4,135 research outputs found

    Contract Exchange Structures: Measures for Multi-Mode Affiliation Networks

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    poster abstractGovernment increasingly contracts out multiple social service programs to a single organization, yet has little understanding of the risk associated with dependence on a single organization. In this paper, I use network concepts to develop structural measures for underlying, common affiliations among programs in service delivery networks. Understanding the underlying structure of common affiliations among contracted programs has practical implications for governance, in terms of understanding government dependence on a particular organization, effects of structure on an individual programs’ incentive to perform, and risk associated with organizational failure. This paper makes three contributions to the public administration literature. First, I explore the influence of structure on individual incentives to perform along with risks of organizational failure for government-funded services. Second, I make the case that contracts are embedded in larger networked system of exchange. Third, I developed a measure that captures the breadth and depth organizational competition within and across sub-networks in multi-mode affiliation networks

    Measuring Risks of Organizational Failure in Contract Exchange Structures

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    Governmental agencies increasingly contract out service delivery, but have little understand- ing of the systemic risk associated with dependence on contractors in service delivery networks. In this study, affiliation network concepts are used to develop a structural index of government dependence on actors in service delivery networks without joint service delivery. Networks in- clude direct links to government funders and indirect links among contracted programs based on shared parent organizations. Understanding the structure of governance arrangements has practical implications for governance, in terms of understanding government dependence on a particular contractor and the risk associated with organizational failure of those contractors. Governance structures may also influence individual incentives to perform. This study makes two contributions to the governance literature. First, the study offers conceptualization of con- tracted programs as networked structures of exchange even where joint production does not oc- cur. Second, an index is proposed to capture the position of individual organizations in complex networks of exchange with government. This index can be used to determine the dependence of government on a specific actor in the service delivery network along with the risk to the network should a particular organization fail. This index can also be incorporated into statistical models of contract performance

    A novel, efficient synthesis of N-aryl pyrroles via reaction of 1-boronodienes with arylnitroso compounds

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    A one-pot hetero-Diels–Alder/ring contraction cascade is presented from the reaction of 1-boronodienes and arylnitroso derivatives to derive N-arylpyrroles in moderate to good yields (up to 82%)

    Super hygroscopic non-stoichiometric cerium oxide particles as electrode component for PEM fuel cells

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    The design of highly efficient promoters for the oxygen reduction reaction (ORR) is an important challenge in the large-scale distribution of proton exchange membrane (PEM) fuel cells. Hygroscopic cerium oxide (CeO2) is here proposed as co-catalyst in combination with Pt. Physical chemical characterizations, by means of X-ray diffraction, vibrational spectroscopy, morphological and thermal analyses, were carried out, demonstrating high water affinity of the synthesized CeO2 nanoparticles. Composite catalysts (i. e., Pt : CeO2 1 : 0.5 and 1 : 1 wt:wt), were studied by either rotating disk electrode (RDE) and fuel cell tests performed at 80 °C and 110 °C. Interestingly, the cell adopting the Pt : CeO2 1 : 0.5 catalyst enabled the achievement of high power densities reaching ∼80 and ∼35 mW cm−2 under low relative humidity and high temperatures. This result demonstrates that tuning material surface properties (e. g. oxygen vacancies) could significantly boost the electrochemical performance of cathodes as a combined result of optimized water retention and improved ORR kinetic

    Increased Expression of Autophagy-Related Genes in Alzheimer’s Disease—Type 2 Diabetes Mellitus Comorbidity Models in Cells

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    The association between Alzheimer’s disease (AD) and type 2 diabetes mellitus (T2DM) has been extensively demonstrated, but despite this, the pathophysiological mechanisms underlying it are still unknown. In previous work, we discovered a central role for the autophagy pathway in the common alterations observed between AD and T2DM. In this study, we further investigate the role of genes belonging to this pathway, measuring their mRNA expression and protein levels in 3xTg-AD transgenic mice, an animal model of AD. Moreover, primary mouse cortical neurons derived from this model and the human H4Swe cell line were used as cellular models of insulin resistance in AD brains. Hippocampal mRNA expression showed significantly different levels for Atg16L1, Atg16L2, GabarapL1, GabarapL2, and Sqstm1 genes at different ages of 3xTg-AD mice. Significantly elevated expression of Atg16L1, Atg16L2, and GabarapL1 was also observed in H4Swe cell cultures, in the presence of insulin resistance. Gene expression analysis confirmed that Atg16L1 was significantly increased in cultures from transgenic mice when insulin resistance was induced. Taken together, these results emphasise the association of the autophagy pathway in AD-T2DM co-morbidity, providing new evidence about the pathophysiology of both diseases and their mutual interaction

