Catálogo de publicaciones - revistas

<jats:p> Tuft dendrites of layer 5 pyramidal neurons form specialized compartments important for motor learning and performance, yet their computational capabilities remain unclear. Structural-functional mapping of the tuft tree from the motor cortex during motor tasks revealed two morphologically distinct populations of layer 5 pyramidal tract neurons (PTNs) that exhibit specific tuft computational properties. Early bifurcating and large nexus PTNs showed marked tuft functional compartmentalization, representing different motor variable combinations within and between their two tuft hemi-trees. By contrast, late bifurcating and smaller nexus PTNs showed synchronous tuft activation. Dendritic structure and dynamic recruitment of the <jats:italic>N</jats:italic> -methyl- <jats:sc>d</jats:sc> -aspartate (NMDA)–spiking mechanism explained the differential compartmentalization patterns. Our findings support a morphologically dependent framework for motor computations, in which independent amplification units can be combinatorically recruited to represent different motor sequences within the same tree. </jats:p>

<jats:p> Intermolecular cross-coupling of terminal olefins with secondary amines to form complex tertiary amines—a common motif in pharmaceuticals—remains a major challenge in chemical synthesis. Basic amine nucleophiles in nondirected, electrophilic metal–catalyzed aminations tend to bind to and thereby inhibit metal catalysts. We reasoned that an autoregulatory mechanism coupling the release of amine nucleophiles with catalyst turnover could enable functionalization without inhibiting metal-mediated heterolytic carbon-hydrogen cleavage. Here, we report a palladium(II)-catalyzed allylic carbon-hydrogen amination cross-coupling using this strategy, featuring 48 cyclic and acyclic secondary amines (10 pharmaceutically relevant cores) and 34 terminal olefins (bearing electrophilic functionality) to furnish 81 tertiary allylic amines, including 12 drug compounds and 10 complex drug derivatives, with excellent regio- and stereoselectivity (&gt;20:1 linear:branched, &gt;20:1 <jats:italic>E</jats:italic> : <jats:italic>Z</jats:italic> ). </jats:p>

<jats:p> On 14 August 2021, the moment magnitude ( <jats:italic>M</jats:italic> <jats:sub>w</jats:sub> ) 7.2 Nippes earthquake in Haiti occurred within the same fault zone as its devastating 2010 <jats:italic>M</jats:italic> <jats:sub>w</jats:sub> 7.0 predecessor, but struck the country when field access was limited by insecurity and conventional seismometers from the national network were inoperative. A network of citizen seismometers installed in 2019 provided near-field data critical to rapidly understand the mechanism of the mainshock and monitor its aftershock sequence. Their real-time data defined two aftershock clusters that coincide with two areas of coseismic slip derived from inversions of conventional seismological and geodetic data. Machine learning applied to data from the citizen seismometer closest to the mainshock allows us to forecast aftershocks as accurately as with the network-derived catalog. This shows the utility of citizen science contributing to our understanding of a major earthquake. </jats:p>

<jats:p> Bulk chemicals such as ethylene glycol (EG) can be industrially synthesized from either ethylene or syngas, but the latter undergoes a bottleneck reaction and requires high hydrogen pressures. We show that fullerene (exemplified by C <jats:sub>60</jats:sub> ) can act as an electron buffer for a copper-silica catalyst (Cu/SiO <jats:sub>2</jats:sub> ). Hydrogenation of dimethyl oxalate over a C <jats:sub>60</jats:sub> -Cu/SiO <jats:sub>2</jats:sub> catalyst at ambient pressure and temperatures of 180° to 190°C had an EG yield of up to 98 ± 1%. In a kilogram-scale reaction, no deactivation of the catalyst was seen after 1000 hours. This mild route for the final step toward EG can be combined with the already-industrialized ambient reaction from syngas to the intermediate of dimethyl oxalate. </jats:p>

