Catalytic molten metals for the direct conversion of methane to hydrogen and separable carbon

<p>Metals that are active catalysts for methane (Ni, Pt, Pd), when dissolved in inactive low&ndash;melting temperature metals (In, Ga, Sn, Pb), produce stable molten metal alloy catalysts for pyrolysis of methane into hydrogen and carbon. All solid catalysts previously used for this reaction have been deactivated by carbon deposition. In the molten alloy system, the insoluble carbon floats to the surface where it can be skimmed off. A 27% Ni&ndash;73% Bi alloy achieved 95% methane conversion at 1065&deg;C in a 1.1-meter bubble column and produced pure hydrogen without CO<SUB>2</SUB> or other by-products. Calculations show that the active metals in the molten alloys are atomically dispersed and negatively charged. There is a correlation between the amount of charge on the atoms and their catalytic activity.</p>

State-to-state chemistry for three-body recombination in an ultracold rubidium gas

<p>Experimental investigation of chemical reactions with full quantum state resolution for all reactants and products has been a long-term challenge. Here we prepare an ultracold few-body quantum state of reactants and demonstrate state-to-state chemistry for the recombination of three spin-polarized ultracold rubidium (Rb) atoms to form a weakly bound Rb<SUB>2</SUB> molecule. The measured product distribution covers about 90% of the final products, and we are able to discriminate between product states with a level splitting as small as 20 megahertz multiplied by Planck&rsquo;s constant. Furthermore, we formulate propensity rules for the distribution of products, and we develop a theoretical model that predicts many of our experimental observations. The scheme can readily be adapted to other species and opens a door to detailed investigations of inelastic or reactive processes.</p>

Evolution of flower color pattern through selection on regulatory small RNAs

<p>Small RNAs (sRNAs) regulate genes in plants and animals. Here, we show that population-wide differences in color patterns in snapdragon flowers are caused by an inverted duplication that generates sRNAs. The complexity and size of the transcripts indicate that the duplication represents an intermediate on the pathway to microRNA evolution. The sRNAs repress a pigment biosynthesis gene, creating a yellow highlight at the site of pollinator entry. The inverted duplication exhibits steep clines in allele frequency in a natural hybrid zone, showing that the allele is under selection. Thus, regulatory interactions of evolutionarily recent sRNAs can be acted upon by selection and contribute to the evolution of phenotypic diversity.</p>

Antibody-dependent enhancement of severe dengue disease in humans

<p>For dengue viruses 1 to 4 (DENV1-4), a specific range of antibody titer has been shown to enhance viral replication in vitro and severe disease in animal models. Although suspected, such antibody-dependent enhancement of severe disease has not been shown to occur in humans. Using multiple statistical approaches to study a long-term pediatric cohort in Nicaragua, we show that risk of severe dengue disease is highest within a narrow range of preexisting anti-DENV antibody titers. By contrast, we observe protection from all symptomatic dengue disease at high antibody titers. Thus, immune correlates of severe dengue must be evaluated separately from correlates of protection against symptomatic disease. These results have implications for studies of dengue pathogenesis and for vaccine development, because enhancement, not just lack of protection, is of concern.</p>

A single mutation in the prM protein of Zika virus contributes to fetal microcephaly

<p>Zika virus (ZIKV) has evolved into a global health threat because of its unexpected causal link to microcephaly. Phylogenetic analysis reveals that contemporary epidemic strains have accumulated multiple substitutions from their Asian ancestor. Here we show that a single serine-to-asparagine substitution [Ser<sup>139</sup>-&gt;Asn<sup>139</sup> (S139N)] in the viral polyprotein substantially increased ZIKV infectivity in both human and mouse neural progenitor cells (NPCs) and led to more severe microcephaly in the mouse fetus, as well as higher mortality rates in neonatal mice. Evolutionary analysis indicates that the S139N substitution arose before the 2013 outbreak in French Polynesia and has been stably maintained during subsequent spread to the Americas. This functional adaption makes ZIKV more virulent to human NPCs, thus contributing to the increased incidence of microcephaly in recent ZIKV epidemics.</p>

