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- ItemFirst oxidation products from the reaction of hydroxyl radicals with isoprene for pristine environmental conditions([London] : Macmillan Publishers Limited, part of Springer Nature, 2019) Berndt, Torsten; Hyttinen, Noora; Herrmann, Hartmut; Hansel, ArminIsoprene, C5H8, inserts about half of the non-methane carbon flux of biogenic origin into the atmosphere. Its degradation is primarily initiated by the reaction with hydroxyl radicals. Here we show experimentally the formation of reactive intermediates and corresponding closed-shell products from the reaction of hydroxyl radicals with isoprene for low nitric oxide and low hydroperoxy radical conditions. Detailed product analysis is achieved by mass spectrometric techniques. Quantum chemical calculations support the usefulness of applied ionization schemes. Observed peroxy radicals are the isomeric HO-C5H8O2 radicals and their isomerization products HO-C5H8(O2)O2, bearing most likely an additional hydroperoxy group, and in traces HO-C5H8(O2)2O2 with two hydroperoxy groups. Main closed-shell products from unimolecular peroxy radical reactions are hydroperoxy aldehydes, C5H8O3, and smaller yield products with the composition C5H8O4 and C4H8O5. Detected signals of C10H18O4, C10H18O6, and C5H10O2 stand for products arising from peroxy radical self- and cross-reactions. © 2019, The Author(s).
- ItemDirect synthesis of benzylic amines by palladium-catalyzed carbonylative aminohomologation of aryl halides([London] : Macmillan Publishers Limited, part of Springer Nature, 2018) Peng, Jin-Bao; Wu, Fu-Peng; Xu, Cong; Qi, Xinxin; Ying, Jun; Wu, Xiao-FengBenzylic amines are valuable compounds with important applications in areas including pharmaceuticals and agrochemicals. The known procedures for their synthesis are limited by difficulties in functionalizing the parent aminomethyl groups. On the other hand, carbonylation reactions offer a potent method to introduce carbonyl groups and homologate carbon chains. However, carbonylative aminohomologation of aryl halides is challenging due to competing reactions and the need to balance multiple sequential steps. Here we report a palladium-catalyzed carbonylative aminohomologation reaction for the direct aminomethylation of aryl halides. The reaction proceeds via a tandem palladium-catalyzed formylation, followed by imine formation and formic acid-mediated reduction. Useful functional groups including chloride, bromide, ester, ketone, nitro, and cyano are compatible with this reaction. Both aryl iodides and bromides are suitable substrates and a wide range of synthetically useful amines are efficiently obtained in moderate to excellent yields.
- ItemPhenotypic, Morphological and Adhesive Differences of Human Hematopoietic Progenitor Cells Cultured on Murine versus Human Mesenchymal Stromal Cells([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Reichert, Doreen; Friedrichs, Jens; Ritter, Steffi; Käubler, Theresa; Werner, Carsten; Bornhäuser, Martin; Corbeil, DenisXenogenic transplantation models have been developed to study human hematopoiesis in immunocompromised murine recipients. They still have limitations and therefore it is important to delineate all players within the bone marrow that could account for species-specific differences. Here, we evaluated the proliferative capacity, morphological and physical characteristics of human CD34+ hematopoietic stem and progenitor cells (HSPCs) after co-culture on murine or human bone marrow-derived mesenchymal stromal cells (MSCs). After seven days, human CD34+CD133– HSPCs expanded to similar extents on both feeder layers while cellular subsets comprising primitive CD34+CD133+ and CD133+CD34– phenotypes are reduced fivefold on murine MSCs. The number of migrating HSPCs was also reduced on murine cells suggesting that MSC adhesion influences cellular polarization of HSPC. We used atomic force microscopy-based single-cell force spectroscopy to quantify their adhesive interactions. We found threefold higher detachment forces of human HSPCs from murine MSCs compared to human ones. This difference is related to the N-cadherin expression level on murine MSCs since its knockdown abolished their differential adhesion properties with human HSPCs. Our observations highlight phenotypic, morphological and adhesive differences of human HSPCs when cultured on murine or human MSCs, which raise some caution in data interpretation when xenogenic transplantation models are used.
