2019, Murugesan, Kathiravan, Wei, Zhihong, Chandrashekhar, Vishwas G., Neumann, Helfried, Spannenberg, Anke, Jiao, Haijun, Beller, Matthias, Jagadeesh, Rajenahally V.

The development of earth abundant 3d metal-based catalysts continues to be an important goal of chemical research. In particular, the design of base metal complexes for reductive amination to produce primary amines remains as challenging. Here, we report the combination of cobalt and linear-triphos (bis(2-diphenylphosphinoethyl)phenylphosphine) as the molecularly-defined non-noble metal catalyst for the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds, gaseous ammonia and hydrogen in good to excellent yields. Noteworthy, this cobalt catalyst exhibits high selectivity and as a result the -NH2 moiety is introduced in functionalized and structurally diverse molecules. An inner-sphere mechanism on the basis of the mono-cationic [triphos-CoH]+ complex as active catalyst is proposed and supported with density functional theory computation on the doublet state potential free energy surface and H2 metathesis is found as the rate-determining step.

2019, Morace, A., Iwata, N., Sentoku, Y., Mima, K., Arikawa, Y., Yogo, A., Andreev, A., Tosaki, S., Vaisseau, X., Abe, Y., Kojima, S., Sakata, S., Hata, M., Lee, S., Matsuo, K., Kamitsukasa, N., Norimatsu, T., Kawanaka, J., Tokita, S., Miyanaga, N., Shiraga, H., Sakawa, Y., Nakai, M., Nishimura, H., Azechi, H., Fujioka, S., Kodama, R.

Increasing the laser energy absorption into energetic particle beams represents a longstanding quest in intense laser-plasma physics. During the interaction with matter, part of the laser energy is converted into relativistic electron beams, which are the origin of secondary sources of energetic ions, γ-rays and neutrons. Here we experimentally demonstrate that using multiple coherent laser beamlets spatially and temporally overlapped, thus producing an interference pattern in the laser focus, significantly improves the laser energy conversion efficiency into hot electrons, compared to one beam with the same energy and nominal intensity as the four beamlets combined. Two-dimensional particle-in-cell simulations support the experimental results, suggesting that beamlet interference pattern induces a periodical shaping of the critical density, ultimately playing a key-role in enhancing the laser-to-electron energy conversion efficiency. This method is rather insensitive to laser pulse contrast and duration, making this approach robust and suitable to many existing facilities.

2019, Scotti, A., Bochenek, S., Brugnoni, M., Fernandez-Rodriguez, M.A., Schulte, M.F., Houston, J.E., Gelissen, A.P.H., Potemkin, I.I., Isa, L., Richtering, W.

Microgels are solvent-swollen nano- and microparticles that show prevalent colloidal-like behavior despite their polymeric nature. Here we study ultra-low crosslinked poly(N-isopropylacrylamide) microgels (ULC), which can behave like colloids or flexible polymers depending on dimensionality, compression or other external stimuli. Small-angle neutron scattering shows that the structure of the ULC microgels in bulk aqueous solution is characterized by a density profile that decays smoothly from the center to a fuzzy surface. Their phase behavior and rheological properties are those of soft colloids. However, when these microgels are confined at an oil-water interface, their behavior resembles that of flexible macromolecules. Once monolayers of ultra-low crosslinked microgels are compressed, deposited on solid substrate and studied with atomic-force microscopy, a concentration-dependent topography is observed. Depending on the compression, these microgels can behave as flexible polymers, covering the substrate with a uniform film, or as colloidal microgels leading to a monolayer of particles.

2019, Reichlova, Helena, Janda, Tomas, Godinho, Joao, Markou, Anastasios, Kriegner, Dominik, Schlitz, Richard, Zelezny, Jakub, Soban, Zbynek, Bejarano, Mauricio, Schultheiss, Helmut, Nemec, Petr, Jungwirth, Tomas, Felser, Claudia, Wunderlich, Joerg, Goennenwein, Sebastian T. B.

