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- ItemSimple ruthenium-catalyzed reductive amination enables the synthesis of a broad range of primary amines([London] : Nature Publishing Group UK, 2018) Senthamarai, Thirusangumurugan; Murugesan, Kathiravan; Schneidewind, Jacob; Kalevaru, Narayana V.; Baumann, Wolfgang; Neumann, Helfried; Kamer, Paul C. J.; Beller, Matthias; Jagadeesh, Rajenahally V.The production of primary benzylic and aliphatic amines, which represent essential feedstocks and key intermediates for valuable chemicals, life science molecules and materials, is of central importance. Here, we report the synthesis of this class of amines starting from carbonyl compounds and ammonia by Ru-catalyzed reductive amination using H2. Key to success for this synthesis is the use of a simple RuCl2(PPh3)3 catalyst that empowers the synthesis of >90 various linear and branched benzylic, heterocyclic, and aliphatic amines under industrially viable and scalable conditions. Applying this catalyst, −NH2 moiety has been introduced in functionalized and structurally diverse compounds, steroid derivatives and pharmaceuticals. Noteworthy, the synthetic utility of this Ru-catalyzed amination protocol has been demonstrated by upscaling the reactions up to 10 gram-scale syntheses. Furthermore, in situ NMR studies were performed for the identification of active catalytic species. Based on these studies a mechanism for Ru-catalyzed reductive amination is proposed.
- ItemAuthor Correction: Interfacial photochemistry at the ocean surface is a global source of organic vapors and aerosols([London] : Nature Publishing Group UK, 2018) Brüggemann, Martin; Hayeck, Nathalie; George, Christian[no abstract available]
- ItemControl of coordinatively unsaturated Zr sites in ZrO2 for efficient C–H bond activation([London] : Nature Publishing Group UK, 2018) Zhang, Yaoyuan; Zhao, Yun; Otroshchenko, Tatiana; Lund, Henrik; Pohl, Marga-Martina; Rodemerck, Uwe; Linke, David; Jiao, Haijun; Jiang, Guiyuan; Kondratenko, Evgenii V.Due to the complexity of heterogeneous catalysts, identification of active sites and the ways for their experimental design are not inherently straightforward but important for tailored catalyst preparation. The present study reveals the active sites for efficient C–H bond activation in C1–C4 alkanes over ZrO2 free of any metals or metal oxides usually catalysing this reaction. Quantum chemical calculations suggest that two Zr cations located at an oxygen vacancy are responsible for the homolytic C–H bond dissociation. This pathway differs from that reported for other metal oxides used for alkane activation, where metal cation and neighbouring lattice oxygen form the active site. The concentration of anion vacancies in ZrO2 can be controlled through adjusting the crystallite size. Accordingly designed ZrO2 shows industrially relevant activity and durability in non-oxidative propane dehydrogenation and performs superior to state-of-the-art catalysts possessing Pt, CrOx, GaOx or VOx species.
- ItemThe influence of Arctic amplification on mid-latitude summer circulation([London] : Nature Publishing Group UK, 2018) Coumou, D.; Di Capua, G.; Vavrus, S.; Wang, L.; Wang, S.Accelerated warming in the Arctic, as compared to the rest of the globe, might have profound impacts on mid-latitude weather. Most studies analyzing Arctic links to mid-latitude weather focused on winter, yet recent summers have seen strong reductions in sea-ice extent and snow cover, a weakened equator-to-pole thermal gradient and associated weakening of the mid-latitude circulation. We review the scientific evidence behind three leading hypotheses on the influence of Arctic changes on mid-latitude summer weather: Weakened storm tracks, shifted jet streams, and amplified quasi-stationary waves. We show that interactions between Arctic teleconnections and other remote and regional feedback processes could lead to more persistent hot-dry extremes in the mid-latitudes. The exact nature of these non-linear interactions is not well quantified but they provide potential high-impact risks for society.
