234 research outputs found

    Limited Failure Censored Life Test Sampling Plan in Burr Type X Distribution

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    The Burr type X distribution is considered as a life time random variable of a product whose lots are to be decided for acceptance or otherwise on the basis of sample lifetimes drawn from the lot. The sample is divided into various groups in order to develop a group sampling plan in such a way that the life testing experiment is terminated as soon as the first failure in each group is observed. The acceptance criterion based on the theory of order statistics is proposed and is shown to be more economical than a criterion proposed in the earlier similar works

    Polymer-anchored palladium catalyst in carbonylation of organic halides - the first example of triphase catalysis

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    Polymer-anchored palladium-catalysed carbonylation of organic halides affords oxo esters in reasonable- yields under solid-liquid-solid phase transfer conditions at mild pressure and short durations

    Estimation and Testing in Type I Generalized Half Logistic Distribution

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    A generalization of the half logistic distribution is developed through exponentiation of its cumulative distribution function and termed the Type I Generalized Half Logistic Distribution (GHLD). GHLD’s distributional characteristics and parameter estimation using maximum likelihood and modified maximum likelihood methods are presented with comparisons. Comparison of Type I GHLD and the exponential distribution is conducted via likelihood ratio criterion

    Likelihood Ratio Type Test for Linear Failure Rate Distribution vs. Exponential Distribution

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    The Linear Failure Rate Distribution (LFRD) is considered. The graphs of its probability density function are examined for selected parameter combinations. Some of them are similar to the well-known exponential distribution. Incidentally exponential distribution is one of the two component models of the LFRD model. In view of the simpler form of exponential model as applicable in inference, looking at the frequency curves of LFRD, a test statistic is proposed based on ratio of likelihood functions containing the standard forms of the density functions of both LFRD and Exponential to discriminate between LFRD and exponential models. The critical values and the powers of the test statistic are developed

    A new bifunctional catalyst for tandem Heck-asymmetric dihydroxylation of olefins

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    A new bifunctional catalyst consisting of active palladium and osmium species anchored on silica gel through a mercaptopropyl spacer and a cinchona alkaloid respectively has been prepared for the first time and used in the heterogeneous tandem Heck-asymmetric dihydroxylation of olefins to afford diols with excellent yields and enantiomeric excesses (ee's) in presence of N-methylmorpholine Noxide or K3Fe(CN)6 as cooxidants

    The first example of direct oxidation of sulfides to sulfones by an osmate molecular oxygen system

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    Osmate-exchanged Mg-Al layered double hydroxides catalysed the delivery of two oxygen atoms simultaneously via a 3 + 1 cycloaddition to sulfide to form sulfone directly for the first time, reminiscent of 3 + 2 cycloaddition in asymmetric dihydroxylation reactions

    Structural and functional insights into asymmetric enzymatic dehydration of alkenols

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    The asymmetric dehydration of alcohols is an important process for the direct synthesis of alkenes. We report the structure and substrate specificity of the bifunctional linalool dehydratase isomerase (LinD) from the bacterium Castellaniella defragrans that catalyzes in nature the hydration of β-myrcene to linalool and the subsequent isomerization to geraniol. Enzymatic kinetic resolutions of truncated and elongated aromatic and aliphatic tertiary alcohols (C5-C15) that contain a specific signature motif demonstrate the broad substrate specificity of LinD. The three-dimensional structure of LinD from Castellaniella defragrans revealed a pentamer with active sites at the protomer interfaces. Furthermore, the structure of LinD in complex with the product geraniol provides initial mechanistic insights into this bifunctional enzyme. Site-directed mutagenesis confirmed active site amino acid residues essential for its dehydration and isomerization activity. These structural and mechanistic insights facilitate the development of hydrating catalysts, enriching the toolbox for novel bond-forming biocatalysis

    Hydrogen-transfer catalysis with Cp*Ir<sup>III</sup> complexes:The influence of the ancillary ligands

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    Fourteen Cp*IrIII complexes, bearing various combinations of N- and C-spectator ligands, are assayed in hydrogen-transfer catalysis from isopropyl alcohol to acetophenone under various conditions to investigate ligand effects in this widely used reaction. The new cationic complexes bearing monodentate pyridine and N-heterocyclic carbene (NHC) ligands were characterized crystallographically and by variable-temperature nuclear magnetic resonance (VT-NMR). Control experiments and mercury poisoning tests showed that iridium(0) nanoparticles, although active in the reaction, are not responsible for the high activity observed for the most active precatalyst [Cp*Ir(IMe) 2Cl]BF4 (6). For efficient catalysis, it was found necessary to have both NHCs in monodentate form; tying them together in a bis-NHC chelate ligand gave greatly reduced activity. The kinetics of the base-assisted reaction showed induction periods as well as deactivation processes, and H/D scrambling experiments cast some doubt on the classical monohydride mechanism. © 2013 American Chemical Society
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