Molecularly selective nanoporous membrane-based wearable organic electrochemical device for noninvasive cortisol sensing Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Onur Parlak, Scott Tom Keene, Andrew Marais, Vincenzo F. Curto, Alberto Salleo
Wearable biosensors have emerged as an alternative evolutionary development in the field of healthcare technology due to their potential to change conventional medical diagnostics and health monitoring. However, a number of critical technological challenges including selectivity, stability of (bio)recognition, efficient sample handling, invasiveness, and mechanical compliance to increase user comfort must still be overcome to successfully bring devices closer to commercial applications. We introduce the integration of an electrochemical transistor and a tailor-made synthetic and biomimetic polymeric membrane, which acts as a molecular memory layer facilitating the stable and selective molecular recognition of the human stress hormone cortisol. The sensor and a laser-patterned microcapillary channel array are integrated in a wearable sweat diagnostics platform, providing accurate sweat acquisition and precise sample delivery to the sensor interface. The integrated devices were successfully used with both ex situ methods using skin-like microfluidics and on human subjects with on-body real-sample analysis using a wearable sensor assembly.
Anomalous Hall effect derived from multiple Weyl nodes in high-mobility EuTiO3 films Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Kei S. Takahashi, Hiroaki Ishizuka, Tomoki Murata, Qing Y. Wang, Yoshinori Tokura, Naoto Nagaosa, Masashi Kawasaki
EuTiO3, a magnetic semiconductor with a simple band structure, is one of the ideal systems to control the anomalous Hall effect (AHE) by tuning the Fermi level. The electrons in the conduction bands of La-doped EuTiO3 are subject to the spin-orbit interaction and Zeeman field from the spontaneous magnetization, which generates rich structures in the electron band such as Weyl nodes. This unique property makes EuTiO3 a relatively simple multiband system with its Berry curvature being controlled by electron doping and magnetic field. We report a nonmonotonic magnetic field dependence of the anomalous Hall resistivity, which is ascribed to the change of electronic bands induced by the Zeeman splitting during the magnetization process. The anomalous Hall resistivity measurement in high-mobility films grown by gas source molecular beam epitaxy shows additional terms in the AHE during the magnetization process, which is not proportional to the magnetization. Our theoretical calculation indicates that the change of Zeeman field in the process of canting the magnetic moments causes the type II Weyl nodes in the conduction band to move, resulting in a peculiar magnetic field dependence of the AHE; this is revealed by the high-quality films with a long scattering lifetime of conduction electrons.
A physical model for efficient ranking in networks Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Caterina De Bacco, Daniel B. Larremore, Cristopher Moore
We present a physically inspired model and an efficient algorithm to infer hierarchical rankings of nodes in directed networks. It assigns real-valued ranks to nodes rather than simply ordinal ranks, and it formalizes the assumption that interactions are more likely to occur between individuals with similar ranks. It provides a natural statistical significance test for the inferred hierarchy, and it can be used to perform inference tasks such as predicting the existence or direction of edges. The ranking is obtained by solving a linear system of equations, which is sparse if the network is; thus, the resulting algorithm is extremely efficient and scalable. We illustrate these findings by analyzing real and synthetic data, including data sets from animal behavior, faculty hiring, social support networks, and sports tournaments. We show that our method often outperforms a variety of others, in both speed and accuracy, in recovering the underlying ranks and predicting edge directions.
Hidden CDW states and insulator-to-metal transition after a pulsed femtosecond laser excitation in layered chalcogenide 1T-TaS2−xSex Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Kai Sun, Shuaishuai Sun, Chunhui Zhu, Huanfang Tian, Huaixin Yang, Jianqi Li
The hidden (H) quantum state in 1T-TaS2 has sparked considerable interest in the field of correlated electron systems. Here, we investigate ultrafast switches to stable H charge density wave (H-CDW) states observed in 1T-TaS2−xSex, with x = 0 and 0.5 crystals, upon excitation with a single femtosecond laser pulse. In situ cooling transmission electron microscopy observations, initiated by a single femtosecond laser pumping with a low fluence, reveal a clear transition from a commensurate CDW phase (qC) to a new CDW order with qH = (1 − δ)qC for the H-CDW state (δ = 1/9) accompanied by an evident phase separation. H-CDW domain relaxation then occurs and yields a stable metallic phase under a high-fluence excitation. Furthermore, electrical resistivity measurements show that the notable drop in x = 0 and 0.5 samples associated with the appearance of H-CDW states depend on laser fluence and temperature. These results potentially provide a new perspective on the photodoping mechanism for the emergence of H-CDW states in the 1T-TaS2−xSex family.
Hybrid chiral domain walls and skyrmions in magnetic multilayers Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 William Legrand, Jean-Yves Chauleau, Davide Maccariello, Nicolas Reyren, Sophie Collin, Karim Bouzehouane, Nicolas Jaouen, Vincent Cros, Albert Fert
Noncollinear spin textures in ferromagnetic ultrathin films are currently the subject of renewed interest since the discovery of the interfacial Dzyaloshinskii-Moriya interaction (DMI). This antisymmetric exchange interaction selects a given chirality for the spin textures and allows stabilizing configurations with nontrivial topology including chiral domain walls (DWs) and magnetic skyrmions. Moreover, it has many crucial consequences on the dynamical properties of these topological structures. In recent years, the study of noncollinear spin textures has been extended from single ultrathin layers to magnetic multilayers with broken inversion symmetry. This extension of the structures in the vertical dimension allows room temperature stability and very efficient current-induced motion for both Néel DWs and skyrmions. We show how, in these multilayered systems, the interlayer interactions can actually lead to hybrid chiral magnetization arrangements. The described thickness-dependent reorientation of DWs is experimentally confirmed by studying demagnetized multilayers through circular dichroism in x-ray resonant magnetic scattering. We also demonstrate a simple yet reliable method for determining the magnitude of the DMI from static domain measurements even in the presence of these hybrid chiral structures by taking into account the actual profile of the DWs. The existence of these novel hybrid chiral textures has far-reaching implications on how to stabilize and manipulate DWs, as well as skymionic structures in magnetic multilayers.
Optical manipulation of magnetic vortices visualized in situ by Lorentz electron microscopy Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Xuewen Fu, Shawn D. Pollard, Bin Chen, Byung-Kuk Yoo, Hyunsoo Yang, Yimei Zhu
Understanding the fundamental dynamics of topological vortex and antivortex naturally formed in microscale/nanoscale ferromagnetic building blocks under external perturbations is crucial to magnetic vortex–based information processing and spintronic devices. All previous studies have focused on magnetic vortex–core switching via external magnetic fields, spin-polarized currents, or spin waves, which have largely prohibited the investigation of novel spin configurations that could emerge from the ground states in ferromagnetic disks and their underlying dynamics. We report in situ visualization of femtosecond laser quenching–induced magnetic vortex changes in various symmetric ferromagnetic Permalloy disks by using Lorentz phase imaging of four-dimensional electron microscopy that enables in situ laser excitation. Besides the switching of magnetic vortex chirality and polarity, we observed with distinct occurrence frequencies a plenitude of complex magnetic structures that have never been observed by magnetic field– or current-assisted switching. These complex magnetic structures consist of a number of newly created topological magnetic defects (vortex and antivortex) strictly conserving the topological winding number, demonstrating the direct impact of topological invariants on magnetization dynamics in ferromagnetic disks. Their spin configurations show mirror or rotation symmetry due to the geometrical confinement of the disks. Combined micromagnetic simulations with the experimental observations reveal the underlying magnetization dynamics and formation mechanism of the optical quenching–induced complex magnetic structures. Their distinct occurrence rates are pertinent to their formation-growth energetics and pinning effects at the disk edge. On the basis of these findings, we propose a paradigm of optical quenching–assisted fast switching of vortex cores for the control of magnetic vortex–based information recording and spintronic devices.
Radical chain repair: The hydroalkylation of polysubstituted unactivated alkenes Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Guillaume Povie, Sankar Rao Suravarapu, Martin Peter Bircher, Melinda Meyer Mojzes, Samuel Rieder, Philippe Renaud
The concept of repair is widely used by nature to heal molecules such as proteins, lipids, sugars, and DNA that are damaged by hydrogen atom abstraction resulting from oxidative stress. We show that this strategy, rather undocumented in the field of synthetic organic chemistry, can be used in a radical chain reaction to enable notoriously intractable transformations. By overcoming the radical chain inhibitor properties of substituted alkenes, the radical-mediated hydroalkylation of mono-, di-, tri-, and even tetrasubstituted unactivated olefins could be performed under mild conditions. With a remarkable functional group tolerance, this reaction provides a general coupling method for the derivatization of olefin-containing natural products.
Beating the channel capacity limit for superdense coding with entangled ququarts Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Xiao-Min Hu, Yu Guo, Bi-Heng Liu, Yun-Feng Huang, Chuan-Feng Li, Guang-Can Guo
Quantum superdense coding protocols enhance channel capacity by using shared quantum entanglement between two users. The channel capacity can be as high as 2 when one uses entangled qubits. However, this limit can be surpassed by using high-dimensional entanglement. We report an experiment that exceeds the limit using high-quality entangled ququarts with fidelities up to 0.98, demonstrating a channel capacity of 2.09 ± 0.01. The measured channel capacity is also higher than that obtained when transmitting only one ququart. We use the setup to transmit a five-color image with a fidelity of 0.952. Our experiment shows the great advantage of high-dimensional entanglement and will stimulate research on high-dimensional quantum information processes.