Atomic model for the dimeric FO region of mitochondrial ATP synthase

<p>Mitochondrial adenosine triphosphate (ATP) synthase produces the majority of ATP in eukaryotic cells, and its dimerization is necessary to create the inner membrane folds, or cristae, characteristic of mitochondria. Proton translocation through the membrane-embedded F<SUB>O</SUB> region turns the rotor that drives ATP synthesis in the soluble F<SUB>1</SUB> region. Although crystal structures of the F<SUB>1</SUB> region have illustrated how this rotation leads to ATP synthesis, understanding how proton translocation produces the rotation has been impeded by the lack of an experimental atomic model for the F<SUB>O</SUB> region. Using cryo&ndash;electron microscopy, we determined the structure of the dimeric F<SUB>O</SUB> complex from <I>Saccharomyces cerevisiae</I> at a resolution of 3.6 angstroms. The structure clarifies how the protons travel through the complex, how the complex dimerizes, and how the dimers bend the membrane to produce cristae.</p>

Metabolic recycling of ammonia via glutamate dehydrogenase supports breast cancer biomass

<p>Ammonia is a ubiquitous by-product of cellular metabolism; however, the biological consequences of ammonia production are not fully understood, especially in cancer. We found that ammonia is not merely a toxic waste product but is recycled into central amino acid metabolism to maximize nitrogen utilization. In our experiments, human breast cancer cells primarily assimilated ammonia through reductive amination catalyzed by glutamate dehydrogenase (GDH); secondary reactions enabled other amino acids, such as proline and aspartate, to directly acquire this nitrogen. Metabolic recycling of ammonia accelerated proliferation of breast cancer. In mice, ammonia accumulated in the tumor microenvironment and was used directly to generate amino acids through GDH activity. These data show that ammonia is not only a secreted waste product but also a fundamental nitrogen source that can support tumor biomass.</p>

Structural basis of bacterial transcription activation

<p>In bacteria, the activation of gene transcription at many promoters is simple and only involves a single activator. The cyclic adenosine 3',5'-monophosphate receptor protein (CAP), a classic activator, is able to activate transcription independently through two different mechanisms. Understanding the class I mechanism requires an intact transcription activation complex (TAC) structure at a high resolution. Here we report a high-resolution cryo&ndash;electron microscopy structure of an intact <I>Escherichia coli</I> class I TAC containing a CAP dimer, a <sup>70</sup>&ndash;RNA polymerase (RNAP) holoenzyme, a complete class I CAP-dependent promoter DNA, and a de novo synthesized RNA oligonucleotide. The structure shows how CAP wraps the upstream DNA and how the interactions recruit RNAP. Our study provides a structural basis for understanding how activators activate transcription through the class I recruitment mechanism.</p>

Natural selection shaped the rise and fall of passenger pigeon genomic diversity

<p>The extinct passenger pigeon was once the most abundant bird in North America, and possibly the world. Although theory predicts that large populations will be more genetically diverse, passenger pigeon genetic diversity was surprisingly low. To investigate this disconnect, we analyzed 41 mitochondrial and 4 nuclear genomes from passenger pigeons and 2 genomes from band-tailed pigeons, which are passenger pigeons&rsquo; closest living relatives. Passenger pigeons&rsquo; large population size appears to have allowed for faster adaptive evolution and removal of harmful mutations, driving a huge loss in their neutral genetic diversity. These results demonstrate the effect that selection can have on a vertebrate genome and contradict results that suggested that population instability contributed to this species&rsquo;s surprisingly rapid extinction.</p>

Comment on "The extent of forest in dryland biomes"

