164 research outputs found

    Pd-catalyzed ethylene/methyl acrylate cooligomerization: the effect of a new nonsymmetric alfa-diimine with the 1,4-diazabutadiene skeleton

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    Palladium(II) complexes with a nonsymmetric bis(aryl-imino)diazabutadiene ligand (ArDAB) have been synthesized and characterized. The new ligand is featured by one aryl ring substituted in ortho positions with methyl groups and the other ring bearing a trifluoromethyl group on the meta positions, leading to a subtle steric and electronic difference on the two nitrogen-donor atoms. This peculiar substitution makes the direct synthesis of the ligand not feasible, and the relevant Pd(II) complex, [Pd(CH3)Cl(ArDAB)], is directly obtained through a template reaction. The corresponding cationic complexes with either acetonitrile or dimethyl sulfoxide have been synthesized and characterized. The X-ray crystal structure of a palladium complex with an \uf061-diimine and dimethyl sulfoxide is reported. The monocationic complexes have been tested as precatalysts in the ethylene/methyl acrylate cooligomerization under mild reaction conditions of temperature and pressure. The comparison with the catalytic behavior of the precatalysts with the corresponding nonsymmetric ArBIAN ligand indicated that the active species with the currently investigated ligand is more productive, leading to the formation of ethylene oligomers and ethylene/methyl acrylate cooligomers

    Imino-phospine palladium (II) and platinum (II) complexes: Synthesis, molecular structures and evaluation as antitumor agents

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    The imino-phosphine ligands L1 and L2 were prepared via condensation reaction of 2-(diphenylphosphino) benzaldehyde with substituted anilines and obtained in very good yields. An equimolar reaction of L1 and L2 with either PdCl2(cod) or PtCl2(cod) gave new palladium(II) and platinum(II) complexes 1–4. The compounds were characterized by elemental analysis, IR, 1H and 31P NMR spectroscopy. The molecular structures of 2, 3 and 4 were confirmed by X-ray crystallography. All the three molecular structures crystallized in monoclinic C2/c space system. The coordination geometry around the palladiumand platinumatoms in respective structures exhibited distorted square planar geometry at the metal centers. The complexes were evaluated in vitro for their cytotoxic activity against human breast (MCF-7) and human colon (HT-29) cancer cells, and they exhibited growth inhibitory activities and selectivity that were superior to the standard compound cisplatin.Web of Scienc

    Association between co-authorship network and scientific productivity and impact indicators in academic medical research centers: A case study in Iran

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    <p>Abstract</p> <p>Background</p> <p>We aimed to examine the co-authorship networks in three successful Iranian academic research centers, in order to find the association between the scientific productivity and impact indicators with network features in a case study.</p> <p>Methods</p> <p>We searched for English articles of the three research centers. We drew co-authorship maps of each center and calculated social network measures.</p> <p>Results</p> <p>The collaboration networks in centers shared many structural features, including a "star-like" pattern of relations. Centers with more successful scientific profile showed denser and more cooperative networks. Key figures in each center were interviewed for their understandings of the reasons for the emergence of these patterns.</p> <p>Conclusion</p> <p>Star shape network structure and dependency on a single big member is a common feature observed in our case study. Scientific output measures correlate with the network structure of research centers. Network analysis seems a useful method to explore the subtle scientific contexts in research organizations.</p

    The embedding of transnational entrepreneurs in diaspora networks:Leveraging the assets of foreignness

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    In this paper we examine how foreign actors capitalize on their ethnic identity to gain skills and capabilities that enable them to operate in a new and strange environment. We explore the mechanisms by which Bulgarian entrepreneurs in London use their ethnic identity to develop competitive advantage and business contacts. We find that the entrepreneurs studied gain access to a diaspora network, which enables them to develop essential business capabilities and integrate knowledge from both home and host country environments. The diaspora community possesses a collective asset (transactive memory) that allows its members to remove competition from the interfirm level to the network level (i.e., diaspora networks vs. networks of native businesspeople). Additionally, the cultural identity and networks to which community members have access provide bridging capabilities that allow diaspora businesspeople to make links to host country business partners and thus embed themselves in the host country environment. Thus, this paper adds to the growing body of work showing how foreignness can serve as an asset in addition to its better-known role as a liability

    Palladium(II) complexes of tridentate bis(benzazole) ligands: Structural, substitution kinetics, DNA interactions and cytotoxicity studies.

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    Reactions of 2,6-bis(benzimidazol-2-yl)pyridine (L1), 2,6-bis(benzoxazol-2-yl)pyridine (L2), and 2,6-bis(benzothiazol-2-yl)pyridine (L3) with [Pd(NCMe)2Cl2] in the presence of NaBF4 afforded the corresponding Pd(II) complexes, [Pd(L1)Cl]BF4, PdL1; [Pd(L2)Cl]BF4, PdL2; [Pd(L3)Cl]BF4, PdL3; respectively, while reaction of bis[(1H-benzimidazol-2-yl)methyl]amine (L4) with [Pd(NCMe)2Cl2] afforded complex [Pd(L4)Cl]Cl, PdL4. Characterisation of the complexes was accomplished using NMR, IR, MS, elemental analyses and single crystal X-ray crystallography. Ligand substitution kinetics of these complexes by biological nucleophiles thiourea (Tu), L-methionine (L-Met) and guanosine 5'-diphosphate disodium salt (5-GMP) were examined under pseudo-first order conditions. The reactivity of the complexes decreased in the order: PdL1 > PdL2 > PdL3 > PdL4, ascribed to electronic effects. Density functional theory (DFT) supported this trend. Studies of interaction of the Pd(II) complexes with calf thymus DNA (CT-DNA) revealed strong binding affinities via intercalative binding mode. Molecular docking studies established associative non-covalent interactions between the Pd complexes and DNA. The in vitro cytotoxic activities of PdL1-PdL4 were assessed in cancer cell lines HeLa and MRC5-SV2 and a normal cell line MRC-5, using the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. PdL1 exhibited cytotoxic potency and selectivity against HeLa cell that was comparable to cisplatin's. Complex PdL1, unlike cisplatin, did not significantly induce caspase-dependent apoptosis
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