Unpacking the polarization of workplace skills Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Ahmad Alabdulkareem, Morgan R. Frank, Lijun Sun, Bedoor AlShebli, César Hidalgo, Iyad Rahwan
Economic inequality is one of the biggest challenges facing society today. Inequality has been recently exacerbated by growth in high- and low-wage occupations at the expense of middle-wage occupations, leading to a “hollowing” of the middle class. Yet, our understanding of how workplace skills drive this process is limited. Specifically, how do skill requirements distinguish high- and low-wage occupations, and does this distinction constrain the mobility of individuals and urban labor markets? Using unsupervised clustering techniques from network science, we show that skills exhibit a striking polarization into two clusters that highlight the specific social-cognitive skills and sensory-physical skills of high- and low-wage occupations, respectively. The connections between skills explain various dynamics: how workers transition between occupations, how cities acquire comparative advantage in new skills, and how individual occupations change their skill requirements. We also show that the polarized skill topology constrains the career mobility of individual workers, with low-skill workers “stuck” relying on the low-wage skill set. Together, these results provide a new explanation for the persistence of occupational polarization and inform strategies to mitigate the negative effects of automation and offshoring of employment. In addition to our analysis, we provide an online tool for the public and policy makers to explore the skill network: skillscape.mit.edu.
A network approach to topic models Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Martin Gerlach, Tiago P. Peixoto, Eduardo G. Altmann
One of the main computational and scientific challenges in the modern age is to extract useful information from unstructured texts. Topic models are one popular machine-learning approach that infers the latent topical structure of a collection of documents. Despite their success—particularly of the most widely used variant called latent Dirichlet allocation (LDA)—and numerous applications in sociology, history, and linguistics, topic models are known to suffer from severe conceptual and practical problems, for example, a lack of justification for the Bayesian priors, discrepancies with statistical properties of real texts, and the inability to properly choose the number of topics. We obtain a fresh view of the problem of identifying topical structures by relating it to the problem of finding communities in complex networks. We achieve this by representing text corpora as bipartite networks of documents and words. By adapting existing community-detection methods (using a stochastic block model (SBM) with nonparametric priors), we obtain a more versatile and principled framework for topic modeling (for example, it automatically detects the number of topics and hierarchically clusters both the words and documents). The analysis of artificial and real corpora demonstrates that our SBM approach leads to better topic models than LDA in terms of statistical model selection. Our work shows how to formally relate methods from community detection and topic modeling, opening the possibility of cross-fertilization between these two fields.
Impaired recovery of the Great Barrier Reef under cumulative stress Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Juan-Carlos Ortiz, Nicholas H. Wolff, Kenneth R. N. Anthony, Michelle Devlin, Stephen Lewis, Peter J. Mumby
Corals of the Great Barrier Reef (GBR) have declined over the past 30 years. While reef state depends on the balance between disturbance and recovery, most studies have focused on the effects of disturbance on reef decline. We show that coral recovery rates across the GBR declined by an average of 84% between 1992 and 2010. Recovery was variable: Some key coral types had close to zero recovery by the end of that period, whereas some reefs exhibited high recovery. Our results indicate that coral recovery is sensitive to chronic but manageable pressures, and is suppressed for several years following acute disturbances. Loss of recovery capacity was partly explained by the cumulative effects of chronic pressures including water quality, warming, and sublethal effects of acute disturbances (cyclones, outbreaks of crown-of-thorns starfish, and coral bleaching). Modeled projections indicate that recovery rates can respond rapidly to reductions in acute and chronic stressors, a result that is consistent with fast recovery observed on some reefs in the central and southern GBR since the end of the study period. A combination of local management actions to reduce chronic disturbances and global action to limit the effect of climate change is urgently required to sustain GBR coral cover and diversity.
Robust estimates of a high Ne/N ratio in a top marine predator, southern bluefin tuna Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Robin S. Waples, Peter M. Grewe, Mark W. Bravington, Richard Hillary, Pierre Feutry
Genetic studies of several marine species with high fecundity have produced “tiny” estimates (≤10−3) of the ratio of effective population size (Ne) to adult census size (N), suggesting that even very large populations might be at genetic risk. A recent study using close-kin mark-recapture methods estimated adult abundance at N ≈ 2 × 106 for southern bluefin tuna (SBT), a highly fecund top predator that supports a lucrative (~$1 billion/year) fishery. We used the same genetic and life history data (almost 13,000 fish collected over 5 years) to generate genetic and demographic estimates of Ne per generation and Nb (effective number of breeders) per year and the Ne/N ratio. Demographic estimates, which accounted for age-specific vital rates, skip breeding, variation in fecundity at age, and persistent individual differences in reproductive success, suggest that Ne/N is >0.1 and perhaps about 0.5. The genetic estimates supported this conclusion. Simulations using true Ne = 5 × 105 (Ne/N = 0.25) produced results statistically consistent with the empirical genetic estimates, whereas simulations using Ne = 2 × 104 (Ne/N = 0.01) did not. Our results show that robust estimates of Ne and Ne/N can be obtained for large populations, provided sufficiently large numbers of individuals and genetic markers are used and temporal replication (here, 5 years of adult and juvenile samples) is sufficient to provide a distribution of estimates. The high estimated Ne/N ratio in SBT is encouraging and suggests that the species will not be compromised by a lack of genetic diversity in responding to environmental change and harvest.
China’s livestock transition: Driving forces, impacts, and consequences Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Zhaohai Bai, Wenqi Ma, Lin Ma, Gerard L. Velthof, Zhibiao Wei, Petr Havlík, Oene Oenema, Michael R. F. Lee, Fusuo Zhang
China’s livestock industry has experienced a vast transition during the last three decades, with profound effects on domestic and global food provision, resource use, nitrogen and phosphorus losses, and greenhouse gas (GHG) emissions. We provide a comprehensive analysis of the driving forces around this transition and its national and global consequences. The number of livestock units (LUs) tripled in China in less than 30 years, mainly through the growth of landless industrial livestock production systems and the increase in monogastric livestock (from 62 to 74% of total LUs). Changes were fueled through increases in demand as well as, supply of new breeds, new technology, and government support. Production of animal source protein increased 4.9 times, nitrogen use efficiency at herd level tripled, and average feed use and GHG emissions per gram protein produced decreased by a factor of 2 between 1980 and 2010. In the same period, animal feed imports have increased 49 times, total ammonia and GHG emissions to the atmosphere doubled, and nitrogen losses to watercourses tripled. As a consequence, China’s livestock transition has significant global impact. Forecasts for 2050, using the Shared Socio-economic Pathways scenarios, indicate major further changes in livestock production and impacts. On the basis of these possible trajectories, we suggest an alternative transition, which should be implemented by government, processing industries, consumers, and retailers. This new transition is targeted to increase production efficiency and environmental performance at system level, with coupling of crop-livestock production, whole chain manure management, and spatial planning as major components.
Religious change preceded economic change in the 20th century Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Damian J. Ruck, R. Alexander Bentley, Daniel J. Lawson
The decline in the everyday importance of religion with economic development is a well-known correlation, but which phenomenon comes first? Using unsupervised factor analysis and a birth cohort approach to create a retrospective time series, we present 100-year time series of secularization in different nations, derived from recent global values surveys, which we compare by decade to historical gross domestic product figures in those nations. We find evidence that a rise in secularization generally has preceded economic growth over the past century. Our multilevel, time-lagged regressions also indicate that tolerance for individual rights predicted 20th century economic growth even better than secularization. These findings hold when we control for education and shared cultural heritage.
Air pollution and visitation at U.S. national parks Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 David Keiser, Gabriel Lade, Ivan Rudik
Hundreds of millions of visitors travel to U.S. national parks every year to visit America’s iconic landscapes. Concerns about air quality in these areas have led to strict, yet controversial pollution control policies. We document pollution trends in U.S. national parks and estimate the relationship between pollution and park visitation. From 1990 to 2014, average ozone concentrations in national parks were statistically indistinguishable from the 20 largest U.S. metropolitan areas. Further, relative to U.S. cities, national parks have seen only modest reductions in days with ozone concentrations exceeding levels deemed unhealthy by the U.S. Environmental Protection Agency. We find a robust, negative relationship between in-park ozone concentrations and park visitation. Still, 35% of all national park visits occur when ozone levels are elevated.
A mid-Cretaceous embryonic-to-neonate snake in amber from Myanmar Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Lida Xing, Michael W. Caldwell, Rui Chen, Randall L. Nydam, Alessandro Palci, Tiago R. Simões, Ryan C. McKellar, Michael S. Y. Lee, Ye Liu, Hongliang Shi, Kuan Wang, Ming Bai
We present the first known fossilized snake embryo/neonate preserved in early Late Cretaceous (Early Cenomanian) amber from Myanmar, which at the time, was an island arc including terranes from Austral Gondwana. This unique and very tiny snake fossil is an articulated postcranial skeleton, which includes posterior precloacal, cloacal, and caudal vertebrae, and details of squamation and body shape; a second specimen preserves a fragment of shed skin interpreted as a snake. Important details of skeletal ontogeny, including the stage at which snake zygosphene-zygantral joints began to form along with the neural arch lamina, are preserved. The vertebrae show similarities to those of fossil Gondwanan snakes, suggesting a dispersal route of Gondwanan faunas to Laurasia. Finally, the new species is the first Mesozoic snake to be found in a forested environment, indicating greater ecological diversity among early snakes than previously thought.