<p>Bastin <I>et al</I>. (Reports, 12 May 2017, p. 635) infer forest as more globally extensive than previously estimated using tree cover data. However, their forest definition does not reflect ecosystem function or biotic composition. These structural and climatic definitions inflate forest estimates across the tropics and undermine conservation goals, leading to inappropriate management policies and practices in tropical grassy ecosystems.</p>

Small vulnerable sets determine large network cascades in power grids

<p>The understanding of cascading failures in complex systems has been hindered by the lack of realistic large-scale modeling and analysis that can account for variable system conditions. Using the North American power grid, we identified, quantified, and analyzed the set of network components that are vulnerable to cascading failures under any out of multiple conditions. We show that the vulnerable set consists of a small but topologically central portion of the network and that large cascades are disproportionately more likely to be triggered by initial failures close to this set. These results elucidate aspects of the origins and causes of cascading failures relevant for grid design and operation and demonstrate vulnerability analysis methods that are applicable to a wider class of cascade-prone networks.</p>

Loci associated with skin pigmentation identified in African populations

<p>Despite the wide range of skin pigmentation in humans, little is known about its genetic basis in global populations. Examining ethnically diverse African genomes, we identify variants in or near <I>SLC24A5</I>, <I>MFSD12</I>, <I>DDB1</I>, <I>TMEM138</I>, <I>OCA2</I>, and <I>HERC2</I> that are significantly associated with skin pigmentation. Genetic evidence indicates that the light pigmentation variant at <I>SLC24A5</I> was introduced into East Africa by gene flow from non-Africans. At all other loci, variants associated with dark pigmentation in Africans are identical by descent in South Asian and Australo-Melanesian populations. Functional analyses indicate that <I>MFSD12</I> encodes a lysosomal protein that affects melanogenesis in zebrafish and mice, and that mutations in melanocyte-specific regulatory regions near <I>DDB1/TMEM138</I> correlate with expression of ultraviolet response genes under selection in Eurasians.</p>

Self-assembling peptide semiconductors

<p>Semiconductors are central to the modern electronics and optics industries. Conventional semiconductive materials bear inherent limitations, especially in emerging fields such as interfacing with biological systems and bottom-up fabrication. A promising candidate for bioinspired and durable nanoscale semiconductors is the family of self-assembled nanostructures comprising short peptides. The highly ordered and directional intermolecular - interactions and hydrogen-bonding network allow the formation of quantum confined structures within the peptide self-assemblies, thus decreasing the band gaps of the superstructures into semiconductor regions. As a result of the diverse architectures and ease of modification of peptide self-assemblies, their semiconductivity can be readily tuned, doped, and functionalized. Therefore, this family of electroactive supramolecular materials may bridge the gap between the inorganic semiconductor world and biological systems.</p>

Comment on "The extent of forest in dryland biomes"

<p>The study by Bastin <I>et al</I>. (Reports, 12 May 2017, p. 635) is based on an incomplete delimitation of dry forest distribution and on an old and incorrect definition of drylands. Its sampling design includes many plots located in humid ecosystems and ignores critical areas for the conservation of dry forests. Therefore, its results and conclusions may be unreliable.</p>

Perovskite in Earths deep interior

<p>Silicate perovskite-type phases are the most abundant constituent inside our planet and are the predominant minerals in Earth&rsquo;s lower mantle more than 660 kilometers below the surface. Magnesium-rich perovskite is a major lower mantle phase and undergoes a phase transition to post-perovskite near the bottom of the mantle. Calcium-rich perovskite is proportionally minor but may host numerous trace elements that record chemical differentiation events. The properties of mantle perovskites are the key to understanding the dynamic evolution of Earth, as they strongly influence the transport properties of lower mantle rocks. Perovskites are expected to be an important constituent of rocky planets larger than Mars and thus play a major role in modulating the evolution of terrestrial planets throughout the universe.</p>

