384 research outputs found

    Hydrogenative Cyclopropanation and Hydrogenative Metathesis

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    The unusual geminal hydrogenation of a propargyl alcohol derivative with [CpXRuCl] as the catalyst entails formation of pianostool ruthenium carbenes in the first place; these reactive intermediates can be intercepted with tethered alkenes to give either cyclopropanes or cyclic olefins as the result of a formal metathesis event. The course of the reaction is critically dependent on the substitution pattern of the alkene trap

    Biodegradable, lignin-based encapsulation enables delivery of Trichoderma reesei with programmed enzymatic release against grapevine trunk diseases

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    Antagonistic fungi such as Trichoderma reesei are promising alternatives to conventional fungicides in agriculture. This is especially true for worldwide occurring grapevine trunk diseases, causing losses of US$1.5 billion every year, at which conventional fungicides are mostly ineffective or prohibited by law. Yet, applications of Trichoderma against grapevine trunk diseases are limited to preventive measures, suffer from poor shelf life, or uncontrolled germination. Therefore, we developed a mild and spore-compatible layer-by-layer assembly to encapsulate spores of a new mycoparasitic strain of T. reesei IBWF 034-05 in a bio-based and biodegradable lignin shell. The encapsulation inhibits undesired premature germination and enables the application as an aqueous dispersion via trunk injection. First injected into a plant, the spores remain in a resting state. Second, when lignin-degrading fungi infect the plant, enzymatic degradation of the shell occurs and germination is selectively triggered by the pathogenic fungi itself, which was proven in vitro. Germinated Trichoderma antagonizes the fungal pathogens and finally supplants them from the plant. This concept enables Trichoderma spores for curative treatment of esca, one of the most infective grapevine trunk diseases worldwide

    C–H Insertion via Ruthenium Catalyzed gem-Hydrogenation of 1,3-Enynes

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    gem-Hydrogenation of an internal alkyne with the aid of [Cp*RuCl]4 as the precatalyst is a highly unorthodox transformation, in which one C atom of the triple bond is transformed into a methylene group, whereas the second C atom gets converted into a ruthenium carbene. In the case of 1,3-enynes bearing a propargylic steering substituent as the substrates, the reaction occurs regioselectively, giving rise to vinyl carbene complexes that adopt interconverting η1/η3-binding modes in solution; a prototypical example of such a reactive intermediate was characterized in detail by spectroscopic means. Although both forms are similarly stable, only the η3-vinyl carbene proved kinetically competent to insert into primary, secondary, or tertiary C–H bonds on the steering group itself or another suitably placed ether, acetal, orthoester, or (sulfon)amide substituent. The ensuing net hydrogenative C–H insertion reaction is highly enabling in that it gives ready access to spirocyclic as well as bridged ring systems of immediate relevance as building blocks for medicinal chemistry. Moreover, the reaction scales well and lends itself to the formation of partly or fully deuterated isotopologues. Labeling experiments in combination with PHIP NMR spectroscopy (PHIP = parahydrogen induced polarization) confirmed that the reactions are indeed triggered by gem-hydrogenation, whereas kinetic data provided valuable insights into the very nature of the turnover-limiting transition state of the actual C–H insertion step

    Optical spectroscopy and the nature of the insulating state of rare-earth nickelates

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    Using a combination of spectroscopic ellipsometry and DC transport measurements, we determine the temperature dependence of the optical conductivity of NdNiO3_3 and SmNiO3_{3} films. The optical spectra show the appearance of a characteristic two-peak structure in the near-infrared when the material passes from the metal to the insulator phase. Dynamical mean-field theory calculations confirm this two-peak structure, and allow to identify these spectral changes and the associated changes in the electronic structure. We demonstrate that the insulating phase in these compounds and the associated characteristic two-peak structure are due to the combined effect of bond-disproportionation and Mott physics associated with half of the disproportionated sites. We also provide insights into the structure of excited states above the gap.Comment: 12 pages, 13 figure

    ResistenzzĂŒchtung in Dresden-Pillnitz - Der Apfel

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    The Institute of Fruit Breeding has a long tradition in breeding resistant apple cultivars. Systematic resistance breeding started in the 1930 ties in MĂŒncheberg. Material developed in MĂŒncheberg was transferred in the 1970 ties to the Institute for Fruit Research, the antecessor of the Institute of Fruit Breeding. Based on this material, a couple of multiple resistant cultivars were generated. The time schedule for combining biotic and abiotic resistant traits which demonstrates the long-lasting period necessary for systematic resistance breeding is given. An overview of resistant cultivars of Dresden-Pillnitz and the respective resistant traits is presented. This assortment of cultivars was developed to provide a resistant cultivar for each ripening group and every application in fruit growing. Modern resistance breeding is focused on quality and combination of different resistance genes for each pathogene to achieve durable resistance. Selection is facilitated by genetic markers. Likewise the look for new resistance genes, the analyses of genetics and the development of basic material are main areas of interest. Practical approaches in apple breeding to reach these aims are reported

    Cultivo orgĂąnico do morangueiro: densidade de plantio, crescimento e produtividade de cultivares de ?dia neutro?

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    Alkyne gem‐Hydrogenation: Formation of Pianostool Ruthenium Carbene Complexes and Analysis of Their Chemical Character

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    Parahydrogen (p‐H2) induced polarization (PHIP) NMR spectroscopy showed that [CpXRu] complexes with greatly different electronic properties invariably engage propargyl alcohol derivatives into gem‐hydrogenation with formation of pianostool ruthenium carbenes; in so doing, less electron rich CpX rings lower the barriers, stabilize the resulting complexes and hence provide opportunities for harnessing genuine carbene reactivity. The chemical character of the resulting ruthenium complexes was studied by DFT‐assisted analysis of the chemical shift tensors determined by solid‐state 13C NMR spectroscopy. The combined experimental and computational data draw the portrait of a family of ruthenium carbenes that amalgamate purely electrophilic behavior with characteristics more befitting metathesis‐active Grubbs‐type catalysts

    Multiple micro-optical atom traps with a spherically aberrated laser beam

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    We report on the loading of atoms contained in a magneto-optic trap into multiple optical traps formed within the focused beam of a CO_{2} laser. We show that under certain circumstances it is possible to create a linear array of dipole traps with well separated maxima. This is achieved by focusing the laser beam through lenses uncorrected for spherical aberration. We demonstrate that the separation between the micro-traps can be varied, a property which may be useful in experiments which require the creation of entanglement between atoms in different micro-traps. We suggest other experiments where an array of these traps could be useful.Comment: 10 pages, 3 figure

    Cultivo e uso de abĂłboras ornamentais.

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