A mathematical model of the response of the semicircular canal and otolith to vestibular system rotation under gravity

A mathematical model of the system composed of two sensors, the semicircular canal and the sacculus, is suggested. The model is described by three lines of blocks, each line of which has the following structure: a biomechanical block, a mechanoelectrical transduction mechanism, and a block describing the hair cell ionic currents and membrane potential dynamics. The response of this system to various stimuli (head rotation under gravity and falling) is investigated. Identification of the model parameters was done with the experimental data obtained for the axolotl (Ambystoma tigrinum) at the Institute of Physiology, Autonomous University of Puebla, Mexico. Comparative analysis of the semicircular canal and sacculus membrane potentials is presented. __________ Translated from Fundamentalnaya i Prikladnaya Matematika, Vol. 11, No. 7, pp. 207–220, 2005.     

Structural and mechanistic look at the orthoplatination of aryl oximes by dichlorobis(sulfoxide or sulfide)platinum(II) complexes

Structural and mechanistic aspects of orthoplatination of acetophenone and benzaldehyde oximes by the platinum(II) sulfoxide and sulfide complexes [PtCl(2)L(2)] (2, L = SOMe(2) (a), rac-SOMePh (b), R-SOMe(C(6)H(4)Me-4) (c), and SMe(2) (d)) to afford the corresponding platinacycles cis-(C,S)-[Pt(II)(C(6)H(3)-2-CR'=NOH-5-R)Cl(L)] (3, R, R' = H, Me) have been investigated. The reaction of acetophenone oxime with sulfoxide complex 2a in methanol solvent occurs noticeably faster than with sulfide complex 2d due to the fact that the sulfoxide is a much better platinum(II) leaving ligand than the sulfide. Evidence is presented that the orthoplatination is a multistep process. The formation of unreactive dichlorobis(N-oxime)platinum(II) cations accounts for the rate retardation by excess acetophenone oxime and suggests the importance of pseudocoordinatively unsaturated species for the C-H bond activation by Pt(II). A comparative X-ray structural study of dimethyl sulfoxide platinacycle 3b (R = R' = Me) and its sulfide analogue 3e (R = H, R' = Me), as well as of SOMePh complex 3c (R = H, R' = Me), indicated that they are structurally similar and a sulfur ligand is coordinated in the cis position with respect to the sigma-bound phenyl carbon. The differences concern the Pt-S bond distance, which is notably longer in the sulfide complex 3e (2.2677(11) A) as compared to that in sulfoxide complexes 3b (2.201(2)-2.215(2) A) and 3c (2.2196(12) A). Whereas the metal plane is practically a plane of symmetry in 3b due to the H-bonding between the sulfoxide oxygen and the proton at carbon ortho to the Pt-C bond, an S-bonded methyl of SOMePh and SMe(2) is basically in the platinum(II) plane in complexes 3c and 3e, respectively. There are intra- and intermolecular hydrogen bond networks in complex 3b. An interesting structural feature of complex 3c is that the two independent molecules in the asymmetric unit of the crystal reveal an extremely short Pt-Pt contact of 3.337 A.     

Eutectic phase polymerization of activated ribonucleotide mixtures yields quasi-equimolar incorporation of purine and pyrimidine nucleobases

The RNA world hypothesis requires a plausible mechanism by which RNA itself (or precursor RNA-like polymers) can be synthesized nonenzymatically from the corresponding building blocks. Simulation experiments have exploited chemically reactive mononucleotides as monomers. Solutions of such monomers in the prebiotic environment were likely to be very dilute, but in experimental simulations of polymerization reactions dilute solutions of activated mononucleotides in the millimolar range hydrolyze extensively, and only trace amounts of dimers and trimers are formed. We report here that random medium-size RNA analogues with mixed sequences (5- to 17-mers with traces of longer products) can be synthesized in ice eutectic phases that are produced when dilute solutions of activated monomers and catalysts (Mg(II) and Pb(II)) are frozen and maintained at -18 degrees C for periods up to 38 days. Under these conditions, the monomers are concentrated as eutectics in an ice matrix. Hydrolysis of the activated mononucleotides was suppressed at low-temperature ranges, and polymerization was enhanced with yields up to 90%. Analysis of the mixed oligomers established that incorporation of both purine and pyrimidine bases proceeded at comparable rates and yields. These results suggest that ice deposits on the early Earth could have facilitated the synthesis of short- and medium-size random sequence RNA analogues and thereby provided a microenvironment suitable for the formation of biopolymers or their precursors.     