Promises and challenges of perovskite solar cells

<p>The efficiencies of perovskite solar cells have gone from single digits to a certified 22.1% in a few years&rsquo; time. At this stage of their development, the key issues concern how to achieve further improvements in efficiency and long-term stability. We review recent developments in the quest to improve the current state of the art. Because photocurrents are near the theoretical maximum, our focus is on efforts to increase open-circuit voltage by means of improving charge-selective contacts and charge carrier lifetimes in perovskites via processes such as ion tailoring. The challenges associated with long-term perovskite solar cell device stability include the role of testing protocols, ionic movement affecting performance metrics over extended periods of time, and determination of the best ways to counteract degradation mechanisms.</p>

Properties and potential optoelectronic applications of lead halide perovskite nanocrystals

<p>Semiconducting lead halide perovskites (LHPs) have not only become prominent thin-film absorber materials in photovoltaics but have also proven to be disruptive in the field of colloidal semiconductor nanocrystals (NCs). The most important feature of LHP NCs is their so-called defect-tolerance&mdash;the apparently benign nature of structural defects, highly abundant in these compounds, with respect to optical and electronic properties. Here, we review the important differences that exist in the chemistry and physics of LHP NCs as compared with more conventional, tetrahedrally bonded, elemental, and binary semiconductor NCs (such as silicon, germanium, cadmium selenide, gallium arsenide, and indium phosphide). We survey the prospects of LHP NCs for optoelectronic applications such as in television displays, light-emitting devices, and solar cells, emphasizing the practical hurdles that remain to be overcome.</p>

Perovskites in catalysis and electrocatalysis

<p>Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.</p>

Lewis acid enhancement by hydrogen-bond donors for asymmetric catalysis

<p>Small-molecule dual hydrogen-bond (H-bond) donors such as ureas, thioureas, squaramides, and guanidinium ions enjoy widespread use as effective catalysts for promoting a variety of enantioselective reactions. However, these catalysts are only weakly acidic and therefore require highly reactive electrophilic substrates to be effective. We introduce here a mode of catalytic activity with chiral H-bond donors that enables enantioselective reactions of relatively unreactive electrophiles. Squaramides are shown to interact with silyl triflates by binding the triflate counterion to form a stable, yet highly Lewis acidic, complex. The silyl triflate-chiral squaramide combination promotes the generation of oxocarbenium intermediates from acetal substrates at low temperatures. Enantioselectivity in nucleophile additions to the cationic intermediates is then controlled through a network of noncovalent interactions between the squaramide catalyst and the oxocarbenium triflate.</p>

Observation of mean path length invariance in light-scattering media

<p>The microstructure of a medium strongly influences how light propagates through it. The amount of disorder it contains determines whether the medium is transparent or opaque. Theory predicts that exciting such a medium homogeneously and isotropically makes some of its optical properties depend only on the medium&rsquo;s outer geometry. Here, we report an optical experiment demonstrating that the mean path length of light is invariant with respect to the microstructure of the medium it scatters through. Using colloidal solutions with varying concentration and particle size, the invariance of the mean path length is observed over nearly two orders of magnitude in scattering strength. Our results can be extended to a wide range of systems&mdash;however ordered, correlated, or disordered&mdash;and apply to all wave-scattering problems.</p>

Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20%

<p>Perovskite solar cells (PSCs) with efficiencies greater than 20% have been realized only with expensive organic hole-transporting materials. We demonstrate PSCs that achieve stabilized efficiencies exceeding 20% with copper(I) thiocyanate (CuSCN) as the hole extraction layer. A fast solvent removal method enabled the creation of compact, highly conformal CuSCN layers that facilitate rapid carrier extraction and collection. The PSCs showed high thermal stability under long-term heating, although their operational stability was poor. This instability originated from potential-induced degradation of the CuSCN/Au contact. The addition of a conductive reduced graphene oxide spacer layer between CuSCN and gold allowed PSCs to retain &gt;95% of their initial efficiency after aging at a maximum power point for 1000 hours under full solar intensity at 60&deg;C. Under both continuous full-sun illumination and thermal stress, CuSCN-based devices surpassed the stability of spiro-OMeTAD&ndash;based PSCs.</p>