Microfluidics-based super-resolution microscopy enables nanoscopic characterization of blood stem cell rolling Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Karmen AbuZineh, Luay I. Joudeh, Bader Al Alwan, Samir M. Hamdan, Jasmeen S. Merzaban, Satoshi Habuchi
Hematopoietic stem/progenitor cell (HSPC) homing occurs via cell adhesion mediated by spatiotemporally organized ligand-receptor interactions. Although molecules and biological processes involved in this multistep cellular interaction with endothelium have been studied extensively, molecular mechanisms of this process, in particular the nanoscale spatiotemporal behavior of ligand-receptor interactions and their role in the cellular interaction, remain elusive. We introduce a microfluidics-based super-resolution fluorescence imaging platform and apply the method to investigate the initial essential step in the homing, tethering, and rolling of HSPCs under external shear stress that is mediated by selectins, expressed on endothelium, with selectin ligands (that is, CD44) expressed on HSPCs. Our new method reveals transient nanoscale reorganization of CD44 clusters during cell rolling on E-selectin. We demonstrate that this mechanical force-induced reorganization is accompanied by a large structural reorganization of actin cytoskeleton. The CD44 clusters were partly disrupted by disrupting lipid rafts. The spatial reorganization of CD44 and actin cytoskeleton was not observed for the lipid raft–disrupted cells, demonstrating the essential role of the spatial clustering of CD44 on its reorganization during cell rolling. The lipid raft disruption causes faster and unstable cell rolling on E-selectin compared with the intact cells. Together, our results demonstrate that the spatial reorganization of CD44 and actin cytoskeleton is the result of concerted effect of E-selectin–ligand interactions, external shear stress, and spatial clustering of the selectin ligands, and has significant effect on the tethering/rolling step in HSPC homing. Our new experimental platform provides a foundation for characterizing complicated HSPC homing.
The equation of motion for supershear frictional rupture fronts Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 David S. Kammer, Ilya Svetlizky, Gil Cohen, Jay Fineberg
The rupture fronts that mediate the onset of frictional sliding may propagate at speeds below the Rayleigh wave speed or may surpass the shear wave speed and approach the longitudinal wave speed. While the conditions for the transition from sub-Rayleigh to supershear propagation have been studied extensively, little is known about what dictates supershear rupture speeds and how the interplay between the stresses that drive propagation and interface properties that resist motion affects them. By combining laboratory experiments and numerical simulations that reflect natural earthquakes, we find that supershear rupture propagation speeds can be predicted and described by a fracture mechanics–based equation of motion. This equation of motion quantitatively predicts rupture speeds, with the velocity selection dictated by the interface properties and stress. Our results reveal a critical rupture length, analogous to Griffith’s length for sub-Rayleigh cracks, below which supershear propagation is impossible. Above this critical length, supershear ruptures can exist, once excited, even for extremely low preexisting stress levels. These results significantly improve our fundamental understanding of what governs the speed of supershear earthquakes, with direct and important implications for interpreting their unique supershear seismic radiation patterns.
Surface-modulated palladium-nickel icosahedra as high-performance non-platinum oxygen reduction electrocatalysts Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Yonggang Feng, Qi Shao, Yujin Ji, Xiaoneng Cui, Youyong Li, Xing Zhu, Xiaoqing Huang
The search for high-performance non-platinum (Pt) electrocatalysts is the most challenging issue for fuel cell technology. Creating bimetallic non-Pt nanocrystals (NCs) with core/shell structures or alloy features has widely been explored as the most effective way for enhancing their electrochemical properties but still suffered from undesirable performance due to the limited interactions between the different components. By addressing the above issue, we report on a new class of active and stable bimetallic non-Pt electrocatalysts with palladium (Pd) icosahedra as the core and nickel (Ni) decorating the surface toward cathodic oxygen reduction reaction (ORR) under alkaline conditions. The optimized Pd6Ni icosahedra with unique interaction between an icosahedral Pd core and surface Ni yield the highest ORR activity with a mass activity of 0.22 A mgPd−1, which is better than those of the conventional Pd6Ni icosahedra with alloy surfaces or Pd-rich surfaces, and even two times higher than that of the commercial Pt/C (0.11 A mgPt−1), representing one of the best non-Pt electrocatalysts. Simulations reveal that the Pd icosahedra decorated with Ni atoms emerged in the subsurface can weaken the interaction between the adsorbed oxygen and Pd (111) facet and enhance the ORR activities due to an obvious shift of d-band center. More significantly, under electrochemical accelerated durability test, the Pd6Ni icosahedra can endure at least 10,000 cycles with negligible activity decay and structural change. The present work demonstrates an important advance in surface tuning of bimetallic NCs as high-performance non-Pt catalysts for catalysis, energy conversion, and beyond.
Addressable electron spin resonance using donors and donor molecules in silicon Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Samuel J. Hile, Lukas Fricke, Matthew G. House, Eldad Peretz, Chin Yi Chen, Yu Wang, Matthew Broome, Samuel K. Gorman, Joris G. Keizer, Rajib Rahman, Michelle Y. Simmons
Phosphorus donor impurities in silicon are a promising candidate for solid-state quantum computing due to their exceptionally long coherence times and high fidelities. However, individual addressability of exchange coupled donors with separations ~15 nm is challenging. We show that by using atomic precision lithography, we can place a single P donor next to a 2P molecule 16 ± 1 nm apart and use their distinctive hyperfine coupling strengths to address qubits at vastly different resonance frequencies. In particular, the single donor yields two hyperfine peaks separated by 97 ± 2.5 MHz, in contrast to the donor molecule that exhibits three peaks separated by 262 ± 10 MHz. Atomistic tight-binding simulations confirm the large hyperfine interaction strength in the 2P molecule with an interdonor separation of ~0.7 nm, consistent with lithographic scanning tunneling microscopy images of the 2P site during device fabrication. We discuss the viability of using donor molecules for built-in addressability of electron spin qubits in silicon.
Dissecting spin-phonon equilibration in ferrimagnetic insulators by ultrafast lattice excitation Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Sebastian F. Maehrlein, Ilie Radu, Pablo Maldonado, Alexander Paarmann, Michael Gensch, Alexandra M. Kalashnikova, Roman V. Pisarev, Martin Wolf, Peter M. Oppeneer, Joseph Barker, Tobias Kampfrath
To gain control over magnetic order on ultrafast time scales, a fundamental understanding of the way electron spins interact with the surrounding crystal lattice is required. However, measurement and analysis even of basic collective processes such as spin-phonon equilibration have remained challenging. Here, we directly probe the flow of energy and angular momentum in the model insulating ferrimagnet yttrium iron garnet. After ultrafast resonant lattice excitation, we observe that magnetic order reduces on distinct time scales of 1 ps and 100 ns. Temperature-dependent measurements, a spin-coupling analysis, and simulations show that the two dynamics directly reflect two stages of spin-lattice equilibration. On the 1-ps scale, spins and phonons reach quasi-equilibrium in terms of energy through phonon-induced modulation of the exchange interaction. This mechanism leads to identical demagnetization of the ferrimagnet’s two spin sublattices and to a ferrimagnetic state of increased temperature yet unchanged total magnetization. Finally, on the much slower, 100-ns scale, the excess of spin angular momentum is released to the crystal lattice, resulting in full equilibrium. Our findings are relevant for all insulating ferrimagnets and indicate that spin manipulation by phonons, including the spin Seebeck effect, can be extended to antiferromagnets and into the terahertz frequency range.
Room temperature in-plane ferroelectricity in van der Waals In2Se3 Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Changxi Zheng, Lei Yu, Lin Zhu, James L. Collins, Dohyung Kim, Yaoding Lou, Chao Xu, Meng Li, Zheng Wei, Yupeng Zhang, Mark T. Edmonds, Shiqiang Li, Jan Seidel, Ye Zhu, Jefferson Zhe Liu, Wen-Xin Tang, Michael S. Fuhrer
Van der Waals (vdW) assembly of layered materials is a promising paradigm for creating electronic and optoelectronic devices with novel properties. Ferroelectricity in vdW layered materials could enable nonvolatile memory and low-power electronic and optoelectronic switches, but to date, few vdW ferroelectrics have been reported, and few in-plane vdW ferroelectrics are known. We report the discovery of in-plane ferroelectricity in a widely investigated vdW layered material, β′-In2Se3. The in-plane ferroelectricity is strongly tied to the formation of one-dimensional superstructures aligning along one of the threefold rotational symmetric directions of the hexagonal lattice in the c plane. Surprisingly, the superstructures and ferroelectricity are stable to 200°C in both bulk and thin exfoliated layers of In2Se3. Because of the in-plane nature of ferroelectricity, the domains exhibit a strong linear dichroism, enabling novel polarization-dependent optical properties.
Domain Meissner state and spontaneous vortex-antivortex generation in the ferromagnetic superconductor EuFe2(As0.79P0.21)2 Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Vasily S. Stolyarov, Ivan S. Veshchunov, Sergey Yu. Grebenchuk, Denis S. Baranov, Igor A. Golovchanskiy, Andrey G. Shishkin, Nan Zhou, Zhixiang Shi, Xiaofeng Xu, Sunseng Pyon, Yue Sun, Wenhe Jiao, Guang-Han Cao, Lev Ya. Vinnikov, Alexander A. Golubov, Tsuyoshi Tamegai, Alexander I. Buzdin, Dimitri Roditchev
The interplay between superconductivity and magnetism is one of the oldest enigmas in physics. Usually, the strong exchange field of ferromagnet suppresses singlet superconductivity via the paramagnetic effect. In EuFe2(As0.79P0.21)2, a material that becomes not only superconducting at 24.2 K but also ferromagnetic below 19 K, the coexistence of the two antagonistic phenomena becomes possible because of the unusually weak exchange field produced by the Eu subsystem. We demonstrate experimentally and theoretically that when the ferromagnetism adds to superconductivity, the Meissner state becomes spontaneously inhomogeneous, characterized by a nanometer-scale striped domain structure. At yet lower temperature and without any externally applied magnetic field, the system locally generates quantum vortex-antivortex pairs and undergoes a phase transition into a domain vortex-antivortex state characterized by much larger domains and peculiar Turing-like patterns. We develop a quantitative theory of this phenomenon and put forth a new way to realize superconducting superlattices and control the vortex motion in ferromagnetic superconductors by tuning magnetic domains—unprecedented opportunity to consider for advanced superconducting hybrids.
