Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Crystal and molecular structures of 1-[3-(3,4-dimethoxyphenyl)-2-propenoyl]pyrrolidine.

The crystal structure of 1-[3-(3,4-dimethoxyphenyl)-2-propenoyl]pyrrolidine (C15H19NO3) (I) has been determined by X-ray analysis. It crystallizes orthorhombic space group Pbca with a = 24.295(3), b = 15.086(3), c = 7.552(3)A, V = 2768(1)A3, Z = 8, Dcalc = 1.254 g/cm3, mu = (Mo K(alpha)) = 0.87 cm(-1). The title compound has analgesic activity of cycloaliphatic amine part. The molecule is deviated from planar configuration.     

Study of adsorption of oxygen on β-Al2O3 + Au and β-Al2O3 + Pt: Work function measurements—proposition of a model

To improve the understanding of the electrochemical effects observed on an original potentiometric gas sensor, interactions of oxygen with the device were investigated. This gas sensor is made of a solid electrolyte (treated Na-β-alumina) associated with two metallic electrodes (gold and platinum) located in the same gas mixture. Adsorption of charged oxygen species, considered responsible for the electrical response developed by the sensor, was investigated by work function measurements. Results showed that charged oxygen species only form on partially gold or platinum covered solid electrolyte. Comparison of these results with those obtained in a previous calorimetric study of interactions between oxygen and the same materials suggests the existence of at least two different oxygen species adsorbed on the surface of the sensitive element. The first one, located on the solid electrolyte surface, is neutral and characterized by an endothermal reaction of formation. The second one is charged and probably produced at the gas/solid electrolyte/metallic electrode interface. A mechanism based on the concept of “three phase boundary” and similar to the “reverse spillover” phenomenon is proposed to account for the adsorption of these oxygen species.     

Cauchy problem in the class of monotone increasing functions

The paper establishes some solvability conditions of the Cauchy problem for linear differential equation in the class of monotone increasing functions. The results are applied for clarifying the possibility of flight along a given trajectory under existence of braking forces.     

Integrable models for vicious and friendly walkers

We consider random walks of two essentially different classes of random walkers, namely, of vicious and friendly ones, on one-dimensional lattices with periodic boundary conditions. The walkers are called vicious since, arriving at a lattice site, they annihilate not only one another but all the remaining walkers as well. On the contrary, an arbitrary number of friendly walkers can share the same lattice sites. It is shown that a natural model describing the behavior of friendly walkers is an integrable model of the boson type. A representation of the generating function for the number of the lattice paths performed by a fixed number of friendly walkers for a certain number of steps is obtained. Bibliography: 22 titles. __________ Translated from Zapiski Nauchnykh Seminarov POMI, Vol. 335, 2006, pp. 59–74.     

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.     

On the dynamical Casimir effect in a one-dimensional contracting cavity

The dynamical Casimir effect is analyzed in the framework of the S-matrix formulation for a one-dimensional cavity that exhibits contraction at a constant rate over a finite time interval. The exact solution to the problem is presented. It is demonstrated that the efficiency of the creation of pairs nonmonotonically depends on the contraction time. This is due to the fact that the particles are only created at the moments corresponding to the acceleration and stopping of the moving boundary, so that the contributions of these processes on the number of the created particles interfere with each other. The parameters that correspond to the optimal creation of pairs and the stability of a vacuum are presented. The effect of the finiteness of the cavity-boundary acceleration on the results obtained is studied.     

Photo-induced evolution of copper sheets from cluster molecules and its application to photolithographic copper patterning

UV photoexcitation of (t-butylethynyl copper)₂₄ cluster films induces segregation of the crystals into metallic and organic phases and leads to evolve the metallic sheets sandwiched by organic polymers. The growth of the metallic crystals in the plane of the photo-electromagnetic field is attributed due to plasmon-plasmon interaction among nanoparticles embedded in dielectric polymer matrices. The surface enhanced photochemical reaction of residual cluster molecules on the photon incident direction is expected to take an important role for joining the metal particles to produce a metallic sheet. We can apply this phenomenon for photolithographic copper pattern generation on a flexible base plate.     

Algebras of Random Operators Associated to Delone Dynamical Systems

We carry out a careful study of operator algebras associated with Delone dynamical systems. A von Neumann algebra is defined using noncommutative integration theory. Features of these algebras and the operators they contain are discussed. We restrict our attention to a certain C ^*-subalgebra to discuss a Shubin trace formula.