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ZnO-based catalysts have been intensively studied because of their extraordinary performance in lower olefin synthesis, methanol synthesis and water–gas shift reactions. However, how ZnO catalyzes these reactions are still not well understood. Herein, we investigate the activations of CO2, O2 and CO on single crystalline ZnO polar surfaces at room temperature, through in-situ near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS). It is revealed that O2 and CO2 can undergo chemisorption on ZnO polar surfaces at elevated pressures. On the ZnO ( 0001 ) surface, molecular CO2 (O2) can chemically interact with the top layer Zn atoms, leading to the formation of C O 2 δ - ( O 2 δ - ) or partially dissociative atomic oxygen ( O - ) and hence the electron depletion layer in ZnO. Therefore, an apparent upward band-bending in ZnO ( 0001 ) is observed under the CO2 and O2 exposure. On the ZnO ( 000 1 ¯ ) surface, the molecular chemisorbed CO2 (O2) mainly bond to the surface oxygen vacancies, which also results in an upward band-bending in ZnO ( 000 1 ¯ ). In contrast, no band-bending is observed for both ZnO polar surfaces upon CO exposure. The electron-acceptor nature of the surface bounded molecules/atoms is responsible for the reversible binding energy shift of Zn 2p3/2 and O 1s in ZnO. Our findings can shed light on the fundamental understandings of CO2 and O2 activation on ZnO surfaces, especially the role of ZnO in heterogeneous catalytic reactions.

Lithium-oxygen batteries with ultrahigh energy densities have drawn considerable attention as next-generation energy storage devices. However, their practical applications are challenged by sluggish reaction kinetics aimed at the formation/decomposition of discharge products on battery cathodes. Developing effective catalysts and understanding the fundamental catalytic mechanism are vital to improve the electrochemical performance of lithium-oxygen batteries. Here, uniformly dispersed ruthenium nanoparticles anchored on nitrogen-doped reduced graphene oxide are prepared by using an

Understanding the interactions between metallic lithium (Li) and the anchoring sites/groups is essential for the design of stable host materials and artificial interphases in lithium metal batteries (LMBs). Here, we investigate the interactions of lithium with the polar organic functional groups in copper(II) hexadecafluorophthalocyanine (F16CuPc) and copper(II) phthalocyanine (CuPc) through the combination of in-situ X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), synchrotron-based near-edge X-ray absorption fine structures (NEXAFS), and density functional theory (DFT) calculations. It is revealed that the highly polar C-F bonds can anchor the Li atom via ionic Li-F interaction around the outer aza bridge N atoms in F16CuPc, while Li tends to interact with the inner pyrrolic N atoms around the central Cu in CuPc. The central Cu(II) ions in both molecules are reduced to Cu(I) upon interaction with Li. Electrons are transferred from Li to the lowest unoccupied molecular orbitals (LUMO) of both F16CuPc and CuPc molecules, as revealed by the UPS and NEXAFS measurements. Our systematic study can shed light on the design of anode materials by adding polar functional groups for applications in lithium metal batteries (LMBs). Ministry of Education (MOE) The authors acknowledge the financial support from the Natural Science Foundation of China (U2032147), Singapore MOE Tier II grant R143-000-A29-112, and Academic Research Fund Tie I grant RG104/18.

ZnO-based catalysts have been widely used in industrial reactions involving syngas conversions. Hydrogen dynamics on the surface of the catalyst is an essential process for understanding the mechan...

The degree of buckling of two-dimensional (2D) materials can have a dramatic impact on their corresponding electronic structures. Antimonene (β-phase), a new 2D material with air stability and promising electronic properties, has been engineered to adopt flat or two-heights-buckling geometries by employing different supporting substrates for epitaxial growth. However, studies of the antimonene monolayer with a more buckled configuration are still lacking. Here, we report the synthesis of an antimonene monolayer with a three-heights-buckling configuration overlaid on SbAg2 surface alloy-covered Ag(111) by molecular beam epitaxy, in which the underlying surface alloy provides interfacial interactions to modulate the structure of the antimonene monolayer. The atomic structure of the synthesized antimonene has been precisely identified through a combination of low-temperature scanning tunneling microscopy and density functional theory calculations. The successful fabrication of a buckled antimonene monolayer could provide a promising way to modulate the structures of 2D materials for future electronic and optoelectronic applications.