Adsorbate-driven reactive interfacial Pt-NiO1−x nanostructure formation on the Pt3Ni(111) alloy surface Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Jeongjin Kim, Woong Hyeon Park, Won Hui Doh, Si Woo Lee, Myung Cheol Noh, Jean-Jacques Gallet, Fabrice Bournel, Hiroshi Kondoh, Kazuhiko Mase, Yousung Jung, Bongjin Simon Mun, Jeong Young Park
The origin of the synergistic catalytic effect between metal catalysts and reducible oxides has been debated for decades. Clarification of this effect, namely, the strong metal-support interaction (SMSI), requires an understanding of the geometric and electronic structures of metal-metal oxide interfaces under operando conditions. We show that the inherent lattice mismatch of bimetallic materials selectively creates surface segregation of subsurface metal atoms. Interfacial metal-metal oxide nanostructures are then formed under chemical reaction environments at ambient pressure, which thus increases the catalytic activity for the CO oxidation reaction. Our in situ surface characterizations using ambient-pressure scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy exhibit (i) a Pt-skin layer on the Pt-Ni alloyed surface under ultrahigh vacuum, (ii) selective Ni segregation followed by the formation of NiO1−x clusters under oxygen gas, and (iii) the coexistence of NiO1−x clusters on the Pt-skin during the CO oxidation reaction. The formation of interfacial Pt-NiO1−x nanostructures is responsible for a highly efficient step in the CO oxidation reaction. Density functional theory calculations of the Pt3Ni(111) surface demonstrate that a CO molecule adsorbed on an exposed Pt atom with an interfacial oxygen from a segregated NiO1−x cluster has a low surface energy barrier of 0.37 eV, compared with 0.86 eV for the Pt(111) surface.
A new strategy to efficiently cleave and form C–H bonds using proton-coupled electron transfer Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Todd F. Markle, Julia W. Darcy, James M. Mayer
Oxidative activation and reductive formation of C–H bonds are crucial in many chemical, industrial, and biological processes. Reported here is a new strategy for these transformations, using a form of proton-coupled electron transfer (PCET): intermolecular electron transfer coupled to intramolecular proton transfer with an appropriately placed cofactor. In a fluorenyl-benzoate, the positioned carboxylate facilitates rapid cleavage of a benzylic C–H bond upon reaction with even weak 1e− oxidants, for example, decamethylferrocenium. Mechanistic studies establish that the proton and electron transfer to disparate sites in a single concerted kinetic step, via multi-site concerted proton-electron transfer. This work represents a new elementary reaction step available to C–H bonds. This strategy is extended to reductive formation of C–H bonds in two systems. Molecular design considerations and possible utility in synthetic and enzymatic systems are discussed.
Accelerating rates of Arctic carbon cycling revealed by long-term atmospheric CO2 measurements Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Su-Jong Jeong, A. Anthony Bloom, David Schimel, Colm Sweeney, Nicholas C. Parazoo, David Medvigy, Gabriela Schaepman-Strub, Chunmiao Zheng, Christopher R. Schwalm, Deborah N. Huntzinger, Anna M. Michalak, Charles E. Miller
The contemporary Arctic carbon balance is uncertain, and the potential for a permafrost carbon feedback of anywhere from 50 to 200 petagrams of carbon (Schuur et al., 2015) compromises accurate 21st-century global climate system projections. The 42-year record of atmospheric CO2 measurements at Barrow, Alaska (71.29 N, 156.79 W), reveals significant trends in regional land-surface CO2 anomalies (ΔCO2), indicating long-term changes in seasonal carbon uptake and respiration. Using a carbon balance model constrained by ΔCO2, we find a 13.4% decrease in mean carbon residence time (50% confidence range = 9.2 to 17.6%) in North Slope tundra ecosystems during the past four decades, suggesting a transition toward a boreal carbon cycling regime. Temperature dependencies of respiration and carbon uptake suggest that increases in cold season Arctic labile carbon release will likely continue to exceed increases in net growing season carbon uptake under continued warming trends.
Chondrules as direct thermochemical sensors of solar protoplanetary disk gas Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Guy Libourel, Marc Portail
Chondrules, millimeter-sized igneous spherules comprising the major component of most chondritic meteorites, formed during the first 4 million to 5 million years of the evolution of the solar protoplanetary disk and, therefore, can potentially offer important constraints on the conditions in the disk, provided that the processes that led to their formation can be understood. High-resolution cathodoluminescence (CL) survey of chondrules from various chondrite groups revealed changes of CL activator concentrations of magnesium-rich olivines. We show that these overlooked internal zoning structures provide evidence for high-temperature gas-assisted near-equilibrium epitaxial growth of olivines during chondrule formation. We argue that this interaction with the surrounding gas, rather than various cooling histories, defined chondrule composition and texture. Chondrules are thus direct thermochemical sensors of their high-temperature gaseous environment, and high partial pressures of gaseous Mg and SiO are required in their solar protoplanetary disk-forming region to maintain olivine saturation in chondrules. The inferred crystallization of olivines, from stable melts approaching equilibrium with the surrounding gas, provides an explanation for the notable absence of large and systematic isotopic fractionations in chondrules.
Molecular signatures and functional analysis of beige adipocytes induced from in vivo intra-abdominal adipocytes Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Huiling Xue, Zhe Wang, Yongjie Hua, Shanshan Ke, Yao Wang, Junpeng Zhang, Yi-Hsuan Pan, Wenjie Huang, David M. Irwin, Shuyi Zhang
Beige adipocytes can be induced from white adipocytes and precursors upon stimulation by cold temperatures and act like brown adipocytes to increase energy expenditure. Most in vivo studies examining the mechanisms for the induction of beige adipocytes have focused on subcutaneous white adipose tissue (sWAT; benign fat) in the mouse. How intra-abdominal WAT (aWAT; malignant fat) develops into beige adipocytes remains obscure, largely because there is a lack of a good animal model for the induction of beige adipocytes from aWAT. To better understand the development of beige adipocytes from mammalian WATs, especially aWAT, we induced beige adipocytes from bat aWAT and mouse sWAT by exposure to cold temperatures and analyzed their molecular signatures. RNA sequencing followed by whole genome–wide expression analysis shows that beige adipocytes induced from bat aWAT, rather than sWAT, have molecular signatures resembling those of mouse sWAT-induced beige adipocytes and exhibit dynamic profiles similar to those of classical brown adipocytes. In addition, we identified molecular markers that were highly enriched in beige adipocytes and conserved between bat aWAT and mouse sWAT, a set that included the genes Uqcrc1 and Letm1. Furthermore, knockdown of Uqcrc1 and Letm1 expression shows that they are required not only for beige adipocyte differentiation but also for preadipocyte maturation. This study presents a new model for research into the induction of beige adipocytes from aWAT in vivo, which, when combined with models where beige adipocytes are induced from sWAT, provides insight into therapeutic approaches for combating obesity-related diseases in humans.
Plasticity reveals hidden resistance to extinction under climate change in the global hotspot of salamander diversity Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Eric A. Riddell, Jonathan P. Odom, Jason D. Damm, Michael W. Sears
Extinction rates are predicted to rise exponentially under climate warming, but many of these predictions ignore physiological and behavioral plasticity that might buffer species from extinction. We evaluated the potential for physiological acclimatization and behavioral avoidance of poor climatic conditions to lower extinction risk under climate change in the global hotspot of salamander diversity, a region currently predicted to lose most of the salamander habitat due to warming. Our approach integrated experimental physiology and behavior into a mechanistic species distribution model to predict extinction risk based on an individual’s capacity to maintain energy balance with and without plasticity. We assessed the sensitivity of extinction risk to body size, behavioral strategies, limitations on energy intake, and physiological acclimatization of water loss and metabolic rate. The field and laboratory experiments indicated that salamanders readily acclimatize water loss rates and metabolic rates in ways that could maintain positive energy balance. Projections with plasticity reduced extinction risk by 72% under climate warming, especially in the core of their range. Further analyses revealed that juveniles might experience the greatest physiological stress under climate warming, but we identified specific physiological adaptations or plastic responses that could minimize the lethal physiological stress imposed on juveniles. We conclude that incorporating plasticity fundamentally alters ecological predictions under climate change by reducing extinction risk in the hotspot of salamander diversity.
Evidence of an early projectile point technology in North America at the Gault Site, Texas, USA Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Thomas J. Williams, Michael B. Collins, Kathleen Rodrigues, William Jack Rink, Nancy Velchoff, Amanda Keen-Zebert, Anastasia Gilmer, Charles D. Frederick, Sergio J. Ayala, Elton R. Prewitt
American archeology has long been polarized over the issue of a human presence in the Western Hemisphere earlier than Clovis. As evidence of early sites across North and South America continues to emerge, stone tool assemblages appear more geographically and temporally diverse than traditionally assumed. Within this new framework, the prevailing models of Clovis origins and the peopling of the Americas are being reevaluated. This paper presents age estimates from a series of alluvial sedimentary samples from the earliest cultural assemblage at the Gault Site, Central Texas. The optically stimulated luminescence age estimates (~16 to 20 thousand years ago) indicate an early human occupation in North America before at least ~16 thousand years ago. Significantly, this assemblage exhibits a previously unknown, early projectile point technology unrelated to Clovis. Within a wider context, this evidence suggests that Clovis technology spread across an already regionalized, indigenous population.
Neurite architecture of the planum temporale predicts neurophysiological processing of auditory speech Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Sebastian Ocklenburg, Patrick Friedrich, Christoph Fraenz, Caroline Schlüter, Christian Beste, Onur Güntürkün, Erhan Genç
The left hemispheric advantage in speech perception is reflected in faster neurophysiological processing. On the basis of postmortem data, it has been suggested that asymmetries in the organization of the intrinsic microcircuitry of the posterior temporal lobe may produce this leftward timing advantage. However, whether this hypothetical structure-function relationship exists in vivo has never been empirically validated. To test this assumption, we used in vivo neurite orientation dispersion and density imaging to quantify microcircuitry in terms of axon and dendrite complexity of the left and right planum temporale in 98 individuals. We found that a higher density of dendrites and axons in the temporal speech area is associated with faster neurophysiological processing of auditory speech, as reflected by electroencephalography. Our results imply that a higher density and higher number of synaptic contacts in the left posterior temporal lobe increase temporal precision and decrease latency of neurophysiological processes in this brain region.
