Robust and Selective Metathesis Catalysts for Oleochemical Applications

The screening of known ruthenium alkylidene complexes in the ethenolysis of methyl oleate shows that the Grubbs-type Ru-catalysts bearing two phosphine donor ligands exhibit high selectivity for the formation of terminal olefins. Second-generation ruthenium catalysts promote almost the exclusive formation of self-metathesis products. Complexes with chelating alkylidene moieties (Hoveyda-type) generally exhibit poor selectivity for both ethenolysis and self-metathesis products. Complexes 2b and 2d promote self-metathesis of methyl oleate with catalyst loading of 2?ppm without significant isomerization up to 110?°C (using 2d) and up to 150?°C (using 2b).     

Towards an evaluation framework for knowledge management systems

In this paper we develop an evaluation framework for Knowledge Management Systems (KMS). The framework builds on the theoretical foundations underlying organizational Knowledge Management (KM) to identify key KM activities and the KMS capabilities required to support each activity. These capabilities are then used to form a benchmark for evaluating KMS. Organizations selecting KMS can use the framework to identify gaps and overlaps in the extent to which the capabilities provided and utilized by their current KMS portfolio meet the KM needs of the organization. Other applications of the framework are also discussed.

Review of Against all odds: Holocaust survivors and the successful lives they made in America.

Reviews the book, Against all odds: Holocaust survivors and the successful lives they made in America by William B. Helmreich (1992). In this book, Helmreich presents us with the results of a large-scale study of the adjustment of Holocaust survivors—Jews who spent World War II under the Third Reich, either in death camps, ghettoes, or in hiding. The research is based on 170 in-depth interviews of randomly selected survivors who had emigrated to America after the war and a control group of American Jews. Helmreich tells us how the survivors managed to start a new life. He highlights their amazing ability to forge strong family bonds again after seeing all their relatives murdered. He illustrates how, in spite of limited education due to the harrowing lost years in concentration camps, the survivors achieved occupational success. He shows us the survivors' capacity for friendship and altruism and their astounding ability to live with their dreadful memories of murder and torture. Against all odds is clearly written, buttressing important generalizations with illuminating vignettes and accounts of individual experiences. It gives us an understanding of how people who have lived through appalling calamity can regain a hold on life. This book will be useful for clinicians working with anyone who has survived tragedy. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Air-drying of human leucocytes for scanning electron microscopy using the GTGO procedure

The utilization of tannic acid and guanidine hydrochloride as mordants for better osmium binding has been shown to serve as an excellent alternative to metal coating of organ tissue specimens for scanning electron microscopy (SEM). The present report describes the GTGO procedure, a modification of the TAO technique introduced by Murakami et al. (1977, 1978), which we have found successful for the preparation of air dried peripheral blood leucocytes for SEM studies. Air dried, GTGO-treated leucocytes show excellent preservation of surface features with minimal cell shrinkage. When critical point dried, GTGO-treated cells are examined, they also show less shrinkage than cells prepared with standard glutaraldehyde fixation and critical point drying. The potential application of this air drying procedure (GTGO-AD) to other soft biological specimens is currently under investigation. This technique is recommended as a new and effective air drying procedure for the successful preparation of cells for SEM.     

Strategies for oxidation catalyzed by polyoxometalates at the interface of homogeneous and heterogeneous catalysis

A basic premise behind the use of polyoxometalates in oxidation chemistry is the fact that polyoxometalates are oxidatively stable. This, a priori, leads to the conclusion that for practical purposes polyoxometalates would have distinct advantages over widely investigated organometallic compounds that are vulnerable to decomposition due to oxidation of the ligand bound to the metal center. Since polyoxometalate synthesis is normally carried out in water by mixing the stoichiometrically required amounts of monomeric metal salts and adjusting the pH to a specific acidic value many structure types are accessible by variation of the reaction stoichiometry, replacement of one or more addenda atoms with other transition or main group metals, and pH control. The structural variety available has enabled the use of polyoxometalates as catalysts for oxidation of hydrocarbons and functionalized organic substrates (alcohols, amines, sulfides, etc.) with a wide range of oxygen donors ranging from molecular oxygen, hydrogen peroxide, nitrous oxide, ozone, alkyl hydroperoxides, periodate, sulfoxide and others. The wide purview of oxidation reactions is enabled because the structural variety leads to oxidation through a number of different mechanistic motifs.From a synthetic organic point of view, the most applicable uses of polyoxometalates as catalysts involve the green oxygen donors – hydrogen peroxide and molecular oxygen. Since practical applications are in hand in this area, practical considerations concerned with catalyst recycle and/or recovery and the elimination of environmentally problematic solvents are also coming to the forefront. In this paper, we will present some of our activities in the area of catalyst engineering for catalytic synthetic applications by polyoxometalates including: (a) catalytic mesoporous solids from organic-polyoxometalate hybrid materials, (b) fluorous phase polyoxometalates with and without fluorous solvents and (c) the use of aqueous biphasic media for oxidation with hydrogen peroxide.     

Yeast hexokinase isoenzyme ScHxk2: stability of a two-domain protein with discontinuous domains

The hexokinase isoenzyme 2 of Saccharomyces cerevisiae (ScHxk2) represents an archetype of a two-domain protein with the active site located in a cleft between the two domains. Binding of the substrate glucose results in a rigid body movement of the two domains leading to a cleft closure of the active site. Both domains of this enzyme are composed of discontinuous peptide sequences. This structural feature is reflected in the stability and folding of the ScHxk2 protein. Structural transitions induced by urea treatment resulted in the population of a thermodynamically stable folding intermediate, which, however, does not correspond to a molecule with one domain folded and the other unfolded. As demonstrated by different spectroscopic techniques, both domains are structurally affected by the partial denaturation. The intermediate possesses only 40% of the native secondary structural content and a substantial increase in the Stokes radius as judged by circular dichroism and dynamic light scattering analyses. One-dimensional 1H NMR data prove that all tryptophan residues are in a non-native environment in the intermediate, indicating substantial changes in the tertiary structure. Still, the intermediate possesses quite a high stability for a transition intermediate of about ΔG = -22 kJ mol?1.     

Rheological properties and stability of NMP based cathode slurries for lithium ion batteries

Slurries for the manufacturing of cathodes for lithium ion batteries are compared regarding to their colloidal stability by means of rheology. Model formulations with nanoscaled LiFePO₄ (LFP) and micron scaled Li(Ni,Mn,Co)O₂ (NMC) were prepared by using N-methyl-2-pyrrolidone (NMP) as solvent. Polyvinylidene difluoride (PVDF) binder and carbon black (CB) conducting additive were added at typical amounts of a few weight percent. The influence of these inactive electrode components on the physical stability of the dispersions was investigated by steady state and oscillation experiments. It is demonstrated that the addition of a high molecular weight PVDF binder is sufficient to establish gel formation by bridging flocculation in case of the nanoscaled cathode material. For the larger micron scaled particles, the formation of a stable coagulated state is also feasible but it requires the combination of a particulate CB gel and a strengthening PVDF polymer network.     

The Enhancement of Metathesis Catalysts via Alkylidene and N-Heterocyclic Carbene Ligand Optimization

Olefin metathesis has the potential to greatly improve the efficiency of organic synthesis. However, its commercial growth has been hampered by the difficulties of catalyst production, a complicated patent situation and expensive licenses. This work describes the design of robust and reproducible metathesis catalysts, deemed royalty free (RF), and their use for ring closing metathesis.