Porous metal-organic frameworks (MOFs) have become one of the fastest growing fields with broad applications due to the presence of various active sites (e.g., cavities, metal nodes, and organic linkers). Notably, an on-surface synthesis represents a facile method for the fabrication of two-dimensional (2D) MOFs, where the substrate not only supports and dictates the symmetry of the surface nanostructures but also provides the metal atoms to form the metal nodes. However, the realization of on-surface synthesized 2D metal-inorganic porous networks is rarely explored, except for a recently reported gold-phosphorus network. Here, we integrate one more dimension into the growth process (activated gas phase atoms) and demonstrate the on-surface synthesis of ternary metal-inorganic gold-phosphorus-nitrogen porous networks on Au(111). The atomic structure is precisely identified through a combination of low-temperature scanning tunneling microscopy, density functional theory calculations, and X-ray photoelectron spectroscopy. Using the thermal energy from the heated Au(111) substrate, the phosphorus precursor can simultaneously grab gold atoms from the surface and nitrogen atoms from activated nitrogen gas to build up a long-range ordered 2D surface porous structure. Our study opens a completely new platform for the on-surface synthesis of tailored metal-inorganic frameworks.

Organic anode materials have attracted considerable interest owing to their high tunability by adopting various active functional groups. However, the interaction mechanisms between the alkali metals and the active functional groups in host materials have been rarely studied systematically. Here, a widely used organic semiconductor of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) was selected as a model system to investigate how alkali metals interact with imide functional groups and induce changes in chemical and electronic structures of PTCDI. The interaction at the alkali/PTCDI interface was probed by in-situ X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), synchrotron-based near edge X-ray absorption fine structure (NEXAFS), and corroborated by density functional theory (DFT) calculations. Our results indicate that the alkali metal replaces the hydrogen atoms in the imide group and interact with the imide nitrogen of PTCDI. Electron transfer induced gap states and downward band-bending like effects are identified on the alkali-deposited PTCDI surface. It was found that Na shows a stronger electron transfer effect than Li. Such a model study of alkali insertion/intercalation in PTCDI gives insights for the exploration of the potential host materials for alkali storage applications.

Nitrogen fixation is a vital process for both nature and industry. Whereas the nitrogenase can reduce nitrogen in ambient environment in nature, the industrialized Haber-Bosch process is a high temperature and high-pressure process. Since the discovery of the first dinitrogen complex in 1965, many dinitrogen complexes are prepared in a homogeneous solution to mimic the nitrogenase enzyme in nature. However, studies of the heterogeneous process on surface are rarely addressed. Moreover, molecular scale characterization for such dinitrogen complex is lacking. Here, we present a simple model system to investigate, at the single-molecule level, the binding of dinitrogen on a surface confined iron phthalocyanine (FePc) monolayer through the combination of in-situ low-temperature scanning tunneling microscopy (LT-STM) and X-ray photoelectron spectroscopy (XPS) measurements. The iron center in FePc molecule deposited on Au(111) and highly oriented pyrolytic graphite (HOPG) surface can adsorb dinitrogen molecule at room temperature and low pressure. A comparative study reveals that the adsorption behaviors of FePc on these two different substrates are identical. Chemical bond is formed between the dinitrogen and the Fe atom in the FePc molecule, which greatly modifies the electronic structure of FePc. The bonding is reversible and can be manipulated by applying bias using a STM tip or by thermal annealing.

Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) has been intensively investigated for decades because of its unique electronic and optical properties and its applications in organic electronics and surface engineering and passivation of 2D materials. Recently, the high demand for achieving selective area deposition in device fabrications drives the research of utilizing organic molecules as a passivation layer on metals in the semiconductor industry. PTCDA molecules show promising potential to be used as a passivation layer on a metal surface because of their ability to form self-assembled compact lying-down layers with the well-exposed inert conjugated molecular π-plane. However, the thermal and chemical stabilities of monolayer PTCDA on metal surfaces have not been thoroughly studied. In this paper, we demonstrate that monolayer PTCDA on Cu(110) and Cu(111) surfaces exhibit good thermal and chemical stabilities, as revealed through the combination of

Metal-organic frameworks (MOFs) have been widely employed as the precursors to obtain functional carbon with tuneable composition and structure. However, the design of 2D carbon nanostructures directly from two-dimensional (2D) nonlayered MOFs is still very scarce, which is mainly hindered by the synthesis of 2D nonlayered MOFs. Herein, 2D nonlayered NH2-MIL-53 (Al) is synthesized via inorganic anion modulation for 2D S, N, O-rich hard carbon nanosheets (SNO-HCN) precursor. Due to the introduction of S-doping, more open edge sites generate, which accordingly promote the formation of pyridinic N and C=O carbonyl groups. When adopted as the anode for the sodium ion batteries, the SNO-HCN electrode delivers high reversible capacity of 522 mAh g−1 and 185 mAh g−1 at 50 mA g−1 and 15000 mA g−1, respectively. The enlarged interlayer spacing, unique 2D structure, heteroatom-rich active sites, and high surface area lead to the improved electrochemical performance. Furthermore, the galvanostatic intermittent titration technique (GITT) test indicates the superior electrochemical kinetics of the SNO-HCN electrode and the quantitative analysis reveals the capacitance contribution dominates during sodium-ion storage process. This represents an universal approach for the preparation of various 2D carbon nanomaterials derived from 2D nonlayered MOFs.

Superoxide (O2-) species play a crucial role in determining the charge kinetics for aprotic lithium-oxygen (Li-O2) batteries. However, the growth of O2--rich lithium peroxide (Li2O2) is challenging since O2- is thermodynamically unfavorable and unstable in an O2 atmosphere. Herein, we reported the synthesis of defective Li2O2 with tunable O2- via K+ doping. The K+ dopants can successfully stabilize O2- species and induce the coordination of Li+ with O2-, leading to increased Li vacancies. Compared to the pristine Li2O2, the as-prepared defective Li2O2 can be charged at a lower overpotential in Li-O2 batteries, which is ascribed to further increased Li vacancies contributed by the depotassiation process at the onset of the charge process. Our findings suggest a new strategy to better control O2- species in Li2O2 by K+ dopants and provide insights into the K+ effects on charge mechanism in Li-O2 batteries.

Two-dimensional (2D) nanomaterials , including metal-free (graphene, carbon nitride , and black phosphorus et al.) and transition metal-based materials (dichalcogenides, oxides, hydroxides, phosphides, and MXenes et al.), have emerged as promising candidates for electrocatalysis due to their unique physical, chemical, and electronic properties. Specifically, 2D materials with ultra-thin thickness usually possess more vacancy-type defects and exposed edges than bulk materials, resulting in different electronic characteristics relative to those of bulk materials and leading to changes in the reactant absorption energy on catalysts. Introducing heteroatom dopants can further alter the charge distribution in 2D materials, thereby facilitating the formation of new defects and catalytic active-sites to improve the electrocatalytic performance. This review highlights recent defect chemistry advances and developments in 2D materials for electrocatalysis. We discuss various defects in 2D materials, such as edge defects, topological defects and vacancy defects so on, and the effects of defects on electrocatalytic performance. Defect engineering and rational design strategies for controlling defects on 2D materials will also be systematically discussed. Finally, various advanced characterization technologies to reveal different types of defects will be discussed.