Barium isotope evidence for pervasive sediment recycling in the upper mantle Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Sune G. Nielsen, Tristan J. Horner, Helena V. Pryer, Jerzy Blusztajn, Yunchao Shu, Mark D. Kurz, Véronique Le Roux
The upper mantle, as sampled by mid-ocean ridge basalts (MORBs), exhibits significant chemical variability unrelated to mechanisms of melt extraction at ridges. We show that barium isotope variations in global MORBs vary systematically with radiogenic isotopes and trace element ratios, which reflects mixing between depleted and enriched MORB melts. In addition, modern sediments and enriched MORBs share similar Ba isotope signatures. Using modeling, we show that addition of ~0.1% by weight of sediment components into the depleted mantle in subduction zones must impart a sedimentary Ba signature to the overlying mantle and induce low-degree melting that produces the enriched MORB reservoir. Subsequently, these enriched domains convect toward mid-ocean ridges and produce radiogenic isotope variation typical of enriched MORBs. This mechanism can explain the chemical and isotopic features of enriched MORBs and provide strong evidence for pervasive sediment recycling in the upper mantle.
Phosphorylation of human TRM9L integrates multiple stress-signaling pathways for tumor growth suppression Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Chen Gu, Jillian Ramos, Ulrike Begley, Peter C. Dedon, Dragony Fu, Thomas J. Begley
The human transfer RNA methyltransferase 9–like gene (TRM9L, also known as KIAA1456) encodes a negative regulator of tumor growth that is frequently silenced in many forms of cancer. While TRM9L can inhibit tumor cell growth in vivo, the molecular mechanisms underlying the tumor inhibition activity of TRM9L are unknown. We show that oxidative stress induces the rapid and dose-dependent phosphorylation of TRM9L within an intrinsically disordered domain that is necessary for tumor growth suppression. Multiple serine residues are hyperphosphorylated in response to oxidative stress. Using a chemical genetic approach, we identified a key serine residue in TRM9L that undergoes hyperphosphorylation downstream of the oxidative stress–activated MEK (mitogen-activated protein kinase kinase)–ERK (extracellular signal–regulated kinase)–RSK (ribosomal protein S6 kinase) signaling cascade. Moreover, we found that phosphorylated TRM9L interacts with the 14-3-3 family of proteins, providing a link between oxidative stress and downstream cellular events involved in cell cycle control and proliferation. Mutation of the serine residues required for TRM9L hyperphosphorylation and 14-3-3 binding abolished the tumor inhibition activity of TRM9L. Our results uncover TRM9L as a key downstream effector of the ERK signaling pathway and elucidate a phospho-signaling regulatory mechanism underlying the tumor inhibition activity of TRM9L.
BAFF inhibition attenuates fibrosis in scleroderma by modulating the regulatory and effector B cell balance Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Takashi Matsushita, Tadahiro Kobayashi, Kie Mizumaki, Miyu Kano, Tomoyo Sawada, Momoko Tennichi, Ai Okamura, Yasuhito Hamaguchi, Yoichiro Iwakura, Minoru Hasegawa, Manabu Fujimoto, Kazuhiko Takehara
Systemic sclerosis (SSc) is an autoimmune disease characterized by skin and lung fibrosis. More than 90% of patients with SSc are positive for autoantibodies. In addition, serum B cell activating factor (BAFF) level is correlated with SSc severity and activity. Thus, B cells are considered to play a pathogenic role in SSc. However, there are two opposing subsets: regulatory B cells (Bregs) and effector B cells (Beffs). Interleukin-10 (IL-10)–producing Bregs negatively regulate the immune response, while IL-6–producing Beffs positively regulate it. Therefore, a protocol that selectively depletes Beffs would represent a potent therapy for SSc. The aims of this study were to investigate the roles of Bregs and Beffs in SSc and to provide a scientific basis for developing a new treatment strategy targeting B cells. A bleomycin-induced scleroderma model was induced in mice with a B cell–specific deficiency in IL-6 or IL-10. We also examined whether BAFF regulates cytokine-producing B cells and its effects on the scleroderma model. IL-6–producing Beffs increased in number and infiltrated the inflamed skin in the scleroderma model. The skin and lung fibrosis was attenuated in B cell–specific IL-6–deficient mice, whereas B cell–specific IL-10–deficient mice showed more severe fibrosis. In addition, BAFF increased Beffs but suppressed Bregs. Furthermore, BAFF antagonist attenuated skin and lung fibrosis in the scleroderma model with reduction of Beffs but not of Bregs. The current study indicates that Beffs play a pathogenic role in the scleroderma model, while Bregs play a protective role. BAFF inhibition is a potential therapeutic strategy for SSc via alteration of B cell balance.
Establishment of environmentally sensitive DNA methylation states in the very early human embryo Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Noah J. Kessler, Robert A. Waterland, Andrew M. Prentice, Matt J. Silver
The molecular mechanisms responsible for the developmental origins of later disease are currently unknown. We previously demonstrated that women’s periconceptional nutrition predicts their offspring’s DNA methylation at metastable epialleles (MEs). We present a genome-wide screen yielding 687 MEs and track their trajectories across nine developmental stages in human in vitro fertilization embryos. MEs exhibit highly unusual methylation dynamics across the implantation-gastrulation transition, producing a large excess of intermediate methylation states, suggesting the potential for differential programming in response to external signals. Using a natural experiment in rural Gambia, we show that genomic regions sensitive to season of conception are highly enriched for MEs and show similar atypical methylation patterns. MEs are enriched for proximal enhancers and transcription start sites and are influenced by genotype. Together, these observations position MEs as distinctive epigenomic features programmed in the early embryo, sensitive to genetic and periconceptional environment, and with the potential to influence phenotype.
A crossbar network for silicon quantum dot qubits Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Ruoyu Li, Luca Petit, David P. Franke, Juan Pablo Dehollain, Jonas Helsen, Mark Steudtner, Nicole K. Thomas, Zachary R. Yoscovits, Kanwal J. Singh, Stephanie Wehner, Lieven M. K. Vandersypen, James S. Clarke, Menno Veldhorst
The spin states of single electrons in gate-defined quantum dots satisfy crucial requirements for a practical quantum computer. These include extremely long coherence times, high-fidelity quantum operation, and the ability to shuttle electrons as a mechanism for on-chip flying qubits. To increase the number of qubits to the thousands or millions of qubits needed for practical quantum information, we present an architecture based on shared control and a scalable number of lines. Crucially, the control lines define the qubit grid, such that no local components are required. Our design enables qubit coupling beyond nearest neighbors, providing prospects for nonplanar quantum error correction protocols. Fabrication is based on a three-layer design to define qubit and tunnel barrier gates. We show that a double stripline on top of the structure can drive high-fidelity single-qubit rotations. Self-aligned inhomogeneous magnetic fields induced by direct currents through superconducting gates enable qubit addressability and readout. Qubit coupling is based on the exchange interaction, and we show that parallel two-qubit gates can be performed at the detuning-noise insensitive point. While the architecture requires a high level of uniformity in the materials and critical dimensions to enable shared control, it stands out for its simplicity and provides prospects for large-scale quantum computation in the near future.
Consecutive crystallographic reorientations and superplasticity in body-centered cubic niobium nanowires Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Qiannan Wang, Jiangwei Wang, Jixue Li, Ze Zhang, Scott X. Mao
Plasticity of metallic nanowires is often controlled by the activities of single deformation mode. It remains largely unclear whether multiple deformation modes can be activated in an individual metallic nanowire and how much plasticity they can contribute. In situ nanomechanical testing reveals a superior plastic deformation ability of body-centered cubic (BCC) niobium nanowires, in which a remarkable elongation of more than 269% is achieved before fracture. This superplastic deformation originates from a synergy of consecutively nucleated multiple reorientation processes that occur for more than five times via three distinct mechanisms, that is, stress-activated phase transformation, deformation twinning, and slip-induced crystal rotation. These three coupled mechanisms work concurrently, resulting in sequential reorientations and therefore superplastic deformation of Nb nanowires. Our findings reveal a superior mechanical property of BCC Nb nanowires through the close coordination of multiple deformation modes, which may have some implications in other metallic nanowire systems.
Stretching vibration is a spectator in nucleophilic substitution Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Martin Stei, Eduardo Carrascosa, Alexander Dörfler, Jennifer Meyer, Balázs Olasz, Gábor Czakó, Anyang Li, Hua Guo, Roland Wester
How chemical reactions are influenced by reactant vibrational excitation is a long-standing question at the core of chemical reaction dynamics. In reactions of polyatomic molecules, where the Polanyi rules are not directly applicable, certain vibrational modes can act as spectators. In nucleophilic substitution reactions, CH stretching vibrations have been considered to be such spectators. While this picture has been challenged by some theoretical studies, experimental insight has been lacking. We show that the nucleophilic substitution reaction of F− with CH3I is minimally influenced by an excitation of the symmetric CH stretching vibration. This contrasts with the strong vibrational enhancement of the proton transfer reaction measured in parallel. The spectator behavior of the stretching mode is supported by both quasi-classical trajectory simulations and the Sudden Vector Projection model.