- ItemWorldwide variations in artificial skyglow([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Kyba, Christopher C.M.; Tong, Kai Pong; Bennie, Jonathan; Birriel, Ignacio; Birriel, Jennifer J.; Cool, Andrew; Danielsen, Arne; Davies, Thomas W.; den Outer, Peter N.; Edwards, William; Ehlert, Rainer; Falchi, Fabio; Fischer, Jürgen; Giacomelli, Andrea; Giubbilini, Francesco; Haaima, Marty; Hesse, Claudia; Heygster, Georg; Hölker, Franz; Inger, Richard; Jensen, Linsey J.; Kuechly, Helga U.; Kuehn, John; Langill, Phil; Lolkema, Dorien E.; Nagy, Matthew; Nievas, Miguel; Ochi, Nobuaki; Popow, Emil; Posch, Thomas; Puschnig, Johannes; Ruhtz, Thomas; Schmidt, Wim; Schwarz, Robert; Schwope, Axel; Spoelstra, Henk; Tekatch, Anthony; Trueblood, Mark; Walker, Constance E.; Weber, Michael; Welch, Douglas L.; Zamorano, Jaime; Gaston, Kevin J.Despite constituting a widespread and significant environmental change, understanding of artificial nighttime skyglow is extremely limited. Until now, published monitoring studies have been local or regional in scope and typically of short duration. In this first major international compilation of monitoring data we answer several key questions about skyglow properties. Skyglow is observed to vary over four orders of magnitude, a range hundreds of times larger than was the case before artificial light. Nearly all of the study sites were polluted by artificial light. A non-linear relationship is observed between the sky brightness on clear and overcast nights, with a change in behavior near the rural to urban landuse transition. Overcast skies ranged from a third darker to almost 18 times brighter than clear. Clear sky radiances estimated by the World Atlas of Artificial Night Sky Brightness were found to be overestimated by ~25%; our dataset will play an important role in the calibration and ground truthing of future skyglow models. Most of the brightly lit sites darkened as the night progressed, typically by ~5% per hour. The great variation in skyglow radiance observed from site-to-site and with changing meteorological conditions underlines the need for a long-term international monitoring program.
- ItemCation-cation clusters in ionic liquids: Cooperative hydrogen bonding overcomes like-charge repulsion([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Knorr, Anne; Ludwig, RalfDirect spectroscopic evidence for H-bonding between like-charged ions is reported for the ionic liquid, 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate. New infrared bands in the OH frequency range appear at low temperatures indicating the formation of H-bonded cation-cation clusters similar to those known for water and alcohols. Supported by DFT calculations, these vibrational bands can be assigned to attractive interaction between the hydroxyl groups of the cations. The repulsive Coulomb interaction is overcome by cooperative hydrogen bonding between ions of like charge. The transition energy from purely cation-anion interacting configurations to those including cation-cation H-bonds is determined to be 3–4 kJmol−1. The experimental findings and DFT calculations strongly support the concept of anti-electrostatic hydrogen bonds (AEHBs) as recently suggested by Weinhold and Klein. The like-charge configurations are kinetically stabilized with decreasing temperatures.
- ItemStructural and electronic properties of epitaxial multilayer h-BN on Ni(111) for spintronics applications([London] : Macmillan Publishers Limited, part of Springer Nature, 2016) Tonkikh, A.A.; Voloshina, E.N.; Werner, P.; Blumtritt, H.; Senkovskiy, B.; Güntherodt, G.; Parkin, S.S.P.; Dedkov, Yu. S.Hexagonal boron nitride (h-BN) is a promising material for implementation in spintronics due to a large band gap, low spin-orbit coupling, and a small lattice mismatch to graphene and to close-packed surfaces of fcc-Ni(111) and hcp-Co(0001). Epitaxial deposition of h-BN on ferromagnetic metals is aimed at small interface scattering of charge and spin carriers. We report on the controlled growth of h-BN/Ni(111) by means of molecular beam epitaxy (MBE). Structural and electronic properties of this system are investigated using cross-section transmission electron microscopy (TEM) and electron spectroscopies which confirm good agreement with the properties of bulk h-BN. The latter are also corroborated by density functional theory (DFT) calculations, revealing that the first h-BN layer at the interface to Ni is metallic. Our investigations demonstrate that MBE is a promising, versatile alternative to both the exfoliation approach and chemical vapour deposition of h-BN.
