Electrochemical reduction of monothiobenzils in the presence of aroyl chlorides. First synthesis of (Z)-α-benzoyloxy-β-benzoylthiostilbenes

The first method for the synthesis of the title compounds has been established involving a stereoselective electrochemical diacylation process. The cathodic reductions of monothiobenzils in an aprotic medium, under constant potential, in the presence of twofold molecular amounts of aroyl chlorides provide previously unknown (Z)-α-benzoyloxy-β-benzoythiostilbenes in high to quantitative yields.     

A sequential injection system for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples.

A sequential injection methodology for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples is proposed. A single manifold is used for the determination of the three analytes, and the same protocol sequence allows the sequential determination of calcium and magnesium (the sum corresponds to the water hardness). The determination of both metals is based on their reaction with cresolphtalein complexone; mutual interference is minimized by using 8-hydroxyquinoline for the determination of calcium and ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) for the determination of magnesium. Alkalinity determination is based on a reaction with acetic acid, and corresponding color change of Bromcresol Green. Working ranges of 0.5 - 5 mg dm(-3) for Ca, 0.5 - 10 mg dm(-3) for Mg, and 10 - 100 mg HCO3- dm(-3), for alkalinity have been achieved. The results for water samples were comparable to those of the reference methods and to a certified reference water sample. RSDs lower than 5% were obtained, a low reagent consumption and a reduced volume of effluent have been accomplished. The determination rate for calcium and magnesium is 80 h(-1), corresponding to 40 h(-1) per element, while 65 determinations of alkalinity per hour could be carried out.     

Synthesis, thermal treatment and characterization of cobalt ferrite-based nanocomposites

We have used time-differential perturbed angular correlation (PAC) spectroscopy with ¹⁸¹Ta-probes to study the electric field gradient at Zr-sites in synthetic zircon and hafnon between room temperature and 1,200°C. PAC spectra are similar to those obtained from naturally occurring zircons. In particular, a change in slope of the quadrupole coupling vs. temperature is observed in the synthetic zircon at the same temperature as seen in natural zircons from the Mud Tank carbonatite (Australia). The synthetic hafnon data also shows this feature but at somewhat higher temperature. Low-temperature PAC spectra of both synthetic zircon and hafnon have a clearly reduced anisotropy. We believe that the cause for this is a electronic defect, possibly created during the β-decay of the probe parent nucleus.     

Maximum diameter of regular digraphs

We prove that every r-biregular digraph with n vertices has its directed diamter bounded by (3n - r - 3)/(r +1). We show that this bound is tight for directed as well as for undirected graphs. The upper bound remains valid for Eulerian digraphs with minimum outdegree r. © 1929 John Wiley & Sons, Inc.     

Risk-neutral valuation with infinitely many trading dates

The first Fundamental Theorem of Asset Pricing establishes the equivalence between the absence of arbitrage in financial markets and the existence of Equivalent Martingale Measures, if appropriate conditions hold. Since the theorem may fail when dealing with infinitely many trading dates, this paper draws on the A.A. Lyapunov Theorem in order to retrieve the equivalence for complete markets such that the Sharpe Ratio is adequately bounded.     

Highly polarized dithiafulvenes: synthesis and nonlinear optical properties

Push-pull dithiafulvenes with reduced bond length alternation (BLA) and high optical nonlinearities have been prepared. The interplay between the proaromaticity of the donor and the structural and optical properties of these merocyanines is discussed. The donor ability of dithiafulvenes can reach that of ferrocene or dialkylaminophenyl groups.     

Effect of excess halide on the palladium‐catalyzed insertion‐triggered radical copolymerization of methyl acrylate and 1‐hexene

[Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) is a very efficient initiator of the radical polymerization of methyl acrylate, but it is not active in the polymerization of methyl methacrylate or in the copolymerization with 1‐hexene. The addition of an excess of NBu₄Cl to solutions of [Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) provides an initiator system that copolymerizes methyl acrylate and 1‐hexene by an insertion‐triggered radical mechanism. Random copolymers are obtained with 11% incorporation of 1‐hexene in moderate yields (about 35%). Studies of the decomposition products obtained after the first insertion of methyl acrylate in the Pd? C₆F₅ bond of 1 show that the addition of excess halide in the presence of monomer favors the homolytic cleavage of the Pd? C bond, and the generation of the radicals that are active species in the polymerization, versus alternative evolution pathways. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5682–5691, 2006     

Mathematical modeling of crystallization analysis fractionation (Crystaf) of polyethylene

Four polyethylene samples (PE) with different molecular weight distributions (MWD) were analyzed by crystallization analysis fractionation (Crystaf) at several cooling rates to investigate the effect of MWD and cooling rate on their Crystaf profiles. Using these results, we developed a mathematical model for Crystaf that considers crystallization kinetic effects, which are ignored in all previous Crystaf models. The Crystaf model we proposed can fit the experimental Crystaf profiles of the 4 polyethylene resins very well. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2749–2759, 2006