Suppression of photo-oxidation of organic chromophores by strong coupling to plasmonic nanoantennas Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Battulga Munkhbat, Martin Wersäll, Denis G. Baranov, Tomasz J. Antosiewicz, Timur Shegai
Intermixed light-matter quasi-particles—polaritons—have unique optical properties owing to their compositional nature. These intriguing hybrid states have been extensively studied over the past decades in a wide range of realizations aiming at both basic science and emerging applications. However, recently, it has been demonstrated that not only optical but also material-related properties, such as chemical reactivity and charge transport, may be significantly altered in the strong coupling regime of light-matter interactions. We show that a nanoscale system, composed of a plasmonic nanoprism strongly coupled to excitons in a J-aggregated form of organic chromophores, experiences modified excited-state dynamics and, therefore, modified photochemical reactivity. Our experimental results reveal that photobleaching, one of the most fundamental photochemical reactions, can be effectively controlled and suppressed by the degree of plasmon-exciton coupling and detuning. In particular, we observe a 100-fold stabilization of organic dyes for the red-detuned nanoparticles. Our findings contribute to understanding of photochemical properties in the strong coupling regime and may find important implications for the performance and improved stability of optical devices incorporating organic dyes.
Enhancing ferroelectric photovoltaic effect by polar order engineering Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Lu You, Fan Zheng, Liang Fang, Yang Zhou, Liang Z. Tan, Zeyu Zhang, Guohong Ma, Daniel Schmidt, Andrivo Rusydi, Le Wang, Lei Chang, Andrew M. Rappe, Junling Wang
Ferroelectric materials for photovoltaics have sparked great interest because of their switchable photoelectric responses and above-bandgap photovoltages that violate conventional photovoltaic theory. However, their relatively low photocurrent and power conversion efficiency limit their potential application in solar cells. To improve performance, conventional strategies focus mainly on narrowing the bandgap to better match the solar spectrum, leaving the fundamental connection between polar order and photovoltaic effect largely overlooked. We report large photovoltaic enhancement by A-site substitutions in a model ferroelectric photovoltaic material, BiFeO3. As revealed by optical measurements and supported by theoretical calculations, the enhancement is accompanied by the chemically driven rotational instability of the polarization, which, in turn, affects the charge transfer at the band edges and drives a direct-to-indirect bandgap transition, highlighting the strong coupling between polarization, lattice, and orbital order parameters in ferroelectrics. Polar order engineering thus provides an additional degree of freedom to further boost photovoltaic efficiency in ferroelectrics and related materials.
Nano-kirigami with giant optical chirality Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Zhiguang Liu, Huifeng Du, Jiafang Li, Ling Lu, Zhi-Yuan Li, Nicholas X. Fang
Kirigami enables versatile shape transformation from two-dimensional (2D) precursors to 3D architectures with simplified fabrication complexity and unconventional structural geometries. We demonstrate a one-step and on-site nano-kirigami method that avoids the prescribed multistep procedures in traditional mesoscopic kirigami or origami techniques. The nano-kirigami is readily implemented by in situ cutting and buckling a suspended gold film with programmed ion beam irradiation. By using the topography-guided stress equilibrium, rich 3D shape transformation such as buckling, rotation, and twisting of nanostructures is precisely achieved, which can be predicted by our mechanical modeling. Benefiting from the nanoscale 3D twisting features, giant optical chirality is achieved in an intuitively designed 3D pinwheel-like structure, in strong contrast to the achiral 2D precursor without nano-kirigami. The demonstrated nano-kirigami, as well as the exotic 3D nanostructures, could be adopted in broad nanofabrication platforms and could open up new possibilities for the exploration of functional micro-/nanophotonic and mechanical devices.
Ultrathin graphdiyne film on graphene through solution-phase van der Waals epitaxy Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Xin Gao, Yihan Zhu, Ding Yi, Jingyuan Zhou, Shishu Zhang, Chen Yin, Feng Ding, Shuqing Zhang, Xiaohui Yi, Jizheng Wang, Lianming Tong, Yu Han, Zhongfan Liu, Jin Zhang
Graphdiyne (GDY) is an ordered two-dimensional (2D) carbon allotrope comprising sp- and sp2-hybridized carbon atoms with high degrees of π-conjugation, which features a natural band gap and superior electric properties. However, the synthesis of one- or few-layer GDY remains challenging because of the free rotation around alkyne-aryl single bonds and the lack of thickness control. We report the facile synthesis of an ultrathin single-crystalline GDY film on graphene through a solution-phase van der Waals epitaxial strategy. The weak admolecule-substrate interaction at the heterojunction drastically relaxes the large lattice mismatch between GDY and graphene. It allows the fast in-plane coupling of admolecules and slow out-of-plane growth toward the formation of an incommensurately stacked heterostructure, which is composed of single-layer graphene and few-layer ABC-stacked GDY, as directly observed by electron microscopy and identified from Raman fingerprints. This study provides a general route not only to the bottom-up synthesis of intriguing 2D acetylenic carbon allotropes but also to the device fabrication for the direct measurement of their intrinsic electrical, mechanical, and thermal properties.
Alternative cereals can improve water use and nutrient supply in India Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Kyle Frankel Davis, Davide Danilo Chiarelli, Maria Cristina Rulli, Ashwini Chhatre, Brian Richter, Deepti Singh, Ruth DeFries
Humanity faces the grand challenge of feeding a growing, more affluent population in the coming decades while reducing the environmental burden of agriculture. Approaches that integrate food security and environmental goals offer promise for achieving a more sustainable global food system, yet little work has been done to link potential solutions with agricultural policies. Taking the case of cereal production in India, we use a process-based crop water model and government data on food production and nutrient content to assess the implications of various crop-shifting scenarios on consumptive water demand and nutrient production. We find that historical growth in wheat production during the rabi (non-monsoon) season has been the main driver of the country’s increased consumptive irrigation water demand and that rice is the least water-efficient cereal for the production of key nutrients, especially for iron, zinc, and fiber. By replacing rice areas in each district with the alternative cereal (maize, finger millet, pearl millet, or sorghum) with the lowest irrigation (blue) water footprint (WFP), we show that it is possible to reduce irrigation water demand by 33% and improve the production of protein (+1%), iron (+27%), and zinc (+13%) with only a modest reduction in calories. Replacing rice areas with the lowest total (rainfall + irrigation) WFP alternative cereal or the cereal with the highest nutritional yield (metric tons of protein per hectare or kilograms of iron per hectare) yielded similar benefits. By adopting a similar multidimensional framework, India and other nations can identify food security solutions that can achieve multiple sustainability goals simultaneously.
Long-term viability of carbon sequestration in deep-sea sediments Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Yihua Teng, Dongxiao Zhang
Sequestration of carbon dioxide in deep-sea sediments has been proposed for the long-term storage of anthropogenic CO2 that can take advantage of the current offshore infrastructure. It benefits from the negative buoyancy effect and hydrate formation under conditions of high pressure and low temperature. However, the multiphysics process of injection and postinjection fate of CO2 and the feasibility of subseabed disposal of CO2 under different geological and operational conditions have not been well studied. With a detailed study of the coupled processes, we investigate whether storing CO2 into deep-sea sediments is viable, efficient, and secure over the long term. We also study the evolution of multiphase and multicomponent flow and the impact of hydrate formation on storage efficiency. The results show that low buoyancy and high viscosity slow down the ascending plume and the forming of the hydrate cap effectively reduces permeability and finally becomes an impermeable seal, thus limiting the movement of CO2 toward the seafloor. We identify different flow patterns at varied time scales by analyzing the mass distribution of CO2 in different phases over time. We observe the formation of a fluid inclusion, which mainly consists of liquid CO2 and is encapsulated by an impermeable hydrate film in the diffusion-dominated stage. The trapped liquid CO2 and CO2 hydrate finally dissolve into the pore water through diffusion of the CO2 component, resulting in permanent storage. We perform sensitivity analyses on storage efficiency under variable geological and operational conditions. We find that under a deep-sea setting, CO2 sequestration in intact marine sediments is generally safe and permanent.
Capacity to support predators scales with habitat size Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Angus R. McIntosh, Peter A. McHugh, Michael J. Plank, Phillip G. Jellyman, Helen J. Warburton, Hamish S. Greig
Habitat reduction could drive biodiversity loss if the capacity of food webs to support predators is undermined by habitat-size constraints on predator body size. Assuming that (i) available space restricts predator body size, (ii) mass-specific energy needs of predators scale with their body size, and (iii) energy availability scales with prey biomass, we predicted that predator biomass per unit area would scale with habitat size (quarter-power exponent) and prey biomass (three-quarter–power exponent). We found that total predator biomass scaled with habitat size and prey resources as expected across 29 New Zealand rivers, such that a unit of habitat in a small ecosystem supported less predator biomass than an equivalent unit in a large ecosystem. The lower energetic costs of large body size likely mean that a unit of prey resource supports more biomass of large-bodied predators compared to small-bodied predators. Thus, contracting habitat size reduces the predator mass that can be supported because of constraints on predator body size, and this may be a powerful mechanism exacerbating reductions in biodiversity due to habitat loss.
Flavivirus serocomplex cross-reactive immunity is protective by activating heterologous memory CD4 T cells Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Wilfried A. A. Saron, Abhay P. S. Rathore, Lim Ting, Eng Eong Ooi, Jenny Low, Soman N. Abraham, Ashley L. St. John
How previous immunity influences immune memory recall and protection against related flaviviruses is largely unknown, yet encounter with multiple flaviviruses in a lifetime is increasingly likely. Using sequential challenges with dengue virus (DENV), yellow fever virus (YFV), and Japanese encephalitis virus (JEV), we induced cross-reactive cellular and humoral immunity among flaviviruses from differing serocomplexes. Antibodies against JEV enhanced DENV replication; however, JEV immunity was protective in vivo during secondary DENV1 infection, promoting rapid gains in antibody avidity. Mechanistically, JEV immunity activated dendritic cells and effector memory T cells, which developed a T follicular helper cell phenotype in draining lymph nodes upon secondary DENV1 infection. We identified cross-reactive epitopes that promote recall from a pool of flavivirus serocomplex cross-reactive memory CD4 T cells and confirmed that a similar serocomplex cross-reactive immunity occurs in humans. These results show that sequential immunizations for flaviviruses sharing CD4 epitopes should promote protection during a subsequent heterologous infection.
