Synthesis of ultra‐low‐molecular‐weight polyethylene wax using a bulky Ti(IV) aryloxide–alkyl aluminum catalytic system

Complexes of titanium(IV) with bulky phenolic ligands such as 2‐tert‐butyl‐4 methylphenol, 2, 4‐di‐tert‐butyl phenol and 3,5‐di‐tert‐butyl phenol were prepared and characterized. These catalyst precursors, formulated as [Ti(OPh*)_n(OPrⁱ)_4?n] (OPh* = substituted phenol), were found to be active in polymerization of ethylene at higher temperatures in combination with ethylaluminum sesquichloride (Et₃Al₂Cl₃) as co‐catalyst. It was observed that the reaction temperature and ethylene pressure had a pronounced effect on polymerization and the molecular weight of polyethylene obtained. In addition, this catalytic system predominantly produced linear, crystalline ultra‐low‐molecular‐weight polyethylenes narrow dispersities. The polyethylene waxes obtained with this catalytic system exhibit unique properties that have potential applications in surface coating and adhesive formulations. Copyright © 2007 John Wiley & Sons, Ltd.     

Reaction pathways and kinetic parameters of sonolytically induced oxidation of dimethyl methylphosphonate in air saturated aqueous solutions

The oxidation of dimethyl methylphosphonate (DMMP) was examined under ultrasonic conditions (640 kHz) in oxygen saturated aqueous solutions. Acetic acid, formic acid, methylphosphonic acid, phosphate, and oxalic acid have been identified as the major products produced during the sonolytic irradiation of DMMP. The initial rates of oxidation were determined as a function of initial DMMP concentration. The kinetic behavior of the system is consistent with the Langmuir-Hinshelwood model implying oxidative processes occur at or near the gas-liquid interface during cavitation. Mechanistic implications and conclusions are discussed based on the product distributions and kinetic parameters.     

On ergodic control of degenerate diffusions

For the ergodic control problem with degenerate diffusions, the existence of an optimal solution is established for various interesting classes of solutions.This research was supported by Grant No. 26/01/92-G from the Department of Atomic Energy, Government of India, Delhi, India.     

A remark on control of partially observed Markov chains

A new state variable is introduced for the problem of controlling a Markov chain under partial observations, which, under a suitably altered probability measure, has a simple evolution.     

Stochastic differential games: Occupation measure based approach

A new approach based on occupation measures is introduced for studying stochastic differential games. For two-person zero-sum games, the existence of values and optimal strategies for both players is established for various payoff criteria. ForN-person games, the existence of equilibria in Markov strategies is established for various cases.     

Single wall carbon nanotube supports for portable direct methanol fuel cells

Single-wall and multiwall carbon nanotubes are employed as carbon supports in direct methanol fuel cells (DMFC). The morphology and electrochemical activity of single-wall and multiwall carbon nanotubes obtained from different sources have been examined to probe the influence of carbon support on the overall performance of DMFC. The improved activity of the Pt-Ru catalyst dispersed on carbon nanotubes toward methanol oxidation is reflected as a shift in the onset potential and a lower charge transfer resistance at the electrode/electrolyte interface. The evaluation of carbon supports in a passive air breathing DMFC indicates that the observed power density depends on the nature and source of carbon nanostructures. The intrinsic property of the nanotubes, dispersion of the electrocatalyst and the electrochemically active surface area collectively influence the performance of the membrane electrode assembly (MEA). As compared to the commercial carbon black support, single wall carbon nanotubes when employed as the support for anchoring the electrocatalyst particles in the anode and cathode sides of MEA exhibited a approximately 30% enhancement in the power density of a single stack DMFC operating at 70 degrees C.     

Erratum to: Risk-Sensitive Control with Near Monotone Cost

The infinite horizon risk-sensitive control problem for non-degenerate controlled diffusions is analyzed under a ‘near monotonicity’ condition on the running cost that penalizes large excursions of the process.     

TDDFT Investigation of the Electronic Structures and Photophysical Properties of Fluorescent Extended Styryl Push-Pull Chromophores Containing Carbazole Unit

Push-pull chromophores attached to carbazole based π-conjugating spacers bearing N-alkylamino donors, cyanovinyl and carbethoxy acceptors have been studied by the means of UV-Visible measurements. The intramolecular charge transfer (ICT) of these π-conjugated systems has also been tested by investigating the ability of the solute molecules to undergo shifts in their fluorescence emission maxima with increasing solvent polarity. Density Functional Theory [B3LYP/6-31G(d)] and Time Dependent Density Functional Theory [TD-B3LYP/6-31G(d)] computations have been used to have more understanding of the structural, molecular, electronic and photophysical parameters of push-pull dyes. The largest wavelength difference between the experimental and computed electronic absorption maxima was 45 nm. For emission, a largest difference of 61 nm was observed. The ground state and excited state dipole moments in different solvents were determined using experimental solvatochromic data and computed Onsager radii. The dipole moments of the molecules in the excited state were observed to be higher than in the ground state.     

Ergodic Control of Partially Degenerate Diffusions in a Compact Domain

The problem of ergodic control of a reflecting diffusion in a compact domain is analysed under the condition of partial degeneracy, i.e. when its transition kernel after some time is absolutely continuous with respect to the Lebesgue measure on a part of the state space. Existence of a value function and a “martingale dynamic programming principle” are established by mapping the problem to a discrete time control problem. Implications for existence of optimal controls are derived.