Fluorinated resveratrol and pterostilbene

A general method for the synthesis of polyhydroxylated stilbene monofluorinated on the central double bond based on the Suzuki reaction between a bromofluoroolefin and a phenylboronic acid is described. Synthesis of fluorinated analogues of resveratrol and pterostilbene was achieved using this strategy.     

Thermodynamic behavior of polyelectrolytes with the lower critical solution temperature (LCST) phenomenon

A series of vinyl polymers with L-valine and L-leucine residues, and related copolymers with N-isopropylacrylamide, were studied in aqueous solution at different temperatures (25, 30 and 35°C) and at two ionic strengths (0.01 M and 0.1 M NaCl). The protonation behavior revealed great differences between the polymers that were attributed to the size of the hydrophobic lateral group. Macromolecular shrinkage, occurring above a critical degree of protonation β, was related to hydrophobic forces outweighing the electrostatic repulsions between COO – groups. Low salt concentrations increased the electrostatic potential while high temperatures increased the hydrophobic interaction at lower β. The release of fewer water molecules structured around the polymer chain, responsible for the lower critical solution temperature phenomenon, revealed lower entropy changes at higher temperatures. The reversible configuration of graft polymer chains instantly responded to changes in pH and temperature, modifying the water filtration rates through the pores of cellulose membranes.     

Standing waves for the NLS on the double-bridge graph and a rational–irrational dichotomy

We study standing waves of NLS equation posed on the double-bridge graph: two semi-infinite half-lines attached at a circle. At the two vertices Kirchhoff boundary conditions are imposed. The configuration of the graph is characterized by two lengths, $L_1$ and $L_2$. We study the solutions with possibly nontrivial components on the half-lines and a cnoidal component on the circle. The problem is equivalent to a nonlinear boundary value problem in which the boundary condition depends on the spectral parameter ω. After classifying the solutions with rational $L_1/L_2$, we turn to $L_1/L_2$ irrational showing that there exist standing waves only in correspondence to a countable set of negative frequencies ${\omega }_n$. Moreover we show that the frequency sequence admits cluster points and any negative real number can be a limit point of frequencies choosing a suitable irrational geometry $L_1/L_2$. These results depend on basic properties of diophantine approximation of real numbers.     

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.     

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.     

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.