Plant phenology, the annually recurring sequence of plant developmental stages, is important for plant functioning and ecosystem services and their biophysical and biogeochemical feedbacks to the climate system. Plant phenology depends on temperature, and the current rapid climate change has revived interest in understanding and modeling the responses of plant phenology to the warming trend and the consequences thereof for ecosystems. Here, we review recent progresses in plant phenology and its interactions with climate change. Focusing on the start (leaf unfolding) and end (leaf coloring) of plant growing seasons, we show that the recent rapid expansion in ground- and remote sensing- based phenology data acquisition has been highly beneficial and has supported major advances in plant phenology research. Studies using multiple data sources and methods generally agree on the trends of advanced leaf unfolding and delayed leaf coloring due to climate change, yet these trends appear to have decelerated or even reversed in recent years. Our understanding of the mechanisms underlying the plant phenology responses to climate warming is still limited. The interactions between multiple drivers complicate the modeling and prediction of plant phenology changes. Furthermore, changes in plant phenology have important implications for ecosystem carbon cycles and ecosystem feedbacks to climate, yet the quantification of such impacts remains challenging. We suggest that future studies should primarily focus on using new observation tools to improve the understanding of tropical plant phenology, on improving process-based phenology modeling, and on the scaling of phenology from species to landscape-level.

Photocatalytic hydrogen peroxide (H2O2) generation represents a promising approach for artificial photosynthesis. However, the sluggish half-reaction of water oxidation significantly limits the efficiency of H2O2 generation. Here, a benzylamine oxidation with more favorable thermodynamics is employed as the half-reaction to couple with H2O2 generation in water by using defective zirconium trisulfide (ZrS3) nanobelts as a photocatalyst. The ZrS3 nanobelts with disulfide (S22−) and sulfide anion (S2−) vacancies exhibit an excellent photocatalytic performance for H2O2 generation and simultaneous oxidation of benzylamine to benzonitrile with a high selectivity of >99%. More importantly, the S22− and S2− vacancies can be separately introduced into ZrS3 nanobelts in a controlled manner. The S22− vacancies are further revealed to facilitate the separation of photogenerated charge carriers. The S2− vacancies can significantly improve the electron conduction, hole extraction, and kinetics of benzylamine oxidation. As a result, the use of defective ZrS3 nanobelts yields a high production rate of 78.1 ± 1.5 and 32.0 ± 1.2 μmol h−1 for H2O2 and benzonitrile, respectively, under a simulated sunlight irradiation.

S. aureus resistant to methicillin (MRSA) is one of the most-concerned multidrug resistant bacteria, due to its role in life-threatening infections. There is an urgent need to develop new antibiotics against MRSA. In this study, we firstly compiled a data set of 2,3-diaminoquinoxalines by chemical synthesis and antibacterial screening against S. aureus, and then performed cheminformatics modeling and virtual screening. The compound with the Specs ID of AG-205/33156020 was discovered as a new antibacterial agent, and was further identified as a Gyrase B (GyrB) inhibitor. In light of the common features, we hypothesized that the 6c as the representative of 2,3-diaminoquinoxalines also inhibited GyrB and eventually proved it. Via molecular docking and molecular dynamics simulations, we identified binding modes of AG-205/33156020 and 6c to the ATPase domain of GyrB. Importantly, these GyrB inhibitors inhibited the MRSA strains and showed selectivity to HepG2 and HUVEC. Taken together, this research work provides an effective ligand-based computational workflow for scaffold hopping in anti-MRSA drug discovery, and discovers two new GyrB inhibitors that are worthy of further development.

The state of ecosystems is influenced strongly by their past, and describing this carryover effect is important to accurately forecast their future behaviors. However, the strength and persistence of this carryover effect on ecosystem dynamics in comparison to that of simultaneous environmental drivers are still poorly understood. Here, we show that vegetation growth carryover (VGC), defined as the effect of present states of vegetation on subsequent growth, exerts strong positive impacts on seasonal vegetation growth over the Northern Hemisphere. In particular, this VGC of early growing-season vegetation growth is even stronger than past and co-occurring climate on determining peak-to-late season vegetation growth, and is the primary contributor to the recently observed annual greening trend. The effect of seasonal VGC persists into the subsequent year but not further. Current process-based ecosystem models greatly underestimate the VGC effect, and may therefore underestimate the CO2 sequestration potential of northern vegetation under future warming., The future of terrestrial systems is influenced by their past, but this carryover effect is rarely quantified. Here, the authors provide the first quantitative evidence that a greener spring begets a greener summer and autumn, and that this carryover effect is even stronger than climate drivers.

