The palladium-catalyzed Heck arylation of olefins with arenediazonium salts as a sustainable strategy in organic synthesis

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Denumerable controlled Markov chains with strong average optimality criterion: Bounded & unbounded costs

This paper studies discrete-time nonlinear controlled stochastic systems, modeled by controlled Markov chains (CMC) with denumerable state space and compact action space, and with an infinite planning horizon. Recently, there has been a renewed interest in CMC with a long-run, expected average cost (AC) optimality criterion. A classical approach to study average optimality consists in formulating the AC case as a limit of the discounted cost (DC) case, as the discount factor increases to 1, i.e., as the discounting effectvanishes. This approach has been rekindled in recent years, with the introduction by Sennott and others of conditions under which AC optimal stationary policies are shown to exist. However, AC optimality is a rather underselective criterion, which completely neglects the finite-time evolution of the controlled process. Our main interest in this paper is to study the relation between the notions of AC optimality andstrong average cost (SAC) optimality. The latter criterion is introduced to asses the performance of a policy over long but finite horizons, as well as in the long-run average sense. We show that for bounded one-stage cost functions, Sennott's conditions are sufficient to guarantee thatevery AC optimal policy is also SAC optimal. On the other hand, a detailed counterexample is given that shows that the latter result does not extend to the case of unbounded cost functions. In this counterexample, Sennott's conditions are verified and a policy is exhibited that is both average and Blackwell optimal and satisfies the average cost inequality.     

Access to the spiro hydrindandione ring system of Fredericamycin A through a Friedel-Crafts reaction.

Condensation of 1,4-dimethoxybenzene with 1,1-cyclopentane dicarboxylic acid or 1,1-indan dicarboxylic acid derivatives led to the title compounds.     

Equivalence of Lyapunov stability criteria in a class of Markov decision processes

We are concerned with Markov decision processes with countable state space and discrete-time parameter. The main structural restriction on the model is the following: under the action of any stationary policy the state space is acommunicating class. In this context, we prove the equivalence of ten stability/ergodicity conditions on the transition law of the model, which imply the existence of average optimal stationary policies for an arbitrary continuous and bounded reward function; these conditions include the Lyapunov function condition (LFC) introduced by A. Hordijk. As a consequence of our results, the LFC is proved to be equivalent to the following: under the action of any stationary policy the corresponding Markov chain has a unique invariant distribution which depends continuously on the stationary policy being used. A weak form of the latter condition was used by one of the authors to establish the existence of optimal stationary policies using an approach based on renewal theory.This research was supported in part by the Third World Academy of Sciences (TWAS) under Grant TWAS RG MP 898-152.     

Spray-drying as a tool to disperse conductive carbon inside Na<Subscript>2</Subscript>FePO<Subscript>4</Subscript>F particles by addition of carbon black or carbon nanotubes to the precursor solution

In this work, Na₂FePO₄F-carbon composite powders were prepared by spray-drying a solution of inorganic precursors with 10 and 20 wt% added carbon black (CB) or carbon nanotubes (CNTs). In order to compare the effect of CB and CNT when added to the precursor solutions, the structural, electrochemical, and morphological properties of the synthesized Na₂FePO₄F-xCB and Na₂FePO₄F-xCNT samples were systematically investigated. In both cases, X-ray diffraction shows that calcination at 600 °C in argon leads to the formation of Na₂FePO₄F as the major inorganic phase. ⁵⁷Fe Mössbauer spectroscopy was used as complementary technique to probe the oxidation states, local environment, and identify the composition of the iron-containing phases. The electrochemical performance is markedly better in the case of Na₂FePO₄F-CNT (20 wt%), with specific capacities of about 100 mAh/g (Na₂FePO₄F-CNT) at C/4 rate vs. 50 mAh/g for Na₂FePO₄F-CB (20 wt%). SEM characterization of Na₂FePO₄F-CB particles revealed different particle morphologies for the Na₂FePO₄F-CNT and Na₂FePO₄F-CB powders. The carbon-poor surface observed for Na₂FePO₄F-CB could be due to a slow diffusion of carbon in the droplets during drying. On the contrary, Na₂FePO₄F-CNT shows a better CNT dispersion inside and at the surface of the NFPF particles that improves the electrochemical performance.     