A strategy for the conservation of biodiversity on mid-ocean ridges from deep-sea mining Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Daniel C. Dunn, Cindy L. Van Dover, Ron J. Etter, Craig R. Smith, Lisa A. Levin, Telmo Morato, Ana Colaço, Andrew C. Dale, Andrey V. Gebruk, Kristina M. Gjerde, Patrick N. Halpin, Kerry L. Howell, David Johnson, José Angel A. Perez, Marta Chantal Ribeiro, Heiko Stuckas, Philip Weaver, SEMPIA Workshop Participants
Mineral exploitation has spread from land to shallow coastal waters and is now planned for the offshore, deep seabed. Large seafloor areas are being approved for exploration for seafloor mineral deposits, creating an urgent need for regional environmental management plans. Networks of areas where mining and mining impacts are prohibited are key elements of these plans. We adapt marine reserve design principles to the distinctive biophysical environment of mid-ocean ridges, offer a framework for design and evaluation of these networks to support conservation of benthic ecosystems on mid-ocean ridges, and introduce projected climate-induced changes in the deep sea to the evaluation of reserve design. We enumerate a suite of metrics to measure network performance against conservation targets and network design criteria promulgated by the Convention on Biological Diversity. We apply these metrics to network scenarios on the northern and equatorial Mid-Atlantic Ridge, where contractors are exploring for seafloor massive sulfide (SMS) deposits. A latitudinally distributed network of areas performs well at (i) capturing ecologically important areas and 30 to 50% of the spreading ridge areas, (ii) replicating representative areas, (iii) maintaining along-ridge population connectivity, and (iv) protecting areas potentially less affected by climate-related changes. Critically, the network design is adaptive, allowing for refinement based on new knowledge and the location of mining sites, provided that design principles and conservation targets are maintained. This framework can be applied along the global mid-ocean ridge system as a precautionary measure to protect biodiversity and ecosystem function from impacts of SMS mining.
Krypton isotopes and noble gas abundances in the coma of comet 67P/Churyumov-Gerasimenko Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Martin Rubin, Kathrin Altwegg, Hans Balsiger, Akiva Bar-Nun, Jean-Jacques Berthelier, Christelle Briois, Ursina Calmonte, Michael Combi, Johan De Keyser, Björn Fiethe, Stephen A. Fuselier, Sebastien Gasc, Tamas I. Gombosi, Kenneth C. Hansen, Ernest Kopp, Axel Korth, Diana Laufer, Léna Le Roy, Urs Mall, Bernard Marty, Olivier Mousis, Tobias Owen, Henri Rème, Thierry Sémon, Chia-Yu Tzou, Jack H. Waite, Peter Wurz
The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis mass spectrometer Double Focusing Mass Spectrometer on board the European Space Agency’s Rosetta spacecraft detected the major isotopes of the noble gases argon, krypton, and xenon in the coma of comet 67P/Churyumov-Gerasimenko. Earlier, it was found that xenon exhibits an isotopic composition distinct from anywhere else in the solar system. However, argon isotopes, within error, were shown to be consistent with solar isotope abundances. This discrepancy suggested an additional exotic component of xenon in comet 67P/Churyumov-Gerasimenko. We show that krypton also exhibits an isotopic composition close to solar. Furthermore, we found the argon to krypton and the krypton to xenon ratios in the comet to be lower than solar, which is a necessity to postulate an addition of exotic xenon in the comet.
The evolution of anti-bat sensory illusions in moths Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Juliette J. Rubin, Chris A. Hamilton, Chris J. W. McClure, Brad A. Chadwell, Akito Y. Kawahara, Jesse R. Barber
Prey transmit sensory illusions to redirect predatory strikes, creating a discrepancy between what a predator perceives and reality. We use the acoustic arms race between bats and moths to investigate the evolution and function of a sensory illusion. The spinning hindwing tails of silk moths (Saturniidae) divert bat attack by reflecting sonar to create a misleading echoic target. We characterized geometric morphometrics of moth hindwings across silk moths, mapped these traits onto a new, robust phylogeny, and found that elaborated hindwing structures have converged on four adaptive shape peaks. To test the mechanism underlying these anti-bat traits, we pit bats against three species of silk moths with experimentally altered hindwings that created a representative gradient of ancestral and extant hindwing shapes. High-speed videography of battles reveals that moths with longer hindwings and tails more successfully divert bat attack. We postulate that sensory illusions are widespread and are underappreciated drivers of diversity across systems.
A nearly complete foot from Dikika, Ethiopia and its implications for the ontogeny and function of Australopithecus afarensis Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Jeremy M. DeSilva, Corey M. Gill, Thomas C. Prang, Miriam A. Bredella, Zeresenay Alemseged
The functional and evolutionary implications of primitive retentions in early hominin feet have been under debate since the discovery of Australopithecus afarensis. Ontogeny can provide insight into adult phenotypes, but juvenile early hominin foot fossils are exceptionally rare. We analyze a nearly complete, 3.32-million-year-old juvenile foot of A. afarensis (DIK-1-1f). We show that juvenile A. afarensis individuals already had many of the bipedal features found in adult specimens. However, they also had medial cuneiform traits associated with increased hallucal mobility and a more gracile calcaneal tuber, which is unexpected on the basis of known adult morphologies. Selection for traits functionally associated with juvenile pedal grasping may provide a new perspective on their retention in the more terrestrial adult A. afarensis.
CH4 mitigation potentials from China landfills and related environmental co-benefits Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Bofeng Cai, Ziyang Lou, Jinnan Wang, Yong Geng, Joseph Sarkis, Jianguo Liu, Qingxian Gao
China’s CH4 emissions from 1955 existing (old) and 495 planned (new) landfills are estimated and projected by adopting a bottom-up method, targeting a 2012 baseline year and a 2030 projected target year. Nine key CH4 mitigation measures are proposed for the CH4 mitigation assessment from landfills. Approximately 0.66 million metric tons (Mt) of CH4 and 1.14 Mt of CH4 will be released, respectively, from new and existing landfills under a 2030 business-as-usual (BAU) scenario, which is 23.5% lower than a U.S. Environmental Protection Agency estimation. It is estimated that 0.60 and 0.97 Mt of CH4 can be reduced under new policies (NP) and low-carbon (LC) policy scenarios, respectively. The combined biocover and landfill gas collection and flaring system is the most promising mitigation measure, while mechanical biological treatment and mineral landfill also contribute substantially to CH4 reduction. The odor-affected population under NP and LC scenarios will decrease by 39.5 and 64.2%, respectively, when compared to the 2030 BAU scenario. The LC scenario is a recommended policy for meeting China’s nationally determined contribution targets and reducing the not-in-my-backyard impact due to this policy’s significant reduction of CH4 emissions.
A BK channel–mediated feedback pathway links single-synapse activity with action potential sharpening in repetitive firing Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Matvey V. Roshchin, Mikhail E. Matlashov, Victor N. Ierusalimsky, Pavel M. Balaban, Vsevolod V. Belousov, György Kemenes, Kevin Staras, Evgeny S. Nikitin
Action potential shape is a major determinant of synaptic transmission, and mechanisms of spike tuning are therefore of key functional significance. We demonstrate that synaptic activity itself modulates future spikes in the same neuron via a rapid feedback pathway. Using Ca2+ imaging and targeted uncaging approaches in layer 5 neocortical pyramidal neurons, we show that the single spike–evoked Ca2+ rise occurring in one proximal bouton or first node of Ranvier drives a significant sharpening of subsequent action potentials recorded at the soma. This form of intrinsic modulation, mediated by the activation of large-conductance Ca2+/voltage-dependent K+ channels (BK channels), acts to maintain high-frequency firing and limit runaway spike broadening during repetitive firing, preventing an otherwise significant escalation of synaptic transmission. Our findings identify a novel short-term presynaptic plasticity mechanism that uses the activity history of a bouton or adjacent axonal site to dynamically tune ongoing signaling properties.
Biogeography of soil bacteria and archaea across France Sci. Adv. (IF 11.511) Pub Date : 2018-07-01 Battle Karimi, Sébastien Terrat, Samuel Dequiedt, Nicolas P. A. Saby, Walid Horrigue, Mélanie Lelièvre, Virginie Nowak, Claudy Jolivet, Dominique Arrouays, Patrick Wincker, Corinne Cruaud, Antonio Bispo, Pierre-Alain Maron, Nicolas Chemidlin Prévost Bouré, Lionel Ranjard
Over the last two decades, a considerable effort has been made to decipher the biogeography of soil microbial communities as a whole, from small to broad scales. In contrast, few studies have focused on the taxonomic groups constituting these communities; thus, our knowledge of their ecological attributes and the drivers determining their composition and distribution is limited. We applied a pyrosequencing approach targeting 16S ribosomal RNA (rRNA) genes in soil DNA to a set of 2173 soil samples from France to reach a comprehensive understanding of the spatial distribution of bacteria and archaea and to identify the ecological processes and environmental drivers involved. Taxonomic assignment of the soil 16S rRNA sequences indicated the presence of 32 bacterial phyla or subphyla and 3 archaeal phyla. Twenty of these 35 phyla were cosmopolitan and abundant, with heterogeneous spatial distributions structured in patches ranging from a 43- to 260-km radius. The hierarchy of the main environmental drivers of phyla distribution was soil pH > land management > soil texture > soil nutrients > climate. At a lower taxonomic level, 47 dominant genera belonging to 12 phyla aggregated 62.1% of the sequences. We also showed that the phylum-level distribution can be determined largely by the distribution of the dominant genus or, alternatively, reflect the combined distribution of all of the phylum members. Together, our study demonstrated that soil bacteria and archaea present highly diverse biogeographical patterns on a nationwide scale and that studies based on intensive and systematic sampling on a wide spatial scale provide a promising contribution for elucidating soil biodiversity determinism.