<jats:p>Optical confinement (OC) structures the optical field and amplifies light intensity inside atmospheric aerosol particles, with major consequences for sunlight-driven aerosol chemistry. Although theorized, the OC-induced spatial structuring has so far defied experimental observation. Here, x-ray spectromicroscopic imaging complemented by modeling provides direct evidence for OC-induced patterning inside photoactive particles. Single iron(III)–citrate particles were probed using the iron oxidation state as a photochemical marker. Based on these results, we predict an overall acceleration of photochemical reactions by a factor of two to three for most classes of atmospheric aerosol particles. Rotation of free aerosol particles and intraparticle molecular transport generally accelerate the photochemistry. Given the prevalence of OC effects, their influence on aerosol particle photochemistry should be considered by atmospheric models.</jats:p>

<jats:p> Animals have evolved mechanisms, such as cell competition, to remove dangerous or nonfunctional cells from a tissue. Tumor necrosis factor signaling can eliminate clonal malignancies from <jats:italic>Drosophila</jats:italic> imaginal epithelia, but why this pathway is activated in tumor cells but not normal tissue is unknown. We show that the ligand that drives elimination is present in basolateral circulation but remains latent because it is spatially segregated from its apically localized receptor. Polarity defects associated with malignant transformation cause receptor mislocalization, allowing ligand binding and subsequent apoptotic signaling. This process occurs irrespective of the neighboring cells’ genotype and is thus distinct from cell competition. Related phenomena at epithelial wound sites are required for efficient repair. This mechanism of polarized compartmentalization of ligand and receptor can generally monitor epithelial integrity to promote tissue homeostasis. </jats:p>

<jats:p>Hydrogels are promising as materials for soft actuators because of qualities such as softness, transparency, and responsiveness to stimuli. However, weak and slow actuations remain challenging as a result of low modulus and osmosis-driven slow water diffusion, respectively. We used turgor pressure and electroosmosis to realize a strong and fast hydrogel-based actuator. A turgor actuator fabricated with a gel confined by a selectively permeable membrane can retain a high osmotic pressure that drives gel swelling; thus, our actuator exerts large stress [0.73 megapascals (MPa) in 96 minutes (min)] with a 1.16 cubic centimeters of hydrogel. With the accelerated water transport caused by electroosmosis, the gel swells rapidly, enhancing the actuation speed (0.79 MPa in 9 min). Our strategies enable a soft hydrogel to break a brick and construct underwater structures within a few minutes.</jats:p>

<jats:p>Glass is increasingly desired as a material for manufacturing complex microscopic geometries, from the micro-optics in compact consumer products to microfluidic systems for chemical synthesis and biological analyses. As the size, geometric, surface roughness, and mechanical strength requirements of glass evolve, conventional processing methods are challenged. We introduce microscale computed axial lithography (micro-CAL) of fused silica components, by tomographically illuminating a photopolymer-silica nanocomposite that is then sintered. We fabricated three-dimensional microfluidics with internal diameters of 150 micrometers, free-form micro-optical elements with a surface roughness of 6 nanometers, and complex high-strength trusses and lattice structures with minimum feature sizes of 50 micrometers. As a high-speed, layer-free digital light manufacturing process, micro-CAL can process nanocomposites with high solids content and high geometric freedom, enabling new device structures and applications.</jats:p>

<jats:p>Directing crystal growth into complex morphologies is challenging, as crystals tend to adopt thermodynamically stable morphologies. However, many organisms form crystals with intricate morphologies, as exemplified by coccoliths, microscopic calcite crystal arrays produced by unicellular algae. The complex morphologies of the coccolith crystals were hypothesized to materialize from numerous crystallographic facets, stabilized by fine-tuned interactions between organic molecules and the growing crystals. Using electron tomography, we examined multiple stages of coccolith development in three dimensions. We found that the crystals express only one set of symmetry-related crystallographic facets, which grow differentially to yield highly anisotropic shapes. Morphological chirality arises from positioning the crystals along specific edges of these same facets. Our findings suggest that growth rate manipulations are sufficient to yield complex crystalline morphologies.</jats:p>