Catálogo de publicaciones - revistas

<jats:p>Abrupt climate changes during the last glacial period have been detected in a global array of palaeoclimate records, but our understanding of their absolute timing and regional synchrony is incomplete. Our compilation of 63 published, independently dated speleothem records shows that abrupt warmings in Greenland were associated with synchronous climate changes across the Asian Monsoon, South American Monsoon, and European-Mediterranean regions that occurred within decades. Together with the demonstration of bipolar synchrony in atmospheric response, this provides independent evidence of synchronous high-latitude–to-tropical coupling of climate changes during these abrupt warmings. Our results provide a globally coherent framework with which to validate model simulations of abrupt climate change and to constrain ice-core chronologies.</jats:p>

<jats:p>Site selectivity and stereocontrol remain major challenges in C–H bond functionalization chemistry, especially in linear aliphatic saturated hydrocarbon scaffolds. We report the highly enantioselective and site-selective catalytic borylation of remote C(sp<jats:sup>3</jats:sup>)–H bonds γ to the carbonyl group in aliphatic secondary and tertiary amides and esters. A chiral C–H activation catalyst was modularly assembled from an iridium center, a chiral monophosphite ligand, an achiral urea-pyridine receptor ligand, and pinacolatoboryl groups. Quantum chemical calculations support an enzyme-like structural cavity formed by the catalyst components, which bind the substrate through multiple noncovalent interactions. Versatile synthetic utility of the enantioenriched γ-borylcarboxylic acid derivatives was demonstrated.</jats:p>

<jats:p>Electronic dynamics in liquids are of fundamental importance, but time-resolved experiments have so far remained limited to the femtosecond time scale. We report the extension of attosecond spectroscopy to the liquid phase. We measured time delays of 50 to 70 attoseconds between the photoemission from liquid water and that from gaseous water at photon energies of 21.7 to 31.0 electron volts. These photoemission delays can be decomposed into a photoionization delay sensitive to the local environment and a delay originating from electron transport. In our experiments, the latter contribution is shown to be negligible. By referencing liquid water to gaseous water, we isolated the effect of solvation on the attosecond photoionization dynamics of water molecules. Our methods define an approach to separating bound and unbound electron dynamics from the structural response of the solvent.</jats:p>

<jats:p>Versatile chemical transformations of surface functional groups in two-dimensional transition-metal carbides (MXenes) open up a previously unexplored design space for this broad class of functional materials. We introduce a general strategy to install and remove surface groups by performing substitution and elimination reactions in molten inorganic salts. Successful synthesis of MXenes with oxygen, imido, sulfur, chlorine, selenium, bromine, and tellurium surface terminations, as well as bare MXenes (no surface termination), was demonstrated. These MXenes show distinctive structural and electronic properties. For example, the surface groups control interatomic distances in the MXene lattice, and Ti<jats:italic><jats:sub>n</jats:sub></jats:italic><jats:sub>+1</jats:sub>C<jats:italic><jats:sub>n</jats:sub></jats:italic> (<jats:italic>n</jats:italic> = 1, 2) MXenes terminated with telluride (Te<jats:sup>2−</jats:sup>) ligands show a giant (&gt;18%) in-plane lattice expansion compared with the unstrained titanium carbide lattice. The surface groups also control superconductivity of niobium carbide MXenes.</jats:p>

<jats:p>Cytoarchitecture is a basic principle of microstructural brain parcellation. We introduce Julich-Brain, a three-dimensional atlas containing cytoarchitectonic maps of cortical areas and subcortical nuclei. The atlas is probabilistic, which enables it to account for variations between individual brains. Building such an atlas was highly data- and labor-intensive and required the development of nested, interdependent workflows for detecting borders between brain areas, data processing, provenance tracking, and flexible execution of processing chains to handle large amounts of data at different spatial scales. Full cortical coverage was achieved by the inclusion of gap maps to complement cortical maps. The atlas is dynamic and will be adapted as mapping progresses; it is openly available to support neuroimaging studies as well as modeling and simulation; and it is interoperable, enabling connection to other atlases and resources.</jats:p>

<jats:p>Pulse-like carbon dioxide release to the atmosphere on centennial time scales has only been identified for the most recent glacial and deglacial periods and is thought to be absent during warmer climate conditions. Here, we present a high-resolution carbon dioxide record from 330,000 to 450,000 years before present, revealing pronounced carbon dioxide jumps (CDJ) under cold and warm climate conditions. CDJ come in two varieties that we attribute to invigoration or weakening of the Atlantic meridional overturning circulation (AMOC) and associated northward and southward shifts of the intertropical convergence zone, respectively. We find that CDJ are pervasive features of the carbon cycle that can occur during interglacial climate conditions if land ice masses are sufficiently extended to be able to disturb the AMOC by freshwater input.</jats:p>