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- ItemXUV excitation followed by ultrafast non-adiabatic relaxation in PAH molecules as a femto-astrochemistry experiment([London] : Nature Publishing Group UK, 2015) Marciniak, A.; Despré, V.; Barillot, T.; Rouzée, A.; Galbraith, M.C.E.; Klei, J.; Yang, C.-H.; Smeenk, C.T.L.; Loriot, V.; Nagaprasad Reddy, S.; Tielens, A.G.G.M.; Mahapatra, S.; Kuleff, A.I.; Vrakking, M.J.J.; Lépine, F.Highly excited molecular species are at play in the chemistry of interstellar media and are involved in the creation of radiation damage in a biological tissue. Recently developed ultrashort extreme ultraviolet light sources offer the high excitation energies and ultrafast time-resolution required for probing the dynamics of highly excited molecular states on femtosecond (fs) (1 fs=10−15s) and even attosecond (as) (1 as=10−18 s) timescales. Here we show that polycyclic aromatic hydrocarbons (PAHs) undergo ultrafast relaxation on a few tens of femtoseconds timescales, involving an interplay between the electronic and vibrational degrees of freedom. Our work reveals a general property of excited radical PAHs that can help to elucidate the assignment of diffuse interstellar absorption bands in astrochemistry, and provides a benchmark for the manner in which coupled electronic and nuclear dynamics determines reaction pathways in large molecules following extreme ultraviolet excitation.
- ItemCubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers([London] : Nature Publishing Group UK, 2017) He, Hongkun; Rahimi, Khosrow; Zhong, Mingjiang; Mourran, Ahmed; Luebke, David R.; Nulwala, Hunaid B.; Möller, Martin; Matyjaszewski, KrzysztofCubosomes are micro- and nanoparticles with a bicontinuous cubic two-phase structure, reported for the self-assembly of low molecular weight surfactants, for example, lipids, but rarely formed by polymers. These objects are characterized by a maximum continuous interface and high interface to volume ratio, which makes them promising candidates for efficient adsorbents and host-guest applications. Here we demonstrate self-assembly to nanoscale cuboidal particles with a bicontinuous cubic structure by amphiphilic poly(ionic liquid) diblock copolymers, poly(acrylic acid)-block-poly(4-vinylbenzyl)-3-butyl imidazolium bis(trifluoromethylsulfonyl)imide, in a mixture of tetrahydrofuran and water under optimized conditions. Structure determining parameters include polymer composition and concentration, temperature, and the variation of the solvent mixture. The formation of the cubosomes can be explained by the hierarchical interactions of the constituent components. The lattice structure of the block copolymers can be transferred to the shape of the particle as it is common for atomic and molecular faceted crystals.
- ItemWeibull-distributed dyke thickness reflects probabilistic character of host-rock strength([London] : Nature Publishing Group UK, 2014) Krumbholz, Michael; Hieronymus, Christoph F.; Burchardt, Steffi; Troll, Valentin R.; Tanner, David C.; Friese, NadineMagmatic sheet intrusions (dykes) constitute the main form of magma transport in the Earth’s crust. The size distribution of dykes is a crucial parameter that controls volcanic surface deformation and eruption rates and is required to realistically model volcano deformation for eruption forecasting. Here we present statistical analyses of 3,676 dyke thickness measurements from different tectonic settings and show that dyke thickness consistently follows the Weibull distribution. Known from materials science, power law-distributed flaws in brittle materials lead to Weibull-distributed failure stress. We therefore propose a dynamic model in which dyke thickness is determined by variable magma pressure that exploits differently sized host-rock weaknesses. The observed dyke thickness distributions are thus site-specific because rock strength, rather than magma viscosity and composition, exerts the dominant control on dyke emplacement. Fundamentally, the strength of geomaterials is scale-dependent and should be approximated by a probability distribution.
- ItemA low pre-infall mass for the Carina dwarf galaxy from disequilibrium modeling([London] : Nature Publishing Group UK, 2015) Ural, Uğur; Wilkinson, Mark I.; Read, Justin I.; Walker, Matthew G.Dark matter-only simulations of galaxy formation predict many more subhalos around a Milky Way-like galaxy than the number of observed satellites. Proposed solutions require the satellites to inhabit dark matter halos with masses 109–1010Msun at the time they fell into the Milky Way. Here we use a modelling approach, independent of cosmological simulations, to obtain a pre-infall mass of Msun for one of the Milky Way’s satellites: Carina. This determination of a low halo mass for Carina can be accommodated within the standard model only if galaxy formation becomes stochastic in halos below ∼1010Msun. Otherwise Carina, the eighth most luminous Milky Way dwarf, would be expected to inhabit a significantly more massive halo. The implication of this is that a population of ‘dark dwarfs’ should orbit the Milky Way: halos devoid of stars and yet more massive than many of their visible counterparts.
- ItemTopological data analysis of contagion maps for examining spreading processes on networks([London] : Nature Publishing Group UK, 2015) Taylor, Dane; Klimm, Florian; Harrington, Heather A.; Kramár, Miroslav; Mischaikow, Konstantin; Porter, Mason A.; Mucha, Peter J.Social and biological contagions are influenced by the spatial embeddedness of networks. Historically, many epidemics spread as a wave across part of the Earth’s surface; however, in modern contagions long-range edges—for example, due to airline transportation or communication media—allow clusters of a contagion to appear in distant locations. Here we study the spread of contagions on networks through a methodology grounded in topological data analysis and nonlinear dimension reduction. We construct ‘contagion maps’ that use multiple contagions on a network to map the nodes as a point cloud. By analysing the topology, geometry and dimensionality of manifold structure in such point clouds, we reveal insights to aid in the modelling, forecast and control of spreading processes. Our approach highlights contagion maps also as a viable tool for inferring low-dimensional structure in networks.
- 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.
- ItemBio-degradable highly fluorescent conjugated polymer nanoparticles for bio-medical imaging applications([London] : Nature Publishing Group UK, 2017) Repenko, Tatjana; Rix, Anne; Ludwanowski, Simon; Go, Dennis; Kiessling, Fabian; Lederle, Wiltrud; Kuehne, Alexander J. C.Conjugated polymer nanoparticles exhibit strong fluorescence and have been applied for biological fluorescence imaging in cell culture and in small animals. However, conjugated polymer particles are hydrophobic and often chemically inert materials with diameters ranging from below 50 nm to several microns. As such, conjugated polymer nanoparticles cannot be excreted through the renal system. This drawback has prevented their application for clinical bio-medical imaging. Here, we present fully conjugated polymer nanoparticles based on imidazole units. These nanoparticles can be bio-degraded by activated macrophages. Reactive oxygen species induce scission of the conjugated polymer backbone at the imidazole unit, leading to complete decomposition of the particles into soluble low molecular weight fragments. Furthermore, the nanoparticles can be surface functionalized for directed targeting. The approach opens a wide range of opportunities for conjugated polymer particles in the fields of medical imaging, drug-delivery, and theranostics.
- 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.