The electron stimulated chemistry of methyl lactate on Cu(1 1 1)

The electron stimulated chemistry of monolayers of (R)/(S)-methyl lactate ((S)/(R)-MLAc) adsorbed on Cu(1 1 1) has been investigated. Monolayers of MLAc undergo highly efficient electron stimulated processes predominately desorption, but also a significant fraction is converted to an adsorbed alkoxide moiety through the selective cleavage of the O–H bond. The efficiency of the depletion of the adsorbed MLAc state and the absence of significant non-selective fragmentation contrasts with previous studies of the electron beam irradiation of monolayers of oxygen containing organic molecules.     

Solubility and preferential solvation of indomethacin in 1,4-dioxane + water solvent mixtures

The solubilities of indomethacin (IMC) in 1,4-dioxane + water cosolvent mixtures were determined at several temperatures, 293.15–313.15 K. The thermodynamic functions: Gibbs energy, enthalpy, and entropy of solution and of mixing were obtained from these data by using the van’t Hoff and Gibbs equations. The solubility was maximal in 0.95 mass fraction of 1,4-dioxane and very low in pure water at all the temperatures. A non-linear plot of ΔH_soln ° vs. ΔG_soln ° with negative slope from pure water up to 0.60 mass fraction of 1,4-dioxane and positive beyond this up to 0.95 mass fraction of 1,4-dioxane was obtained. Accordingly, the driving mechanism for IMC solubility in water-rich mixtures is the entropy, probably due to water-structure loss around the drug non-polar moieties by 1,4-dioxane, whereas, above 0.60 mass fraction of 1,4-dioxane the driving mechanism is the enthalpy, probably due to IMC solvation increase by the co-solvent molecules. The preferential solvation of IMC by the components of the solvent was estimated by means of the quasi-lattice quasi-chemical method, whereas the inverse Kirkwood-Buff integral method could not be applied because of divergence of the integrals in intermediate compositions.     

C-metalated nitriles: electrophile-dependent alkylations and acylations

Sequential carbonyl addition-conjugate addition of Grignard reagents to 3-oxocyclohex-1-ene-1-carbonitrile generates C-magnesiated nitriles whose alkylation stereoselectivities intimately depend on the nature of the electrophile. The alkylation of these C-magnesiated nitriles with alkyl halides, sulfonates, and unstrained ketones occurs with the retention of the C-Mg configuration, whereas aldehyde and acyl cyanide acylations proceed with inversion of the stereochemistry. Mechanistic probes indicate that the stereoselectivity is controlled by stereoelectronic effects for most electrophiles, except allylic, benzylic, and cyclopropyl halides where single-electron-transfer processes intervene. Screening numerous alkylations of C-magnesiated nitriles with a diverse range of electrophiles reveals the reaction scope and delineates the fundamental stereoelectronic effects responsible for the highly unusual electrophile-dependent alkylations.     

Simultaneous diode-laser-based in situ measurement of liquid water content and oxygen mole fraction in dense water mist environments

We performed what we believe are the first simultaneous in situ measurements of liquid water and oxygen concentrations in a dense water mist environment. Direct absorption tunable diode laser absorption spectroscopy was used to make oxygen concentrations and simultaneously quantify the liquid water via optical density measurements. This spectrometer with an absorption path length of only 36.8 cm was successfully tested during full-scale fire suppression tests with scattering losses up to 99.9%. The simultaneous oxygen and liquid water concentration measurements agree with fire suppression model calculations.     

Max-Plus Stochastic Control and Risk-Sensitivity

In the Maslov idempotent probability calculus, expectations of random variables are defined so as to be linear with respect to max-plus addition and scalar multiplication. This paper considers control problems in which the objective is to minimize the max-plus expectation of some max-plus additive running cost. Such problems arise naturally as limits of some types of risk sensitive stochastic control problems. The value function is a viscosity solution to a quasivariational inequality (QVI) of dynamic programming. Equivalence of this QVI to a nonlinear parabolic PDE with discontinuous Hamiltonian is used to prove a comparison theorem for viscosity sub- and super-solutions. An example from mathematical finance is given, and an application in nonlinear H-infinity control is sketched.     

Accelerating the DC algorithm for smooth functions

We introduce two new algorithms to minimise smooth difference of convex (DC) functions that accelerate the convergence of the classical DC algorithm (DCA). We prove that the point computed by DCA can be used to define a descent direction for the objective function evaluated at this point. Our algorithms are based on a combination of DCA together with a line search step that uses this descent direction. Convergence of the algorithms is proved and the rate of convergence is analysed under the ?ojasiewicz property of the objective function. We apply our algorithms to a class of smooth DC programs arising in the study of biochemical reaction networks, where the objective function is real analytic and thus satisfies the ?ojasiewicz property. Numerical tests on various biochemical models clearly show that our algorithms outperform DCA, being on average more than four times faster in both computational time and the number of iterations. Numerical experiments show that the algorithms are globally convergent to a non-equilibrium steady state of various biochemical networks, with only chemically consistent restrictions on the network topology.     

Temperature effects on femtosecond transient absorption kinetics of semiconducting single-walled carbon nanotubes

We report femtosecond transient absorption kinetics measured for selected semiconducting single-walled carbon nanotubes at different temperatures between 77 and 290 K. The nanotubes are embedded in a thin polymethylmethacrylate film, and the dominance of individual species enabled to probe selectively the kinetics associated with two desired tube types, the (6,5) and (7,5) tubes. A strikingly similar temperature dependence is found between the maximum change in the amplitude of transient absorption kinetics, the overall decay time and steady-state fluorescence emission intensity. The simplest explanation for our data is that the temperature dependence of the fluorescence intensity and the exciton decay kinetics are dominated by nonradiative decay and that the radiative decay rate is weakly temperature dependent.     

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