While climate warming reduces the occurrence of frost events, the warming-induced lengthening of the growing season of plants in the Northern Hemisphere may actually induce more frequent frost days during the growing season (GSFDs, days with minimum temperature, Plant growing season increases under a warming climate, but it is not known whether this will alter plant exposure to frost days. Here Liu et al. investigate trends in the Northern Hemisphere over 30 years and find increased exposure to frost days in regions that have longer growing seasons.

Agriculture is expanding in tropical mountainous areas, yet its climatic effect is poorly understood. Here, we investigate how elevation regulates the biophysical climate impacts of deforestation over tropical mountainous areas by integrating satellite-observed forest cover changes into a high-resolution land–atmosphere coupled model. We show that recent forest conversion between 2000 and 2014 increased the regional warming by 0.022 ± 0.002 °C in the Southeast Asian Massif, 0.010 ± 0.007 °C in the Barisan Mountains (Maritime Southeast Asia), 0.042 ± 0.010 °C in the Serra da Espinhaco (South America) and 0.047 ± 0.008 °C in the Albertine Rift mountains (Africa) during the local dry season. The deforestation-driven local temperature anomaly can reach up to 2 °C where forest conversion is extensive. The warming from mountain deforestation depends on elevation, through the intertwined and opposing effects of increased albedo causing cooling and decreased evapotranspiration causing warming. As the elevation increases, the albedo effect increases in importance and the warming effect decreases, analogous to previously highlighted decreases of deforestation-induced warming with increasing latitude. As most new croplands are encroaching lands at low to moderate elevations, deforestation produces higher warming from suppressed evapotranspiration. Impacts of this additional warming on crop yields, land degradation and biodiversity of nearby intact ecosystems should be incorporated into future assessments. Deforestation causes elevation-dependent warming over tropical mountain regions, according to high-resolution climate simulations.

The global monsoon is characterised by transitions between pronounced dry and wet seasons, affecting food security for two-thirds of the world’s population. Rising atmospheric CO2 influences the terrestrial hydrological cycle through climate-radiative and vegetation-physiological forcings. How these two forcings affect the seasonal intensity and characteristics of monsoonal precipitation and runoff is poorly understood. Here we use four Earth System Models to show that in a CO2-enriched climate, radiative forcing changes drive annual precipitation increases for most monsoon regions. Further, vegetation feedbacks substantially affect annual precipitation in North and South America and Australia monsoon regions. In the dry season, runoff increases over most monsoon regions, due to stomatal closure-driven evapotranspiration reductions and associated atmospheric circulation change. Our results imply that flood risks may amplify in the wet season. However, the lengthening of the monsoon rainfall season and reduced evapotranspiration will shorten the water resources scarcity period for most monsoon regions.

The growth of entirely synthetic two-dimensional (2D) materials could further expand the library of naturally occurring layered solids and provide opportunities to design materials with finely tunable properties. Among them, the synthesis of elemental 2D materials is of particular interest as they represent the chemically simplest case and serve as a model system for exploring the on-surface synthesis mechanism. Here, a pure atomically thin blue phosphorus (BlueP) monolayer is synthesized

This paper is concerned with the free boundary value problem (FBVP) for the cylindrically symmetric barotropic compressible Navier-Stokes equations (CNS) with density-dependent viscosity coefficients in the case that across the free surface stress tensor is balanced by a constant exterior pressure. Under certain assumptions imposed on the initial data, the unique cylindrically symmetric strong solution is shown to exist globally in time and tend to a non-vacuum equilibrium state exponentially as time tends to infinity.

Aberrant Wnt signaling has been implicated in a variety of disease. Inhibition of the Wnt pathway is an attractive approach for developing new therapeutics for the treatment of various types of fibrosis and cancers. We have discovered the phthalimide-phenylpyridine conjugate as a novel hit compound for the Wnt pathway inhibitors from cellular screening. The structure-activity relationship of these compounds suggested both of the substituent group on the phthalimide fragment and the structure of the linker were critical to the inhibitory activity. The most potent compound was about 10-folds more potent than the hit compound, with IC50 value of 0.28 ± 0.01 µM.

