Ligand design for site-selective installation of Pd and Pt centers to generate homo- and heteropolymetallic motifs

The modular synthesis of a series of nitrogen-rich polydentate ligands that feature a common pincer-type framework is reported. These ligands allow for site-selective installation of palladium and platinum to give rise to bi- and trimetallic complexes that have d^(8)–d^(8) interactions

Superconductivity in Weyl semimetal NbP: Bulk vs. surface

Transition metal monopnictides belong to the new class of semimetals where the bulk properties are determined by the presence of pairs of nodes with different chirality formed by linear dispersive states in the k-space. Beside the anomaly in the bulk magnetotransport superconductivity is frequently found in some Weyl semimetals. We found signatures of superconductivity in ac and dc magnetization measurements of highly pure and stoichiometric NbP powder. We determined the lower and upper critical field and the Ginzburg-Landau parameter. The relative small superconducting volume fraction is related to either effect of finite grain size and/or surface superconductivity. The last mentioned may originate from either off stoichiometric (Nb-rich) surface layers or a strained surface with different electronic properties. Furthermore the intrinsic normal state susceptibility is determined taking into account a paramagnetic contribution of a few ppm of magnetic impurities

Past the Edge of the Forest

This fictional work traces the superstitions around No Name Forest as members of the town just beyond the forest begin to disappear. While set in present day, the piece draws on the way fairy tales use the inexplicable and strange to engage readers in questioning the human experience. The story details the disappearances of several people from the town of Little Haven. While each of these disappearances are presented in individual tales, they are linked together through the voice of a girl who has been tracking the disappearances. In search of the father who abandoned her, Gwynn Halpert is interested in discovering the truth of No Name Forest. Through various characters’ interactions with the forest, the story interrogates the complicated nature of desire

A CO-Derived Iron Dicarbyne That Releases Olefin upon Hydrogenation

An iron diphosphineborane platform that was previously reported to facilitate a high degree of N_2 functionalization is herein shown to effect reductive CO coupling. Disilylation of an iron dicarbonyl precursor furnishes a structurally unprecedented iron dicarbyne complex. Several complexes related to this process are also characterized which allows for a comparative analysis of their respective Fe–B and Fe–C bonding. Facile hydrogenation of the iron dicarbyne at ambient temperature and 1 atm H_2 results in release of a CO-derived olefin

H–H and Si–H Bond Addition to Fe≡NNR_2 Intermediates Derived from N_2

The synthesis and characterization of Fe–diphosphineborane complexes are described in the context of N_2 functionalization chemistry. Iron aminoimides can be generated at room temperature under 1 atm N_2 and are shown to react with E–H bonds from PhSiH_3 and H_2. The resulting products derive from delivery of the E fragment to Nα and the H atom to B. The flexibility and lability of the Fe–BPh interactions in these complexes engender this reactivity

Authigenic carbonates from the Cascadia subduction zone and their relation to gas hydrate stability

Authigenic carbonates are intercalated with massive gas hydrates in sediments of the Cascadia margin. The deposits were recovered from the uppermost 50 cm of sediments on the southern summit of the Hydrate Ridge during the RV Sonne cruise SO110. Two carbonate lithologies that differ in chemistry, mineralogy, and fabric make up these deposits. Microcrystalline high-magnesium calcite (14 to 19 mol% MgCO3) and aragonite are present in both semiconsolidated sediments and carbonate-cemented clasts. Aragonite occurs also as a pure phase without sediment impurities. It is formed by precipitation in cavities as botryoidal and isopachous aggregates within pure white, massive gas hydrate. Variations in oxygen isotope values of the carbonates reflect the mineralogical composition and define two end members: a Mg-calcite with δ18O =4.86‰ PDB and an aragonite with δ18O =3.68‰ PDB. On the basis of the ambient bottom-water temperature and accepted equations for oxygen isotope fractionation, we show that the aragonite phase formed in equilibrium with its pore-water environment, and that the Mg-calcite appears to have precipitated from pore fluids enriched in 18O. Oxygen isotope enrichment probably originates from hydrate water released during gas-hydrate destabilization

Platelet polyphosphate induces fibroblast chemotaxis and myofibroblast differentiation

BackgroundPlatelets secrete many pro‐wound healing molecules such as growth factors and cytokines. We found that releasates from activated human platelets induced the differentiation of cultured murine and human fibroblasts into a myofibroblast phenotype. Surprisingly, most of this differentiation‐inducing activity was heat‐stable, suggesting it was not due to the protein component of the releasates. Inorganic polyphosphate is a major constituent of platelet‐dense granules and promotes blood coagulation and inflammation.ObjectivesWe aim to investigate the contribution of polyphosphate on myofibroblast differentiating activity of platelet releasates.MethodsUsing NIH‐3T3 cells and primary human fibroblasts, we examined the effect of human platelet releasates and chemically synthesized polyphosphate on fibroblast differentiation and migration.ResultsWe found that the myofibroblast‐inducing activity of platelet releasates was severely attenuated after incubation with a polyphosphate‐degrading enzyme, and that fibroblasts responded to platelet‐sized polyphosphate by increased levels of α‐smooth muscle actin, stress fibers, and collagen. Furthermore, fibroblasts were chemotactic toward polyphosphate.ConclusionsThese findings indicate that platelet‐derived polyphosphate acts as a cell signaling molecule by inducing murine and human fibroblasts to differentiate into myofibroblasts, a cell type known to drive both wound healing and fibrosing diseases. Polyphosphate therefore not only promotes early wound responses through enhancing fibrin clot formation, but also may play roles in the later stages of wound healing, and, potentially, progression of fibrotic diseases, by recruiting fibroblasts and inducing their differentiation into myofibroblasts.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/163376/2/jth15066_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/163376/1/jth15066.pd