Ascorbic acid as a potential masking agent in the tanning process. Olated chromium complexes involving ligating ascorbate and bridging sulfate groups

Two polynuclear complexes, a dimer and a tetramer, involving sulfate and hydroxo bridges and ligating ascorbate were isolated from aqueous solutions. Structural formulae are proposed on the basis of microanalytical and thermal analysis results, i.r., ¹³C-n.m.r., mass spectral data and magnetic measurements.     

On estimating a density using Hellinger distance and some other strange facts

Résumé On s'intéresse ici aux possibles vitesses d'estimation d'une densité à support compact dans ^m sous des hypothèses de régularité, lorsque la perte est mesurée par le carré de la distance de Hellinger (on regardera aussi le cas connu des normes pour 1q2) et le risque est le risque minimax sur la famille. On donne une méthode générale permettant de traiter les problèmes dans le cadre de la théorie de l'approximation sous des conditions concernant l'entropie métrique et l' -capacité des familles à estimer. Les rapports entre régularité et entropie métrique étant bien connus, nous pourrons aussi traiter les cas classiques et d'autres qui le sont moins. Sous des conditions de bornes inférieures les vitesses sont celles observées pour la norme mais elles diffèrent dans le cas général. On montre aussi que les restrictions sur la compacité du support ou la régularité sont indispensables et que leur absence mène à l'impossibilité d'obtenir une estimation raisonnable en ce sens que n'importe quelle suite d'estimateurs sera arbitrairement mauvaise en un point au moins. Un résultat analogue est vrai sous des conditions de régularité.

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This work was carried out during a visit of the author at the Mathematical Sciences Research Institute at Berkeley     

Copper(II) and zinc(II) complexes of thiophene/furan carboxamides: Synthesis,structure and properties

Cu(II) and Zn(II) complexes were synthesized from equimolar amounts of carboxamides; 1,8-bis(2-thiophenecarboxamido)-p-menthane (tkdam) and 1,8-bis(2-furancarboxamido)-p-menthane (furdam). The structure of the carboxamides were determined by elemental analysis; ¹H NMR, ¹³C NMR, FT-IR and LC-MS spectra. The relative energies and the electronic properties (LUMO, HOMO, LUMO-HOMO gap) of the ligands were investigated theoretically by performing Semi-empirical molecular orbital theory PM3 method in Hyperchem 7 (Release). Carboxamide complexes having general formula as; monomeric, [ML]Cl₂ and dimeric [Cu(tkdam)Cl]₂Cl₂ · 5H₂O were synthesized and characterized by using element analysis; FT-IR, LC-MS spectra; magnetic susceptibility, molar conductivity and thermal (TGA/DTA curve) studies. It was found that the coordination number of the monomeric complexes is four whereas dimeric’s is six. The changes in the selected vibration bands in FT-IR indicate that, carboxamides behave as tetradentate ligands and coordinate to metal ions from acyl ring (through S/O) and amide carbonyl (C=O). Molar conductivity measurements indicate the 1: 2 ionic nature of the carboxamide complexes.     

Polyurethane Films for Wound Dressing Applications

Polyurethane films based on renewable sources were prepared as an alternative to petroleum-based polyurethane. The effects of the structure and ratio of diisocyanate components on polymer properties were investigated. Hexamethylene diisocyanate (HMDI) and diphenylmethylene diisocyanate (MDI) were chosen as the diisocyanate components in polymer synthesis. Membranes were prepared by casting-evaporation technique and characterized for their gas permeability, film and mechanical properties. The oil-based membranes were found to be suitable for wound dressing applications.     

Risk bounds for model selection via penalization

Performance bounds for criteria for model selection are developed using recent theory for sieves. The model selection criteria are based on an empirical loss or contrast function with an added penalty term motivated by empirical process theory and roughly proportional to the number of parameters needed to describe the model divided by the number of observations. Most of our examples involve density or regression estimation settings and we focus on the problem of estimating the unknown density or regression function. We show that the quadratic risk of the minimum penalized empirical contrast estimator is bounded by an index of the accuracy of the sieve. This accuracy index quantifies the trade-off among the candidate models between the approximation error and parameter dimension relative to sample size. If we choose a list of models which exhibit good approximation properties with respect to different classes of smoothness, the estimator can be simultaneously minimax rate optimal in each of those classes. This is what is usually called adaptation. The type of classes of smoothness in which one gets adaptation depends heavily on the list of models. If too many models are involved in order to get accurate approximation of many wide classes of functions simultaneously, it may happen that the estimator is only approximately adaptive (typically up to a slowly varying function of the sample size). We shall provide various illustrations of our method such as penalized maximum likelihood, projection or least squares estimation. The models will involve commonly used finite dimensional expansions such as piecewise polynomials with fixed or variable knots, trigonometric polynomials, wavelets, neural nets and related nonlinear expansions defined by superposition of ridge functions. Received: 7 July 1995 / Revised version: 1 November 1997     

Aufbau von Erdalkalimetall‐Arsen‐Käfigstrukturen durch die Metallierung von Triisopropylsilylarsan mit Calcium‐, Strontiumund Barium‐bis[bis(trimethylsilyl)amid] in Tetrahydrofuran

Formation of Alkaline Earth Metal‐Arsenic Cages via the Metalation of Triisopropylsilylarsane with Calcium, Strontium, and Barium Bis[bis(trimethylsilyl)amide] in Tetrahydrofuran The metalation of triisopropylsilylarsane with the alkaline earth metal bis[bis(trimethylsilyl)amides] in tetrahydrofuran yields the THF complexes of calcium ( 1 ), strontium ( 2 ), and barium‐bis(triisopropylsilylarsanide) ( 3 ). Dissolving of these compounds in toluene leads to the elimination of triisopropylsilylarsane and the formation of the THF complexes of tetraalkaline earth metal hexakis(triisopropylsilylarsanide)‐triisopropylsilylarsanediide of calcium ( 4 ), strontium ( 5 ), and barium ( 6 ), respectively. The central polyhedron of compound 4 can be described as two trigonal bipyramids with the metal atoms in apical positions, connected via the arsanediide substituent as a common corner. The central moieties of the compounds 5 and 6 consist of four trigonal bipyramids which are connected by common edges as well as common faces.     

Estimating the intensity of a random measure by histogram type estimators

The purpose of this paper is to estimate the intensity of some random measure N on a set ${\mathcal{X}}$ by a piecewise constant function on a finite partition of ${\mathcal{X}}$ . Given a (possibly large) family ${\mathcal{M}}$ of candidate partitions, we build a piecewise constant estimator (histogram) on each of them and then use the data to select one estimator in the family. Choosing the square of a Hellinger-type distance as our loss function, we show that each estimator built on a given partition satisfies an analogue of the classical squared bias plus variance risk bound. Moreover, the selection procedure leads to a final estimator satisfying some oracle-type inequality, with, as usual, a possible loss corresponding to the complexity of the family ${\mathcal{M}}$ . When this complexity is not too high, the selected estimator has a risk bounded, up to a universal constant, by the smallest risk bound obtained for the estimators in the family. For suitable choices of the family of partitions, we deduce uniform risk bounds over various classes of intensities. Our approach applies to the estimation of the intensity of an inhomogenous Poisson process, among other counting processes, or the estimation of the mean of a random vector with nonnegative components.     

Copper-deposited aluminum anode for aluminum-air battery

Journal of Solid State Electrochemistry - For Al-air batteries, it is important to develop efficient and economical anodes. In this study, the effect of aluminum anodes treated with copper by...