Contractive Approximations in Risk-Sensitive Average Semi-Markov Decision Chains on a Finite State Space

Journal of Optimization Theory and Applications - This work concerns with semi-Markov decision chains evolving on a finite state space. The controller has a positive and constant risk sensitivity...     

The Photobiological Differences of Gilvocarcins V and M Are not Related to their Transient Intermediates and Triplet Yields

Abstract— The transient absorption spectra of the intermediates produced by the 355 nm laser excitation of gilvocarcin derivatives have been investigated in various solvents. The spectra consist of a triplet-triplet absorption in the visible region and a residual absorption observed between 340 and 700 nm due to a long-lived species, assigned to the radical cation. A broad-fast decaying band with a maximum at around 700 nm attributed to the solvated electron is also seen in solutions containing a low DMSO/water volume ratio and at 266 nm irradiation of a 50% methanol/water solvent mixture. The molar absorption coefficient of the triplet state of gilvocarcin V (GV) and gilvocarcin M (GM), determined by the energy transfer method, is independent of the solvent properties and has a value of 3.0 × 10⁴/ M cm. The triplet decay rate constants for both drugs are between 1 and 5 × 10⁴/s. A similar initial yield and triplet decay rate constant of GV were observed in the presence of 3.4 m M thymine. Thus, a quenching rate constant of the GV's triplet state by thymine is estimated to be lower than 10⁶/Ms. The triplet quantum yields of both antibiotics determined by using the comparative method are higher in dimethylsulfoxide (DMSO) (0.18) than are those corresponding to 25% DMSO/water (0.06). The decrease in φ_T in the presence of water could be attributed to an enhanced internal conversion rate constant from the S₁ state or to an increase in the photoionization yield. The similarity of the transient intermediates and their yields for GV and GM suggest that their photobiological differences are due to other factors such as DNA binding constants, preferential localization of the drugs in the cell or the enhanced reactivity of the vinyl group toward cellular components.     

Cyclodextrins as hosts for poorly water-soluble compounds in enzyme catalysis

The capability of cyclodextrins to enhance greatly the solubility in water of poorly water-soluble substances makes them an ideal alter native for investigating the expression of enzyme activity with such substrates in aqueous solution. This capability is demonstrated by using soybean lipoxygenase with linoleic acid/β-cyclodextrin and di ethylstilbestrol/γ-cyclodextrin, and cholesterol oxidase with choles terol/methyl-β-cyclodextrin.     

The CuII−CuI−Cu0(Hg) system in the presence of benzotriazole: Part I. A polarographic investigation

A polarographic investigation of Cu^II electroreduction from solutions of benzotriazole (BTA) of pH from 1 to 3 at a dropping mercury electrode shows the presence of two successive adsorption waves of equal height (waves Ic and IIIc) due, respectively, to the formation and to the subsequent dissolution of an adsorbed film of a Cu^I compound. The dependence of the half-wave potential of wave IIIc, which is polarographically reversible, upon pH and BTA concentration indicates that the adsorbed film has the composition [Cu^I(BTA^?)], where BTA^? denotes the deprotonated anionic form of benzotriazole. Moreover, the maximum height of wave IIIc indicates that this film is one monolayer thick. A third cathodic wave (wave IIc), lying between waves Ic and IIIc, stems from the reduction to the metal state of the Cu^II ions diffusing from the bulk solution. Copper(0) oxidation at dropping amalgam electrodes in BTA solutions yields two successive adsorption waves (waves Ia and IIa). Wave Ia is due to the same electrode process, Cu⁰ (Hg)+BTA?Cu^I(BTA^?)+H⁺+e, responsible for the cathodic wave IIIc. On the other hand, wave IIa is due to the formation of roughly two adsorbed monolayers of [Cu^I(BTA^?)] upon that formed along wave Ia.     

Symmetrisation of β-alkoxyalkylmercury(II) acetates

β-Alkoxyalkylmercury(II) acetates have been symmetrised in situ with alkaline sodium stannite to afford good yields of bis(β-alkoxyalkyl)mercurials, [R¹R²C(OR)CHR³]₂ Hg.