Silver-carboxymethyl chitin nanocomposites

Nanocomposite macromolecular systems consisting of silver nanoparticles immobilized in a carboxymethyl chitin matrix are obtained. The method of ultrasonic treatment of a heterophase system (isooctane-water) in the presence of antioxidants of plant origin is used to transfer silver nanoparticles from their micellar solution in isooctane to an aqueous polymer solution. The formation of hydrogen bonds between the functional groups of carboxymethyl chitin and hydroxyl groups of antioxidants is confirmed by Fourier transform infrared spectroscopy. This interaction can provide additional stabilization of metal nanoparticles in the macromolecular system. The transmission electron microscopy data shows that the size of silver nanoparticles increases in a series of antioxidants (gallic acid, dihydroquercetin, and syringic acid). The increase is presumably caused by significant differences in the structures of these antioxidants and their interaction with the polymer matrix.     

Wetting behavior of pulmonary surfactant aqueous solutions

The wetting properties of pulmonary surfactant aqueous solutions with respect to solid surfaces with different degree of hydrophobicity have been studied. The contact angles θ of drops from a pulmonary surfactant solution onto SiO₂-glass surfaces have been measured as a function of their degree of hydrophobicity θ _w. The completely hydrophilic SiO₂-glass surface is essentially hydrophobized by the animal-derived pulmonary surfactant Curosurf. The hydrophobization depends on the surfactant concentration—the contact angles increase with increasing the Curosurf concentration C _s in the low concentration range, but they remain almost constant in a wide range of C _s >90 μg/ml. Additions like NaCl and bovine serum albumin influence the θ-values. The contact angles θ naturally increase with increasing θ _w but this dependence is not linear—the curve steepens at larger θ _w values. The thickness h of the wetting thin liquid films from Curosurf aqueous solutions depends on the hydrophobicity θ _w of the solid surface and the h(θ _w) curves always pass a minimum. The h-values, as well as the h(θ _w) curve, are mainly determined by the steric and hydrophobic disjoining pressures, which depend on the orientations and conformations of the molecules adsorbed on the solid surface from the very complicated multi-component aqueous solutions.     

Fiber laser cleaning of metal mirror surfaces for optical diagnostic systems of the ITER

The results of experimental studies into efficiency of removal of films with a complex composition from metal mirrors by pulsed fiber laser irradiation are presented. It is shown that the initial reflectivity of optical elements can be restored by the selection of modes of irradiation impacting the surface with the sputtered film. Effective cleaning is performed by radiation with a power density lower than 10⁷ W/cm². The removal of contaminations at such a relatively low power density occurs in a solid phase, owing to which the thermal effect on the mirror is insignificant.     

Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane

Boron‐containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface‐mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure‐dependent relative formation of the main product propylene and by‐product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium‐based catalysts.     

Some novel photosensitive diacetylene diurethanes and their mixtures in common polymers

Some new octa-3,5-diynylene diurethanes were prepared using 3-butyn-1-ol, and all were found to be highly light-sensitive and to undergo topochemical polymerization on exposure to irradiation. The di-n-octyldiurethane was mixed with vinyl polymers such as poly(vinyl acetate) and poly(N,N-dimethylamino-ethyl methacrylate) and the mixtures were made into thin films by spin coating. The films were then irradiated by an electron beam to polymerize the diacetylene. The purple films thus obtained showed third-order nonlinear susceptibility, χ⁽³⁾, of the order of 10⁻¹⁰–10⁻¹¹ e.s.u.     

On The Maximum Friction Law for Rigid/Plastic,Hardening Materials

For a rigid/plastic, hardening material model, it is shown that the velocity fields adjacent to surfaces of maximum friction must satisfy the sticking condition. This means that the stress boundary condition, the maximum friction law, may be replaced by the velocity boundary condition. Axisymmetric flows without rotation and planar flows are considered.