optical fiber sensor based on the intensity modulation is reported in this article. Two distinct mechanisms are considered for the optical power loss and the sensor operation is explained in terms of these effects. The dominant loss mechanism is found to be the evanescent loss and based on this phenomenon the optical fiber sensor is designed. Performance of this sensor is tested as a liquid level sensor for water and the experimental results are reported. The dry and wet signals for this probe are measured for a series of measurements and important factors concerning the design and operation of sensor are described. The precision of measured values, reproducibility of the results, and the stability of sensing operation as a function of time are reported. Variation of the output reading of the sensor system for different launching power is also investigated. The output signal of an optical fiber sensor in general is nonlinear, but both the signal difference (dry minus wet) and diff/dry signal ratio for the reported sensor show linear dependence with the launching power at intensities below threshold. The reported results are promising and verify the successful operation of such a device as an on/off level switch and also as a liquid level sensor.     

Investigation of the Diels-Alder cycloadditions of 2(H)-1,4-oxazin-2-ones

[Reaction: see text]. A variety of 5-chloro-2(H)-1,4-oxazin-2-ones bearing a range of substituents at their 3- and 6-positions undergo Diels-Alder cycloaddition as a 2-azadiene component with electron-rich, electron-deficient, and electron-neutral dienophiles. These reactions proceed with moderate regio- and stereoselectivity to afford relatively stable and readily isolable bridged bicyclic lactone cycloadducts. Chemical manipulation of these cycloadducts affords highly substituted and functionally rich piperidines. The regio- and stereochemical preferences of the cycloadditions of 5-chloro-2(H)-1,4-oxazin-2-ones are investigated computationally using density functional theory (B3LYP/6-31G).     

On decompositions of continuity and some weaker forms of continuity via idealization

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Precise measurement of B meson lifetimes with hadronic decay final states

The lifetimes of the B(0) and B- mesons are extracted from 29.1 fb(-1) of data collected with the Belle detector at the KEK B factory. A fit to the decay length differences of neutral and charged B meson pairs, measured in events where one of the B mesons is fully reconstructed in several hadronic modes, yields tau(B(0)) = 1.554+/-0.030(stat)+/-0.019(syst) ps, tau(B-) = 1.695+/-0.026(stat)+/-0.015(syst) ps, and tau(B-)/tau(B(0)) = 1.091+/-0.023(stat)+/-0.014(syst).