Distinguishing a Majorana zero mode using spin-resolved measurements

<p>One-dimensional topological superconductors host Majorana zero modes (MZMs), the nonlocal property of which could be exploited for quantum computing applications. We use spin-polarized scanning tunneling microscopy to show that MZMs realized in self-assembled Fe chains on the surface of Pb have a spin polarization that exceeds that stemming from the magnetism of these chains. This feature, captured by our model calculations, is a direct consequence of the nonlocality of the Hilbert space of MZMs emerging from a topological band structure. Our study establishes spin-polarization measurements as a diagnostic tool to distinguish topological MZMs from trivial in-gap states of a superconductor.</p>

How the news media activate public expression and influence national agendas

<p>We demonstrate that exposure to the news media causes Americans to take public stands on specific issues, join national policy conversations, and express themselves publicly&mdash;all key components of democratic politics&mdash;more often than they would otherwise. After recruiting 48 mostly small media outlets, we chose groups of these outlets to write and publish articles on subjects we approved, on dates we randomly assigned. We estimated the causal effect on proximal measures, such as website pageviews and Twitter discussion of the articles&rsquo; specific subjects, and distal ones, such as national Twitter conversation in broad policy areas. Our intervention increased discussion in each broad policy area by ~62.7% (relative to a day&rsquo;s volume), accounting for 13,166 additional posts over the treatment week, with similar effects across population subgroups.</p>

Cordilleran Ice Sheet mass loss preceded climate reversals near the Pleistocene Termination

<p>The Cordilleran Ice Sheet (CIS) once covered an area comparable to that of Greenland. Previous geologic evidence and numerical models indicate that the ice sheet covered much of westernmost Canada as late as 12.5 thousand years ago (ka). New data indicate that substantial areas throughout westernmost Canada were ice free prior to 12.5 ka and some as early as 14.0 ka, with implications for climate dynamics and the timing of meltwater discharge to the Pacific and Arctic oceans. Early B&oslash;lling-Aller&oslash;d warmth halved the mass of the CIS in as little as 500 years, causing 2.5 to 3.0 meters of sea-level rise. Dozens of cirque and valley glaciers, along with the southern margin of the CIS, advanced into recently deglaciated regions during the B&oslash;lling-Aller&oslash;d and Younger Dryas.</p>

Genomic history of the seventh pandemic of cholera in Africa

<p>The seventh cholera pandemic has heavily affected Africa, although the origin and continental spread of the disease remain undefined. We used genomic data from 1070 <I>Vibrio cholerae</I> O1 isolates, across 45 African countries and over a 49-year period, to show that past epidemics were attributable to a single expanded lineage. This lineage was introduced at least 11 times since 1970, into two main regions, West Africa and East/Southern Africa, causing epidemics that lasted up to 28 years. The last five introductions into Africa, all from Asia, involved multidrug-resistant sublineages that replaced antibiotic-susceptible sublineages after 2000. This phylogenetic framework describes the periodicity of lineage introduction and the stable routes of cholera spread, which should inform the rational design of control measures for cholera in Africa.</p>

Integrated view of Vibrio cholerae in the Americas

<p>Latin America has experienced two of the largest cholera epidemics in modern history; one in 1991 and the other in 2010. However, confusion still surrounds the relationships between globally circulating pandemic <I>Vibrio cholerae</I> clones and local bacterial populations. We used whole-genome sequencing to characterize cholera across the Americas over a 40-year time span. We found that both epidemics were the result of intercontinental introductions of seventh pandemic El Tor <I>V. cholerae</I> and that at least seven lineages local to the Americas are associated with disease that differs epidemiologically from epidemic cholera. Our results consolidate historical accounts of pandemic cholera with data to show the importance of local lineages, presenting an integrated view of cholera that is important to the design of future disease control strategies.</p>