Non-collinear antiferromagnets are revealing many unexpected phenomena and they became crucial for the field of antiferromagnetic spintronics. To visualize and prepare a well-defined domain structure is of key importance. The spatial magnetic contrast, however, remains extraordinarily difficult to be observed experimentally. Here, we demonstrate a magnetic imaging technique based on a laser induced local thermal gradient combined with detection of the anomalous Nernst effect. We employ this method in one the most actively studied representatives of this class of materials—Mn3Sn. We demonstrate that the observed contrast is of magnetic origin. We further show an algorithm to prepare a well-defined domain pattern at room temperature based on heat assisted recording principle. Our study opens up a prospect to study spintronics phenomena in non-collinear antiferromagnets with spatial resolution.

2019, Wu, Lipeng, Annibale, Vincent T., Jiao, Haijun, Brookfield, Adam, Collison, David, Manners, Ian

Catalytic chemistry that involves the activation and transformation of main group substrates is relatively undeveloped and current examples are generally mediated by expensive transition metal species. Herein, we describe the use of inexpensive and readily available tBuOK as a catalyst for P–P and P–E (E = O, S, or N) bond formation. Catalytic quantities of tBuOK in the presence of imine, azobenzene hydrogen acceptors, or a stoichiometric amount of tBuOK with hydrazobenzene, allow efficient homodehydrocoupling of phosphines under mild conditions (e.g. 25 °C and < 5 min). Further studies demonstrate that the hydrogen acceptors play an intimate mechanistic role. We also show that our tBuOK catalysed methodology is general for the heterodehydrocoupling of phosphines with alcohols, thiols and amines to generate a range of potentially useful products containing P–O, P–S, or P–N bonds.

2019, Rupp, Philipp, Burger, Christian, Kling, Nora G, Kübel, Matthias, Mitra, Sambit, Rosenberger, Philipp, Weatherby, Thomas, Saito, Nariyuki, Itatani, Jiro, Alnaser, Ali S., Raschke, Markus B., Rühl, Eckart, Schlander, Annika, Gallei, Markus, Seiffert, Lennart, Fennel, Thomas, Bergues, Boris, Kling, Matthias F.

Nanoparticles offer unique properties as photocatalysts with large surface areas. Under irradiation with light, the associated near-fields can induce, enhance, and control molecular adsorbate reactions on the nanoscale. So far, however, there is no simple method available to spatially resolve the near-field induced reaction yield on the surface of nanoparticles. Here we close this gap by introducing reaction nanoscopy based on three-dimensional momentum-resolved photoionization. The technique is demonstrated for the spatially selective proton generation in few-cycle laser-induced dissociative ionization of ethanol and water on SiO2 nanoparticles, resolving a pronounced variation across the particle surface. The results are modeled and reproduced qualitatively by electrostatic and quasi-classical mean-field Mie Monte-Carlo (M3C) calculations. Reaction nanoscopy is suited for a wide range of isolated nanosystems and can provide spatially resolved ultrafast reaction dynamics on nanoparticles, clusters, and droplets.

2019, Hofmann, M., Mathesius, S., Kriegler, E., van Vuuren, D.P., Schellnhuber, H.J.

In Paris in 2015, the global community agreed to limit global warming to well below 2 ∘C, aiming at even 1.5 ∘C. It is still uncertain whether these targets are sufficient to preserve marine ecosystems and prevent a severe alteration of marine biogeochemical cycles. Here, we show that stringent mitigation strategies consistent with the 1.5 ∘C scenario could, indeed, provoke a critical difference for the ocean’s carbon cycle and calcium carbonate saturation states. Favorable conditions for calcifying organisms like tropical corals and polar pteropods, both of major importance for large ecosystems, can only be maintained if CO2 emissions fall rapidly between 2025 and 2050, potentially requiring an early deployment of CO2 removal techniques in addition to drastic emissions reduction. Furthermore, this outcome can only be achieved if the terrestrial biosphere remains a carbon sink during the entire 21st century.