- ItemOn the Dynamical Regimes of Pattern-Accelerated Electroconvection([London] : Macmillan Publishers Limited, part of Springer Nature, 2016) Davidson, Scott M.; Wessling, Matthias; Mani, AliRecent research has established that electroconvection can enhance ion transport at polarized surfaces such as membranes and electrodes where it would otherwise be limited by diffusion. The onset of such overlimiting transport can be influenced by the surface topology of the ion selective membranes as well as inhomogeneities in their electrochemical properties. However, there is little knowledge regarding the mechanisms through which these surface variations promote transport. We use high-resolution direct numerical simulations to develop a comprehensive analysis of electroconvective flows generated by geometric patterns of impermeable stripes and investigate their potential to regularize electrokinetic instabilities. Counterintuitively, we find that reducing the permeable area of an ion exchange membrane, with appropriate patterning, increases the overall ion transport rate by up to 80%. In addition, we present analysis of nonpatterned membranes and find a novel regime of electroconvection where a multivalued current is possible due to the coexistence of multiple convective states.
- ItemYield trends, variability and stagnation analysis of major crops in France over more than a century([London] : Macmillan Publishers Limited, part of Springer Nature, 2018) Schauberger, Bernhard; Ben-Ari, Tamara; Makowski, David; Kato, Tomomichi; Kato, Hiromi; Ciais, PhilippeFrance is a major crop producer, with a production share of approx. 20% within the European Union. Yet, a discussion has recently started whether French yields are stagnating. While for wheat previous results are unanimously pointing to recent stagnation, there is contradictory evidence for maize and few to no results for other crops. Here we analyse a data set with more than 120,000 yield observations from 1900 to 2016 for ten crops (barley, durum and soft wheat, maize, oats, potatoes, rapeseed, sugar beet, sunflower and wine) in the 96 mainland French départements (NUTS3 administrative division). We dissect the evolution of yield trends over time and space, analyse yield variation and evaluate whether growth of yields has stalled in recent years. Yields have, on average across crops, multiplied four-fold over the course of the 20th century. While absolute yield variability has increased, the variation relative to the mean has halved – mean yields have increased faster than their variability. But growth of yields has stagnated since the 1990’s for winter wheat, barley, oats, durum wheat, sunflower and wine on at least 25% of their areas. Reaching yield potentials is unlikely as a cause for stagnation. Maize, in contrast, shows no evidence for stagnation.
- ItemAqueous Black Colloids of Reticular Nanostructured Gold([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Stanca, S.E.; Fritzsche, W.; Dellith, J.; Froehlich, F.; Undisz, A.; Deckert, V.; Krafft, C.; Popp, J.Since ancient times, noble gold has continuously contributed to several aspects of life from medicine to electronics. It perpetually reveals its new features. We report the finding of a unique form of gold, reticular nanostructured gold (RNG), as an aqueous black colloid, for which we present a one-step synthesis. The reticules consist of gold crystals that interconnect to form compact strands. RNG exhibits high conductivity and low reflection and these features, coupled with the high specific surface area of the material, could prove valuable for applications in electronics and catalysis. Due to high absorption throughout the visible and infrared domain, RNG has the potential to be applied in the construction of sensitive solar cells or as a substrate for Raman spectroscopy.
- ItemStrong magnetic frustration and anti-site disorder causing spin-glass behavior in honeycomb Li2RhO3([London] : Macmillan Publishers Limited, part of Springer Nature, 2015) Katukuri, Vamshi M.; Nishimoto, Satoshi; Rousochatzakis, Ioannis; Stoll, Hermann; van den Brink, Jeroen; Hozoi, LiviuWith large spin-orbit coupling, the electron configuration in d-metal oxides is prone to highly anisotropic exchange interactions and exotic magnetic properties. In 5d5 iridates, given the existing variety of crystal structures, the magnetic anisotropy can be tuned from antisymmetric to symmetric Kitaev-type, with interaction strengths that outsize the isotropic terms. By many-body electronic-structure calculations we here address the nature of the magnetic exchange and the intriguing spin-glass behavior of Li2RhO3, a 4d5 honeycomb oxide. For pristine crystals without Rh-Li site inversion, we predict a dimerized ground state as in the isostructural 5d5 iridate Li2IrO3, with triplet spin dimers effectively placed on a frustrated triangular lattice. With Rh-Li anti-site disorder, we explain the observed spin-glass phase as a superposition of different, nearly degenerate symmetry-broken configurations.