A neural algorithm for a fundamental computing problem

<p>Similarity search&mdash;for example, identifying similar images in a database or similar documents on the web&mdash;is a fundamental computing problem faced by large-scale information retrieval systems. We discovered that the fruit fly olfactory circuit solves this problem with a variant of a computer science algorithm (called locality-sensitive hashing). The fly circuit assigns similar neural activity patterns to similar odors, so that behaviors learned from one odor can be applied when a similar odor is experienced. The fly algorithm, however, uses three computational strategies that depart from traditional approaches. These strategies can be translated to improve the performance of computational similarity searches. This perspective helps illuminate the logic supporting an important sensory function and provides a conceptually new algorithm for solving a fundamental computational problem.</p>

Redox-sensitive alteration of replisome architecture safeguards genome integrity

<p>DNA replication requires coordination between replication fork progression and deoxynucleotide triphosphate (dNTP)&ndash;generating metabolic pathways. We find that perturbation of ribonucleotide reductase (RNR) in humans elevates reactive oxygen species (ROS) that are detected by peroxiredoxin 2 (PRDX2). In the oligomeric state, PRDX2 forms a replisome-associated ROS sensor, which binds the fork accelerator TIMELESS when exposed to low levels of ROS. Elevated ROS levels generated by RNR attenuation disrupt oligomerized PRDX2 to smaller subunits, whose dissociation from chromatin enforces the displacement of TIMELESS from the replisome. This process instantly slows replication fork progression, which mitigates pathological consequences of replication stress. Thus, redox signaling couples fluctuations of dNTP biogenesis with replisome activity to reduce stress during genome duplication. We propose that cancer cells exploit this pathway to increase their adaptability to adverse metabolic conditions.</p>

Calibrated mitotic oscillator drives motile ciliogenesis

<p>Cell division and differentiation depend on massive and rapid organelle remodeling. The mitotic oscillator, centered on the cyclin-dependent kinase 1&ndash;anaphase-promoting complex/cyclosome (CDK1-APC/C) axis, spatiotemporally coordinates this reorganization in dividing cells. Here we discovered that nondividing cells could also implement this mitotic clocklike regulatory circuit to orchestrate subcellular reorganization associated with differentiation. We probed centriole amplification in differentiating mouse-brain multiciliated cells. These postmitotic progenitors fine-tuned mitotic oscillator activity to drive the orderly progression of centriole production, maturation, and motile ciliation while avoiding the mitosis commitment threshold. Insufficient CDK1 activity hindered differentiation, whereas excessive activity accelerated differentiation yet drove postmitotic progenitors into mitosis. Thus, postmitotic cells can redeploy and calibrate the mitotic oscillator to uncouple cytoplasmic from nuclear dynamics for organelle remodeling associated with differentiation.</p>

Lysosomal metabolomics reveals V-ATPase- and mTOR-dependent regulation of amino acid efflux from lysosomes

<p>The lysosome degrades and recycles macromolecules, signals to the cytosol and nucleus, and is implicated in many diseases. Here, we describe a method for the rapid isolation of mammalian lysosomes and use it to quantitatively profile lysosomal metabolites under various cell states. Under nutrient-replete conditions, many lysosomal amino acids are in rapid exchange with those in the cytosol. Loss of lysosomal acidification through inhibition of the vacuolar H<sup>+</sup>&ndash;adenosine triphosphatase (V-ATPase) increased the luminal concentrations of most metabolites but had no effect on those of the majority of essential amino acids. Instead, nutrient starvation regulates the lysosomal concentrations of these amino acids, an effect we traced to regulation of the mechanistic target of rapamycin (mTOR) pathway. Inhibition of mTOR strongly reduced the lysosomal efflux of most essential amino acids, converting the lysosome into a cellular depot for them. These results reveal the dynamic nature of lysosomal metabolites and that V-ATPase- and mTOR-dependent mechanisms exist for controlling lysosomal amino acid efflux.</p>