    Rhodium-catalyzed asymmetric hydrogenation of olefins with PhthalaPhos, a new class of chiral supramolecular ligands

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    A library of 19 binol-derived chiral monophosphites that contain a phthalic acid diamide group (Phthala- Phos) has been designed and synthesized in four steps. These new ligands were screened in the rhodium-catalyzed enantioselective hydrogenation of prochiral dehydroamino esters and enamides. Several members of the library showed excellent enantioselectivity with methyl 2-acetamido acrylate (6 ligands gave >97% ee), methyl (Z)-2- acetamido cinnamate (6 ligands gave >94% ee), and N-(1-phenylvinyl)acetamide (9 ligands gave >95% ee), whilst only a few representatives afforded high enantioselectivities for challenging and industrially relevant substrates N-(3,4-dihydronaphthalen-1- yl)-acetamide (96% ee in one case) and methyl (E)-2-(acetamidomethyl)-3- phenylacrylate (99% ee in one case). In most cases, the new ligands were more active and more stereoselective than their structurally related monodentate phosphites (which are devoid of functional groups that are capable of hydrogen-bonding interactions). Control experiments and kinetic studies were carried out that allowed us to demonstrate that hydrogen-bonding interactions involving the diamide group of the PhthalaPhos ligands strongly contribute to their outstanding catalytic properties. Computational studies carried out on a rhodium precatalyst and on a conceivable intermediate in the hydrogenation catalytic cycle shed some light on the role played by hydrogen bonding, which is likely to act in a substrate-orientation effect. \ua9 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim

    Towards a More Sustainable Photocatalyzed α-Arylation of Amines: Green Solvents, Catalyst Recycling and Low Loading

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    A more sustainable and efficient protocol for the photocatalytic α-amino arylation promoted by fac-Ir(ppy)3 was developed. Three noteworthy results were achieved: i) the replacement of toxic medium DMA with the greener solvents NBP and NHP, and the concurrent improvement of the process efficiency by lowering both the amine and the base amount; ii) the development of a recycling protocol for both the sustainable solvent NHP and the commercially available costly photocatalyst fac-Ir(ppy)3, achieving environmental and economic benefits. This approach to the photocatalyst recovery avoids very demanding catalyst structural modifications; iii) the protocol in green solvents proved to be scalable up to 10 mmol of limiting reagent, maintaining excellent performance also lowering the photocatalyst loading down to 0.05 mol%. This is the first example of photocatalytic α-arylation of amines promoted by such a low amount of catalyst. Lastly, the versatility of this approach was demonstrated by extending the use of the green solvent NBP to another photoredox process

    Identification of genes and gene pathways associated with major depressive disorder by integrative brain analysis of rat and human prefrontal cortex transcriptomes

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    Despite moderate heritability estimates, progress in uncovering the molecular substrate underpinning major depressive disorder (MDD) has been slow. In this study, we used prefrontal cortex (PFC) gene expression from a genetic rat model of MDD to inform probe set prioritization in PFC in a human post-mortem study to uncover genes and gene pathways associated with MDD. Gene expression differences between Flinders sensitive (FSL) and Flinders resistant (FRL) rat lines were statistically evaluated using the RankProd, non-parametric algorithm. Top ranking probe sets in the rat study were subsequently used to prioritize orthologous selection in a human PFC in a case?control post-mortem study on MDD from the Stanley Brain Consortium. Candidate genes in the human post-mortem study were then tested against a matched control sample using the RankProd method. A total of 1767 probe sets were differentially expressed in the PFC between FSL and FRL rat lines at (qless than or equal to0.001). A total of 898 orthologous probe sets was found on Affymetrix?s HG-U95A chip used in the human study. Correcting for the number of multiple, non-independent tests, 20 probe sets were found to be significantly dysregulated between human cases and controls at qless than or equal to0.05. These probe sets tagged the expression profile of 18 human genes (11 upregulated and seven downregulated). Using an integrative rat?human study, a number of convergent genes that may have a role in pathogenesis of MDD were uncovered. Eighty percent of these genes were functionally associated with a key stress response signalling cascade, involving NF-?B (nuclear factor kappa-light-chain-enhancer of activated B cells), AP-1 (activator protein 1) and ERK/MAPK, which has been systematically associated with MDD, neuroplasticity and neurogenesis
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