- ItemPolymerization driven monomer passage through monolayer chemical vapour deposition graphene([London] : Nature Publishing Group UK, 2018-10-3) Zhang, Tao; Liao, Zhongquan; Sandonas, Leonardo Medrano; Dianat, Arezoo; Liu, Xiaoling; Xiao, Peng; Amin, Ihsan; Gutierrez, Rafael; Chen, Tao; Zschech, Ehrenfried; Cuniberti, Gianaurelio; Jordan, RainerMass transport through graphene is receiving increasing attention due to the potential for molecular sieving. Experimental studies are mostly limited to the translocation of protons, ions, and water molecules, and results for larger molecules through graphene are rare. Here, we perform controlled radical polymerization with surface-anchored self-assembled initiator monolayer in a monomer solution with single-layer graphene separating the initiator from the monomer. We demonstrate that neutral monomers are able to pass through the graphene (via native defects) and increase the graphene defects ratio (Raman ID/IG) from ca. 0.09 to 0.22. The translocations of anionic and cationic monomers through graphene are significantly slower due to chemical interactions of monomers with the graphene defects. Interestingly, if micropatterned initiator-monolayers are used, the translocations of anionic monomers apparently cut the graphene sheet into congruent microscopic structures. The varied interactions between monomers and graphene defects are further investigated by quantum molecular dynamics simulations.
- ItemDiverging importance of drought stress for maize and winter wheat in Europe([London] : Nature Publishing Group UK, 2018) Webber, Heidi; Ewert, Frank; Olesen, Jørgen E.; Müller, Christoph; Fronzek, Stefan; Ruane, Alex C.; Bourgault, Maryse; Martre, Pierre; Ababaei, Behnam; Bindi, Marco; Ferrise, Roberto; Finger, Robert; Fodor, Nándor; Gabaldón-Leal, Clara; Gaiser, Thomas; Jabloun, Mohamed; Kersebaum, Kurt-Christian; Lizaso, Jon I.; Lorite, Ignacio J.; Manceau, Loic; Moriondo, Marco; Nendel, Claas; Rodríguez, Alfredo; Ruiz-Ramos, Margarita; Semenov, Mikhail A.; Siebert, Stefan; Stella, Tommaso; Stratonovitch, Pierre; Trombi, Giacomo; Wallach, DanielUnderstanding the drivers of yield levels under climate change is required to support adaptation planning and respond to changing production risks. This study uses an ensemble of crop models applied on a spatial grid to quantify the contributions of various climatic drivers to past yield variability in grain maize and winter wheat of European cropping systems (1984–2009) and drivers of climate change impacts to 2050. Results reveal that for the current genotypes and mix of irrigated and rainfed production, climate change would lead to yield losses for grain maize and gains for winter wheat. Across Europe, on average heat stress does not increase for either crop in rainfed systems, while drought stress intensifies for maize only. In low-yielding years, drought stress persists as the main driver of losses for both crops, with elevated CO2 offering no yield benefit in these years.
- ItemIce-volume-forced erosion of the Chinese Loess Plateau global Quaternary stratotype site([London] : Nature Publishing Group UK, 2018) Stevens, T.; Buylaert, J.-P.; Thiel, C.; Újvári, G.; Yi, S.; Murray, A.S.; Frechen, M.; Lu, H.The International Commission on Stratigraphy (ICS) utilises benchmark chronostratigraphies to divide geologic time. The reliability of these records is fundamental to understand past global change. Here we use the most detailed luminescence dating age model yet published to show that the ICS chronology for the Quaternary terrestrial type section at Jingbian, desert marginal Chinese Loess Plateau, is inaccurate. There are large hiatuses and depositional changes expressed across a dynamic gully landform at the site, which demonstrates rapid environmental shifts at the East Asian desert margin. We propose a new independent age model and reconstruct monsoon climate and desert expansion/contraction for the last ~250 ka. Our record demonstrates the dominant influence of ice volume on desert expansion, dust dynamics and sediment preservation, and further shows that East Asian Summer Monsoon (EASM) variation closely matches that of ice volume, but lags insolation by ~5 ka. These observations show that the EASM at the monsoon margin does not respond directly to precessional forcing.
