Hydrogenative Cyclopropanation and Hydrogenative Metathesis

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

Disentangling lattice and electronic contributions to the metal–insulator transition from bulk vs. layer confined RNiO₃

In complex oxide materials, changes in electronic properties are often associated with changes in crystal structure, raising the question of the relative roles of the electronic and lattice effects in driving the metal–insulator transition. This paper presents a combined theoretical and experimental analysis of the dependence of the metal–insulator transition of NdNiO3 on crystal structure, specifically comparing properties of bulk materials to 1- and 2-layer samples of NdNiO3 grown between multiple electronically inert NdAlO3 counterlayers in a superlattice. The comparison amplifies and validates a theoretical approach developed in previous papers and disentangles the electronic and lattice contributions, through an independent variation of each. In bulk NdNiO3, the correlations are not strong enough to drive a metal–insulator transition by themselves: A lattice distortion is required. Ultrathin films exhibit 2 additional electronic effects and 1 lattice-related effect. The electronic effects are quantum confinement, leading to dimensional reduction of the electronic Hamiltonian and an increase in electronic bandwidth due to counterlayer-induced bond-angle changes. We find that the confinement effect is much more important. The lattice effect is an increase in stiffness due to the cost of propagation of the lattice disproportionation into the confining material

Low-energy description of the metal-insulator transition in the rare-earth nickelates

We propose a simple theoretical description of the metal-insulator transition of rare-earth nickelates. The theory involves only two orbitals per nickel site, corresponding to the low-energy antibonding eg states. In the monoclinic insulating state, bond-length disproportionation splits the manifold of eg bands, corresponding to a modulation of the effective on-site energy. We show that, when subject to a local Coulomb repulsion U and Hund's coupling J, the resulting bond-disproportionated state is a paramagnetic insulator for a wide range of interaction parameters. Furthermore, we find that when U−3J is small or negative, a spontaneous instability to bond disproportionation takes place for large enough J. This minimal theory emphasizes that a small or negative charge-transfer energy, a large Hund's coupling, and a strong coupling to bond disproportionation are the key factors underlying the transition. Experimental consequences of this theoretical picture are discussed

Resistance Breeding in Apple at Dresden-Pillnitz

Resistance breeding in apple has a long tradition at the Institute of Fruit Breeding now Julius Kuehn-institute in Dresden-Pillnitz. The breeding was aimed at the production of multiple resistance cultivars to allow a more sustainable and environmentally friendly production of apple. In the last decades a series of resistant cultivars (Re®-cultivars) bred in Dresden-Pillnitz has been released, ‘Recolor’ and ‘Rekarda’ in 2006. The main topic in the resistance breeding programme was scab resistance and the donor of scab resistance in most cultivars was Malus x floribunda 821. Due to the development of strains that are able to overcome resistance genes inherited by M. x floribunda 821 and due to the fact that single resistance genes can be broken easily, pyramiding of resistance genes is necessary. Besides scab, fire blight and powdery mildew are the main disease for which a pyramiding of genes is aspired in Pillnitz. Biotechnical approaches are necessary for the early detection of pyramided resistance genes in breeding clones. This paper will give an overview of the resistance breeding of apple in Pillnitz and the methods used

Breeding of resistant strawberry cultivars for organic fruit production – Diallel crossing strategies and resistance tests for Botrytis cinerea and Xanthomonas fragariae

Organic strawberry production suffers from high yield losses caused by numerous fungal and bacterial diseases. Two of the most important diseases are the grey mould disease caused by Botrytis cinerea Pers. (teleomorph Botryotinia fuckeliana), and the bacterial angular leaf spot disease caused by Xanthomonas fragariae (Kennedy & King). Beside cultivation methods and organic plant protection measures, the development of resistant cultivars seems to be the most promising strategy in order to improve the productivity in organic strawberry cultivation. Therefore, we established resistance tests to determine resistant and susceptible strawberry cultivars and breeding selections. In a first run, 40 different cultivars and selections were tested for their susceptibility towards B. cinerea by artificial inoculation of fruits and leaves and evaluation of the disease symptoms. Plants of 40 cultivars were tested for susceptibility to X. fragariae by artificial inoculation in the greenhouse. In a diallel crossing approach, 12 commonly cultivated strawberry cultivars have been crossed reciprocally and propagated in a field trial. Important characteristics of the progeny such as ripening time, yield, morphological traits and occurrence of diseases have been evaluated for a period of two consecutive years and lead to the determination of general (GCA) and specific (SCA) combining abilities. Together with the results of the resistance tests we identified a set of genotypes that show resistant characteristics towards B. cinerea and might be suitable for use in organic cultivation systems. Furthermore, they can be used for targeted breeding experiments in the future

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

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

A phased array-based method for damage detection and localization in thin plates

A method for damage localization based on the phased array idea has been developed. Four arrays oftransducers are used to perform a beam-forming procedure. Each array consists of nine transducersplaced along a line, which are able to excite and register elastic waves. The A0 Lamb wave mode hasbeen chosen for the localization method. The arrays are placed in such a way that the angulardifference between them is 458 and the rotation point is the middle transducer, which is common for allthe arrays. The idea has been tested on a square aluminium plate modeled by the Spectral Element Method. Two types of damage were considered, namely distributed damage, which was modeled asstiffness reduction, and cracks, modeled as separation of nodes between selected spectral elements.The plate is excited by a wave packet. The whole array system is placed in the middle of the plate.Each linear phased array in the system acts independently and produces maps of a scanned fieldbased on the beam-forming procedure. These maps are made of time signals (transferred to spacedomain) that represent the difference between the damaged plate signals and those from the intactplate. An algorithm was developed to join all four maps. The final map is modified by proposed signal processing algorithm to indicate the damaged area of the plate more precisely. The problem fordamage localization was investigated and exemplary maps confirming the effectiveness of theproposed system were obtained. It was also shown that the response of the introduced configurationremoves the ambiguity of damage localization normally present when a linear phased array is utilized.The investigation is based exclusively on numerical data

Zero-lag long-range synchronization via dynamical relaying

We show that simultaneous synchronization between two delay-coupled oscillators can be achieved by relaying the dynamics via a third mediating element, which surprisingly lags behind the synchronized outer elements. The zero-lag synchronization thus obtained is robust over a considerable parameter range. We substantiate our claims with experimental and numerical evidence of these synchronization solutions in a chain of three coupled semiconductor lasers with long inter-element coupling delays. The generality of the mechanism is validated in a neuronal model with the same coupling architecture. Thus, our results show that synchronized dynamical states can occur over long distances through relaying, without restriction by the amount of delay.Comment: 10 pages, 4 figure

Protein-RNA linkage and post-translational modifications of two sobemovirus VPgs

Sobemoviruses possess a viral genome-linked protein (VPg) attached to the 5' end of viral RNA. VPg is processed from the viral polyprotein. In the current study, Cocksfoot mottle virus (CfMV) and Rice yellow mottle virus (RYMV) VPgs were purified from virions and analysed by mass spectrometry. The cleavage sites in the polyprotein and thereof the termini of VPg were experimentally proven. The lengths of the mature VPgs were determined to be 78 and 79 aa residues, respectively. The amino acid residues covalently linked to RNA in the two VPgs were, surprisingly, not conserved; it is a tyrosine at position 5 of CfMV VPg and serine at position 1 of RYMV VPg. Phosphorylations were identified in CfMV and RYMV VPgs with two positionally similar locations T20/S14 and S71/S72, respectively. RYMV VPg contains an additional phosphorylation site at S41