Notes on the Lightlike Hypersurfaces Along Spacelike Submanifolds

Ukrainian Mathematical Journal - In connection with the method of construction of lightlike hypersurfaces along spacelike submanifolds, we present a relation between the second fundamental form of...     

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.     

A monostyryl-boradiazaindacene (BODIPY) derivative as colorimetric and fluorescent probe for cyanide ions

We developed a novel boradiazaindacene derivative to detect cyanide ions in solution at micromolar concentrations. This structurally simple chemosensor displays a large decrease in emission intensity and a reversible color change from red to blue on contact with cyanide ions. Highly fluorescent polymeric films can be obtained by doping with the chemosensor. Such polymeric materials can be used for the sensing of the cyanide ions in polymer matrices.     

The phase diagram of simple metamagnets as determined by the cluster variation method

In order to explore the global properties of a simple Ising metamagnet we computed the values of the coupling parameters for which the tricritical behavior is replaced by bicritical endpoints (Lifshitz point). The transition points are determined by means of the cluster variation method. The metamagnets studied have an antiferromagnetic coupling between the spins on two chosen sublattices and a ferromagnetic coupling between spins on the same sublattice. The following lattices and sublatices were considered: two-dimensional square, simple cubic and two different subdivisions of the fcc and bcc lattices each. The method used is based on the coincidence of two roots for the bicritical endpoints and of three roots for the tricritical point. In contrast to the molecular field and the pair approximation results, the presence or absence of the Lifshitz point depends on the lattice structure considered. We discuss the comparison of our results with the results from the renormalization theories.     

Preparation and application of a new glucose sensor based on iodide ion selective electrode

An electrode for glucose has been prepared by using an iodide selective electrode with the glucose oxidase enzyme. The iodide selective electrode used was prepared from 10% TDMAI and PVC according our previous study. The enzyme was immobilized on the iodide electrode by holding it at pH 7 phosphate buffer for 10 min at room temperature. The H₂O₂ formed from the reaction of glucose was determined from the decrease of iodide concentration that was present in the reaction cell. The iodide concentration was followed from the change of potential of iodide selective electrode. The potential change was linear in the 4×10⁻⁴ to 4×10⁻³ M glucose concentration (75-650 mg glucose/100ml blood) range. The slope of the linear portion was about 79 mV per decade change in glucose concentration. Glucose contents of some blood samples were determined with the new electrode and consistency was obtained with a colorimetric method. The effects of pH, iodide concentration, the amount of enzyme immobilized and the operating temperature were studied. No interference of ascorbic acid, uric acid, iron(III) and Cu(II) was observed. Since the iodide electrode used was not an AgI-Ag₂S electrode, there was no interference of common ions such as chloride present in biological fluids. The slope of the electrode did not change for about 65 days when used 3 times a day.     

Self-sustained oscillations of shear flow past a slotted plate coupled with cavity resonance

Shear flow past a slotted plate configuration can give rise to highly coherent, self-sustained oscillations when coupling occurs with a resonant mode of an adjacent cavity. The distinctive feature of these oscillations is that the wavelength of the coherent instability along the plate is of the order of the plate length. This observation is in contrast to previous investigations of flow past perforated or slotted surfaces, where the instability scales on the diameter of the perforation or the gap length of a slot. The present oscillations occur even when the inflow boundary layer is turbulent and an inflectional form of the shear flow cannot develop along the cavity opening, due to the presence of the slotted plate. Instigation of a resonant mode of the cavity, in conjunction with an inherent instability of the shear flow along the plate, gives rise to ordered clusters of instantaneous vorticity and instantaneous velocity correlation. During the oscillation, ejection of flow occurs from the cavity to the region of the shear flow; this ejection is in accord with the convection of the large-scale cluster of vorticity along the slotted plate. This oscillation can be effectively detuned by adjusting the inflow velocity, such that the inherent instability of the shear flow past the slotted plate is no longer coincident with the resonant frequency of the cavity. Certain features of this self-sustained oscillation are directly analogous to recent findings of oscillations due to shear flow past a perforated plate bounded by a cavity, but in the absence of cavity resonance effects.     

Control of flow past a circular cylinder via a spanwise surface wire: effect of the wire scale

Flow phenomena induced by a single spanwise wire on the surface of a circular cylinder are investigated via a cinema technique of particle image velocimetry (PIV). The primary aim of this investigation is to assess the effect of the wire scale. To this end, consideration is given to wires with different diameters that are 0.5, 1.2, and 2.9% of the cylinder diameter. The Reynolds number has a subcritical value of 10,000. Compared to the thickness of the unperturbed boundary layer developing around the cylinder between 5° and 75° from the forward stagnation point, the former two wires have smaller scales and the latter has a larger scale. Two angular locations of the wire, defined with respect to the forward stagnation point of the cylinder, are found to be critical. When the wire is located at these critical angles, either the most significant extension or the contraction of the time-mean separation bubble occurs in the near wake. These critical angles depend on the wire scale: the smaller the wire, the larger the critical angle. The small-scale and large-scale wires that have diameters of 1.2 and 2.9% of the cylinder diameter induce bistable shear-layer oscillations between different separation modes when placed at their respective critical angles corresponding to maximum extension of the near-wake bubble. These oscillations have irregular time intervals that are much longer than the time scale associated with the classical Kármán instability. Moreover, the large-scale wire can either significantly attenuate or intensify the Kármán mode of vortex shedding at the critical states; in contrast, the small-scale wires do not notably alter the strength of the Kármán instability.     

Probing the protein–nanoparticle interface: the role of aromatic substitution pattern on affinity

A new class of cationic gold nanoparticles (NPs) has been synthesised bearing benzyl moieties featuring –NO₂ and –OMe groups to investigate the regioisomeric control of aromatic NP–protein recognition. In general, NPs bearing electron-withdrawing groups demonstrated higher binding affinities towards green fluorescent protein (GFP) than NPs bearing electron-donating groups. Significantly, a ～7.5- and ～4.3-fold increase in binding with GFP was observed for –NO₂ groups in meta-position and para-position, respectively, while ortho-substitution showed binding similar to the unsubstituted ring. These findings demonstrated that the NP–protein interaction can be controlled by tuning the spatial orientation and the relative electronic properties of the aromatic substituents. This improved biomolecular recognition provides opportunities for enhanced biosensing and functional protein delivery to the cells.     

Water soluble distyryl-boradiazaindacenes as efficient photosensitizers for photodynamic therapy

We introduce a novel class of water soluble, extended conjugation boradiazaindacene dyes which are efficient singlet oxygen generators and have spectacular photoinduced cytotoxicity when excited in the "therapeutic window" of the electromagnetic spectrum.