2019, Zvyagin, S.A., Graf, D., Sakurai, T., Kimura, S., Nojiri, H., Wosnitza, J., Ohta, H., Ono, T., Tanaka, H.

Quantum triangular-lattice antiferromagnets are important prototype systems to investigate numerous phenomena of the geometrical frustration in condensed matter. Apart from highly unusual magnetic properties, they possess a rich phase diagram (ranging from an unfrustrated square lattice to a quantum spin liquid), yet to be confirmed experimentally. One major obstacle in this area of research is the lack of materials with appropriate (ideally tuned) magnetic parameters. Using Cs2CuCl4 as a model system, we demonstrate an alternative approach, where, instead of the chemical composition, the spin Hamiltonian is altered by hydrostatic pressure. The approach combines high-pressure electron spin resonance and r.f. susceptibility measurements, allowing us not only to quasi-continuously tune the exchange parameters, but also to accurately monitor them. Our experiments indicate a substantial increase of the exchange coupling ratio from 0.3 to 0.42 at a pressure of 1.8 GPa, revealing a number of emergent field-induced phases.

2019, Schewe, Jacob, Gosling, Simon N., Reyer, Christopher, Zhao, Fang, Ciais, Philippe, Elliott, Joshua, Francois, Louis, Huber, Veronika, Lotze, Heike K., Seneviratne, Sonia I., van Vliet, Michelle T. H., Vautard, Robert, Wada, Yoshihide, Breuer, Lutz, Büchner, Matthias, Carozza, David A., Chang, Jinfeng, Coll, Marta, Deryng, Delphine, de Wit, Allard, Eddy, Tyler D., Folberth, Christian, Frieler, Katja, Friend, Andrew D., Gerten, Dieter, Gudmundsson, Lukas, Hanasaki, Naota, Ito, Akihiko, Khabarov, Nikolay, Kim, Hyungjun, Lawrence, Peter, Morfopoulos, Catherine, Müller, Christoph, Müller Schmied, Hannes, Orth, René, Ostberg, Sebastian, Pokhrel, Yadu, Pugh, Thomas A. M., Sakurai, Gen, Satoh, Yusuke, Schmid, Erwin, Stacke, Tobias, Steenbeek, Jeroen, Steinkamp, Jörg, Tang, Qiuhong, Tian, Hanqin, Tittensor, Derek P., Volkholz, Jan, Wang, Xuhui, Warszawski, Lila

Global impact models represent process-level understanding of how natural and human systems may be affected by climate change. Their projections are used in integrated assessments of climate change. Here we test, for the first time, systematically across many important systems, how well such impact models capture the impacts of extreme climate conditions. Using the 2003 European heat wave and drought as a historical analogue for comparable events in the future, we find that a majority of models underestimate the extremeness of impacts in important sectors such as agriculture, terrestrial ecosystems, and heat-related human mortality, while impacts on water resources and hydropower are overestimated in some river basins; and the spread across models is often large. This has important implications for economic assessments of climate change impacts that rely on these models. It also means that societal risks from future extreme events may be greater than previously thought.

2019, Ribeiro, Haroldo V., Rybski, Diego, Kropp, Jürgen P.

The question of whether urbanization contributes to increasing carbon dioxide emissions has been mainly investigated via scaling relationships with population or population density. However, these approaches overlook the correlations between population and area, and ignore possible interactions between these quantities. Here, we propose a generalized framework that simultaneously considers the effects of population and area along with possible interactions between these urban metrics. Our results significantly improve the description of emissions and reveal the coupled role between population and density on emissions. These models show that variations in emissions associated with proportionate changes in population or density may not only depend on the magnitude of these changes but also on the initial values of these quantities. For US areas, the larger the city, the higher is the impact of changing its population or density on its emissions; but population changes always have a greater effect on emissions than population density.