The neuronal S100B protein is a calcium-tuned suppressor of amyloid-β aggregation Sci. Adv. (IF 11.511) Pub Date : 2018-06-01 Joana S. Cristóvão, Vanessa K. Morris, Isabel Cardoso, Sónia S. Leal, Javier Martínez, Hugo M. Botelho, Christoph Göbl, Rodrigo David, Katrin Kierdorf, Mobina Alemi, Tobias Madl, Günter Fritz, Bernd Reif, Cláudio M. Gomes
Amyloid-β (Aβ) aggregation and neuroinflammation are consistent features in Alzheimer’s disease (AD) and strong candidates for the initiation of neurodegeneration. S100B is one of the most abundant proinflammatory proteins that is chronically up-regulated in AD and is found associated with senile plaques. This recognized biomarker for brain distress may, thus, play roles in amyloid aggregation which remain to be determined. We report a novel role for the neuronal S100B protein as suppressor of Aβ42 aggregation and toxicity. We determined the structural details of the interaction between monomeric Aβ42 and S100B, which is favored by calcium binding to S100B, possibly involving conformational switching of disordered Aβ42 into an α-helical conformer, which locks aggregation. From nuclear magnetic resonance experiments, we show that this dynamic interaction occurs at a promiscuous peptide-binding region within the interfacial cleft of the S100B homodimer. This physical interaction is coupled to a functional role in the inhibition of Aβ42 aggregation and toxicity and is tuned by calcium binding to S100B. S100B delays the onset of Aβ42 aggregation by interacting with Aβ42 monomers inhibiting primary nucleation, and the calcium-bound state substantially affects secondary nucleation by inhibiting fibril surface–catalyzed reactions through S100B binding to growing Aβ42 oligomers and fibrils. S100B protects cells from Aβ42-mediated toxicity, rescuing cell viability and decreasing apoptosis induced by Aβ42 in cell cultures. Together, our findings suggest that molecular targeting of S100B could be translated into development of novel approaches to ameliorate AD neurodegeneration.
Probing measurement-induced effects in quantum walks via recurrence Sci. Adv. (IF 11.511) Pub Date : 2018-06-01 Thomas Nitsche, Sonja Barkhofen, Regina Kruse, Linda Sansoni, Martin Štefaňák, Aurél Gábris, Václav Potoček, Tamás Kiss, Igor Jex, Christine Silberhorn
Measurements on a quantum particle unavoidably affect its state, since the otherwise unitary evolution of the system is interrupted by a nonunitary projection operation. To probe measurement-induced effects in the state dynamics using a quantum simulator, the challenge is to implement controlled measurements on a small subspace of the system and continue the evolution from the complementary subspace. A powerful platform for versatile quantum evolution is represented by photonic quantum walks because of their high control over all relevant parameters. However, measurement-induced dynamics in such a platform have not yet been realized. We implement controlled measurements in a discrete-time quantum walk based on time-multiplexing. This is achieved by adding a deterministic outcoupling of the optical signal to include measurements constrained to specific positions resulting in the projection of the walker’s state on the remaining ones. With this platform and coherent input light, we experimentally simulate measurement-induced single-particle quantum dynamics. We demonstrate the difference between dynamics with only a single measurement at the final step and those including measurements during the evolution. To this aim, we study recurrence as a figure of merit, that is, the return probability to the walker’s starting position, which is measured in the two cases. We track the development of the return probability over 36 time steps and observe the onset of both recurrent and transient evolution as an effect of the different measurement schemes, a signature which only emerges for quantum systems. Our simulation of the observed one-particle conditional quantum dynamics does not require a genuine quantum particle but is demonstrated with coherent light.
Permselectivity limits of biomimetic desalination membranes Sci. Adv. (IF 11.511) Pub Date : 2018-06-01 Jay R. Werber, Menachem Elimelech
Water scarcity and inadequate membrane selectivity have spurred interest in biomimetic desalination membranes, in which biological or synthetic water channels are incorporated in an amphiphilic bilayer. As low channel densities (0.1 to 10%) are required for sufficient water permeability, the amphiphilic bilayer matrix will play a critical role in separation performance. We determine selectivity limits for biomimetic membranes by studying the transport behavior of water, neutral solutes, and ions through the bilayers of lipid and block-copolymer vesicles and projecting performance for varying water channel densities. We report that defect-free biomimetic membranes would have water/salt permselectivities ~108-fold greater than current desalination membranes. In contrast, the solubility-based permeability of lipid and block-copolymer bilayers (extending Overton’s rule) will result in poor rejection of hydrophobic solutes. Defect-free biomimetic membranes thus offer great potential for seawater desalination and ultrapure water production, but would perform poorly in wastewater reuse. Potential strategies to limit neutral solute permeation are discussed.
Inward growth by nucleation: Multiscale self-assembly of ordered membranes Sci. Adv. (IF 11.511) Pub Date : 2018-06-01 Jasper Landman, Samia Ouhajji, Sylvain Prévost, Theyencheri Narayanan, Jan Groenewold, Albert P. Philipse, Willem K. Kegel, Andrei V. Petukhov
Striking morphological similarities found between superstructures of a wide variety of seemingly unrelated crystalline membrane systems hint at the existence of a common formation mechanism. Resembling systems such as multiwalled carbon nanotubes, bacterial protein shells, or peptide nanotubes, the self-assembly of SDS/β-cyclodextrin complexes leads to monodisperse multilamellar microtubes. We uncover the mechanism of this hierarchical self-assembly process by time-resolved small- and ultrasmall-angle x-ray scattering. In particular, we show that symmetric crystalline bilayers bend into hollow cylinders as a consequence of membrane line tension and an anisotropic elastic modulus. Starting from single-walled microtubes, successive nucleation of new cylinders inside preexisting ones drives an inward growth. As both the driving forces that underlie the self-assembly behavior and the resulting morphologies are common to systems of ordered membranes, we believe that this formation mechanism has a similarly general applicability.
Passive radiofrequency x-ray dosimeter tag based on flexible radiation-sensitive oxide field-effect transistor Sci. Adv. (IF 11.511) Pub Date : 2018-06-01 Tobias Cramer, Ilaria Fratelli, Pedro Barquinha, Ana Santa, Cristina Fernandes, Franck D’Annunzio, Christophe Loussert, Rodrigo Martins, Elvira Fortunato, Beatrice Fraboni
Distributed x-ray radiation dosimetry is crucial in diverse security areas with significant environmental and human impacts such as nuclear waste management, radiotherapy, or radioprotection devices. We present a fast, real-time dosimetry detection system based on flexible oxide thin-film transistors that show a quantitative shift in threshold voltage of up to 3.4 V/gray upon exposure to ionizing radiation. The transistors use indium-gallium-zinc-oxide as a semiconductor and a multilayer dielectric based on silicon oxide and tantalum oxide. Our measurements demonstrate that the threshold voltage shift is caused by the accumulation of positive ionization charge in the dielectric layer due to high-energy photon absorption in the high-Z dielectric. The high mobility combined with a steep subthreshold slope of the transistor allows for fast, reliable, and ultralow-power readout of the deposited radiation dose. The order-of-magnitude variation in transistor channel impedance upon exposure to radiation makes it possible to use a low-cost, passive radiofrequency identification sensor tag for its readout. In this way, we demonstrate a passive, programmable, wireless sensor that reports in real time the excess of critical radiation doses.
A general printing approach for scalable growth of perovskite single-crystal films Sci. Adv. (IF 11.511) Pub Date : 2018-06-01 Zhenkun Gu, Zhandong Huang, Chang Li, Mingzhu Li, Yanlin Song
Perovskite single-crystal films, which exhibit exceptionally low trap density and nearly perfect translational symmetry, are believed to achieve the highest performance of perovskite-based optoelectronic devices. However, fabrication of these perovskite single-crystal films is quite difficult because of the uncontrollable nucleation caused by the rapid reaction of two perovskite precursors. We report a facile seed printing approach to selectively create millimeter-sized perovskite single-crystal films with controlled thickness and high yield. We show that perovskite single-crystal films can be perfectly transferred to almost arbitrary substrates through the printing process. The as-grown perovskite single-crystal films have excellent crystalline quality and morphology. We further demonstrate that perovskite single-crystal films can be directly printed for scalable fabrication of photodetectors and effective image sensors. This strategy allows high-yield fabrication of large perovskite single-crystal films for functional devices and may extend to other solution-processed materials for wide applications.
Sampling molecular conformations and dynamics in a multiuser virtual reality framework Sci. Adv. (IF 11.511) Pub Date : 2018-06-01 Michael O’Connor, Helen M. Deeks, Edward Dawn, Oussama Metatla, Anne Roudaut, Matthew Sutton, Lisa May Thomas, Becca Rose Glowacki, Rebecca Sage, Philip Tew, Mark Wonnacott, Phil Bates, Adrian J. Mulholland, David R. Glowacki
We describe a framework for interactive molecular dynamics in a multiuser virtual reality (VR) environment, combining rigorous cloud-mounted atomistic physics simulations with commodity VR hardware, which we have made accessible to readers (see isci.itch.io/nsb-imd). It allows users to visualize and sample, with atomic-level precision, the structures and dynamics of complex molecular structures “on the fly” and to interact with other users in the same virtual environment. A series of controlled studies, in which participants were tasked with a range of molecular manipulation goals (threading methane through a nanotube, changing helical screw sense, and tying a protein knot), quantitatively demonstrate that users within the interactive VR environment can complete sophisticated molecular modeling tasks more quickly than they can using conventional interfaces, especially for molecular pathways and structural transitions whose conformational choreographies are intrinsically three-dimensional. This framework should accelerate progress in nanoscale molecular engineering areas including conformational mapping, drug development, synthetic biology, and catalyst design. More broadly, our findings highlight the potential of VR in scientific domains where three-dimensional dynamics matter, spanning research and education.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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