Influence of substituents in the salicylaldehyde‐derived Schiff bases on vanadium‐catalyzed asymmetric oxidation of sulfides

A series of chiral Schiff bases ( L ¹ – L ⁵ ) with different substituents in the salicylidenyl unit were prepared from condensation of 3‐aryl‐5‐ tert ‐butylsalicylaldehyde derivatives and optically active amino alcohols. Bromination of 3‐phenyl‐5‐ tert ‐butylsalicylaldehyde gave an unexpected product 3‐(4‐bromophenyl)‐5‐bromosalicylaldehyde, from which the corresponding Schiff base ligands L ⁶ and L ⁷ , derived from (S)‐valinol and (S)‐ tert ‐leucinol, respectively, were prepared. Ligands L ¹ – L ⁷ were applied to the vanadium‐catalyzed asymmetric oxidation of aryl methyl sulfides. Under the optimal conditions, the oxidation of the thioanisole with H₂O₂ as oxidant in CH₂Cl₂ catalyzed by VO(acac)₂‐ L ¹ – L ⁷ gives good yields (74–83%) with moderate enantioselectivity (58–77% ee). Ligand L ⁷ , containing a 4‐bromophenyl group on the 3‐position and a Br atom on the 5‐position of the salicylidenyl moiety, displays an 80–90% ee for vanadium‐catalyzed oxidation of methyl 4‐bromophenyl sulfide and methyl 2‐naphthyl sulfide. Copyright © 2008 John Wiley & Sons, Ltd.     

A rapid and green approach to chiral α-hydroxy esters: asymmetric transfer hydrogenation (ATH) of α-keto esters in water by use of surfactants

A series of α-hydroxy esters were rapidly prepared (1.5 h) from α-keto esters via asymmetric transfer hydrogenation (ATH) in water by the use of surfactants for the first time. This green method, catalyzed by a water-soluble and recyclable Ru(II) complex, gave moderate to high enantioselectivities (up to 99.7% ee) with DTAB as an additive and HCOONa as the hydrogen source.     

An Algorithm Based on Active Sets and Smoothing for Discretized Semi-Infinite Minimax Problems

We present a new active-set strategy which can be used in conjunction with exponential (entropic) smoothing for solving large-scale minimax problems arising from the discretization of semi-infinite minimax problems. The main effect of the active-set strategy is to dramatically reduce the number of gradient calculations needed in the optimization. Discretization of multidimensional domains gives rise to minimax problems with thousands of component functions. We present an application to minimizing the sum of squares of the Lagrange polynomials to find good points for polynomial interpolation on the unit sphere in ℝ³. Our numerical results show that the active-set strategy results in a modified Armijo gradient or Gauss-Newton like methods requiring less than a quarter of the gradients, as compared to the use of these methods without our active-set strategy. Finally, we show how this strategy can be incorporated in an algorithm for solving semi-infinite minimax problems.     

Tadpole‐shaped amphiphilic copolymers prepared via RAFT polymerization and click reaction

The tadpole‐shaped amphiphilic copolymers with cyclic polystyrene as the head and a linear poly(N‐isopropylacrylamide) as the tail have been successfully synthesized by combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and “click” reaction. The synthesis involves two main steps: (1) preparation of a linear acetylene‐terminated PNIPAAM‐b‐PS with a side azido group anchored at the junction between two blocks; (2) intramolecular cyclization reaction to produce the cyclic PS block using “click” chemistry under high dilution. The structures, molecular weights, and molecular weight distributions of the resulted intermediates and the target polymers were characterized by their ¹H NMR, FTIR, and gel permeation chromatography. The difference of surface property between tadpole‐shaped polymer and its linear precursor was observed, and the water contact angles on the former surface are larger than that of the latter surface. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2390–2401, 2008     

Asymptotics for solutions of a defective renewal equation with applications

In this paper, we derive non-exponential asymptotic forms for solutions of defective renewal equations. These include as special cases asymptotics for compound geometric distribution and the convolution of a compound geometric distribution with a distribution function. As applications of these results, we study the Gerber-Shiu discounted penalty function in the classical risk model and the reliability of a two-unit cold standby system in reliability theory.      

Thermal plasma deposition of nanostructured films

A thermal plasma process for the synthesis of nanoparticles and their immediate assembly into nanostructured films is discussed. In this process, known as hypersonic plasma particle deposition, a thermal plasma with injected precursors is expanded through a nozzle to nucleate nanoparticles, which are then inertially deposited onto a cooled substrate in vacuum. A lightly consolidated nanostructured film results. Particle and film diagnostics along with images of the plasma flow are used to explain the formation of nanostructured silicon carbide films by this process     

Polyplatinayne/polyoxometalate composite Langmuir‐Blodgett films: Preparation,structural characterization,and potential optoelectronic applications

A new family of organometallic/inorganic composite Langmuir‐Blodgett (LB) films consisting of rigid‐rod polyplatinayne polymer ([Pt‐T(OMe‐Fl)T]_∞ or [Pt‐T(F‐Fl)T]_∞, where the triplet bonds are abbreviated by T, and fluorene ring by Fl) as the π‐conjugated organometallic molecule, polyoxometalate (POM, POM = K₃PMo₁₂O₄₀, H₃PW₁₂O₄₀, or H₆P₂W₁₈O₆₂) of the Keggin and Dawson structures as the inorganic component, and dimethyldioctadecylammonium bromide (DODA) or a mixture of octadecanoic acid (OA) and docosanoic acid (DA) as the auxiliary film‐forming agent were prepared and characterized by π–A isotherms, UV–Vis absorption spectra, photoluminescence spectra, atomic force microscopy imaging, scanning tunneling microscopy, and low‐angle X‐ray diffraction. Our experimental results indicate that steady, even, and ordered Langmuir and LB films are formed in pure water and polyoxometalate subphases. It was shown that the POM molecules are probably embedded inside the polyplatinayne molecules in the LB film structure and they can quench the luminescence of the Pt polyyne. These Pt‐polyyne based LB films display interesting electric conductivity behavior. [Pt‐T(OMe‐Fl)T]_∞/DODA/HPW₁₂ monolayer film shows a good electrical conductivity, and the tunneling current amounts to ±100 nA when the voltage is set at ±8 V. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3193–3206, 2008     

A Test of Multivariate Independence Based on a Single Factor Model

A test of the independence of two sets of variables is developed to have high power against a special family of dependence. In this each set of variables has the structure of a single factor model and the dependence is solely via the correlation γ between the underlying latent variables. This is a model with only one nonzero canonical correlation. It is shown that a test based on the maximum likelihood estimate of γ is appreciably more powerful than that based on r₁, the largest sample canonical correlation. If, however, the model is used, not just as a family of alternatives but as the basis for interpretation, and if substantial cross-correlation is present then the procedure is essentially equivalent to the use of r₁.