- ItemGate-controlled quantum dots and superconductivity in planar germanium([London] : Nature Publishing Group UK, 2018) Hendrickx, N.W.; Franke, D.P.; Sammak, A.; Kouwenhoven, M.; Sabbagh, D.; Yeoh, L.; Li, R.; Tagliaferri, M.L.V.; Virgilio, M.; Capellini, G.; Scappucci, G.; Veldhorst, M.Superconductors and semiconductors are crucial platforms in the field of quantum computing. They can be combined to hybrids, bringing together physical properties that enable the discovery of new emergent phenomena and provide novel strategies for quantum control. The involved semiconductor materials, however, suffer from disorder, hyperfine interactions or lack of planar technology. Here we realise an approach that overcomes these issues altogether and integrate gate-defined quantum dots and superconductivity into germanium heterostructures. In our system, heavy holes with mobilities exceeding 500,000 cm2 (Vs)−1 are confined in shallow quantum wells that are directly contacted by annealed aluminium leads. We observe proximity-induced superconductivity in the quantum well and demonstrate electric gate-control of the supercurrent. Germanium therefore has great promise for fast and coherent quantum hardware and, being compatible with standard manufacturing, could become a leading material for quantum information processing.
- ItemCompetition between proton transfer and intermolecular Coulombic decay in water([London] : Nature Publishing Group UK, 2018) Richter, Clemens; Hollas, Daniel; Saak, Clara-Magdalena; Förstel, Marko; Miteva, Tsveta; Mucke, Melanie; Björneholm, Olle; Sisourat, Nicolas; Slavíček, Petr; Hergenhahn, UweIntermolecular Coulombic decay (ICD) is a ubiquitous relaxation channel of electronically excited states in weakly bound systems, ranging from dimers to liquids. As it is driven by electron correlation, it was assumed that it will dominate over more established energy loss mechanisms, for example fluorescence. Here, we use electron–electron coincidence spectroscopy to determine the efficiency of the ICD process after 2a1 ionization in water clusters. We show that this efficiency is surprisingly low for small water clusters and that it gradually increases to 40–50% for clusters with hundreds of water units. Ab initio molecular dynamics simulations reveal that proton transfer between neighboring water molecules proceeds on the same timescale as ICD and leads to a configuration in which the ICD channel is closed. This conclusion is further supported by experimental results from deuterated water. Combining experiment and theory, we infer an intrinsic ICD lifetime of 12–52 fs for small water clusters.
- ItemIn situ single-shot diffractive fluence mapping for X-ray free-electron laser pulses([London] : Nature Publishing Group UK, 2018) Schneider, Michael; Günther, Christian M.; Pfau, Bastian; Capotondi, Flavio; Manfredda, Michele; Zangrando, Marco; Mahne, Nicola; Raimondi, Lorenzo; Pedersoli, Emanuele; Naumenko, Denys; Eisebitt, StefanFree-electron lasers (FELs) in the extreme ultraviolet (XUV) and X-ray regime opened up the possibility for experiments at high power densities, in particular allowing for fluence-dependent absorption and scattering experiments to reveal non-linear light-matter interactions at ever shorter wavelengths. Findings of such non-linear effects are met with tremendous interest, but prove difficult to understand and model due to the inherent shot-to-shot fluctuations in photon intensity and the often structured, non-Gaussian spatial intensity profile of a focused FEL beam. Presently, the focused beam is characterized and optimized separately from the actual experiment. Here, we present the simultaneous measurement of XUV diffraction signals from solid samples in tandem with the corresponding single-shot spatial fluence distribution on the actual sample. Our in situ characterization scheme enables direct monitoring of the sample illumination, providing a basis to optimize and quantitatively understand FEL experiments.