(±)-7-O-galloyltricetiflavan (1a) was synthesized successfully in five steps from the commercially available trihydroxyacetophenone (2) and trimethoxybenzoyl chloride (3). The flavone 4a was prepared in a one-pot reaction and it gave hex-O-methylflavan 6 followed by acylation and reduction. However, the demethylation of flavan 6, 5-O-acetylflavan 10 and 5-O-phenylacetylflavan 11 by BBr3 gave all the hydrolyzed fragments 7 and 8 as the major products. By contrast, in the same condition, hept-O-methylflavan 9 could provide the desired product (±)-7-O-galloyltricetiflavan (1a) in 91% yield. The additional 5-O-B-Br2 complex may stabilize the ester bond during the demethylation process.

Two conformationally restricted salinomycin derivatives by tethering the hydroxyl groups at C1 and C20 with different chain length were designed and synthesized. The cyclic derivatives showed better biological activities than C1/C20 modified derivatives, indicating the importance of the compact conformation for the ion binding capacity. In addition, the length of the connective chain plays critical role in the biological activities, thus cyclic the derivative 7 preserved some pharmacological activity but derivative 5 with two carbon atom shorter chain showed significantly reduced activity. The conformations of the two cyclic salinomycin derivatives were analyzed by ROESY spectrum in DMSO-d6, indicating derivative 7 may adopt more appropriate conformations for the coordinate with alkali metal ion than derivative 5, which has a closer distance between H3 and H25.

In the recent IPCC assessment, multi-model ensembles (AMA) were constructed with equal weights given to Earth system models, without considering the performance of each model at reproducing current conditions. Here, we use Bayesian model averaging (BMA) to construct a weighted model ensemble for runoff projections. Higher weights are given to models with better performance in estimating historical decadal mean runoff. Using the BMA method, we find that by the end of this century, the increase of global runoff (9.8 ± 1.5%) under RCP8.5 is significantly lower than estimated from AMA (12.2 ± 1.3%). BMA presents a less severe runoff increase than AMA at northern high latitudes and a more severe decrease in Amazonia. Runoff decrease in Amazonia is stronger than the inter-model difference. The inter-model difference in runoff changes is mainly caused by precipitation differences among models, but also by evapotranspiration differences at the high northern latitudes.

Significant increases in remotely sensed vegetation indices in the northern latitudes since the 1980s have been detected and attributed at annual and growing season scales. However, we presently lack a systematic understanding of how vegetation responds to asymmetric seasonal environmental changes. In this study, we first investigated trends in the seasonal mean leaf area index (LAI) at northern latitudes (north of 30 degrees N) between 1982 and 2009 using three remotely sensed long-term LAI data sets. The most significant LAI increases occurred in summer (0.009 m(2) m(-2) year(-1), p

Extra water loss from earlier spring greening dries soils locally in summer, but can moisten soils in areas downwind., Earlier vegetation greening under climate change raises evapotranspiration and thus lowers spring soil moisture, yet the extent and magnitude of this water deficit persistence into the following summer remain elusive. We provide observational evidence that increased foliage cover over the Northern Hemisphere, during 1982–2011, triggers an additional soil moisture deficit that is further carried over into summer. Climate model simulations independently support this and attribute the driving process to be larger increases in evapotranspiration than in precipitation. This extra soil drying is projected to amplify the frequency and intensity of summer heatwaves. Most feedbacks operate locally, except for a notable teleconnection where extra moisture transpired over Europe is transported to central Siberia. Model results illustrate that this teleconnection offsets Siberian soil moisture losses from local spring greening. Our results highlight that climate change adaptation planning must account for the extra summer water and heatwave stress inherited from warming-induced earlier greening.

The frequency and intensity of droughts have increased over the decades, leading to increased forest decline. The response of forest to drought can be evaluated by both its sensitivity to drought (resistance) and its post-drought recovery rate (resilience). However, it remains uncertain how drought resistance and resilience of forests change over time under climate change. We assessed the spatiotemporal dynamics of forest resistance and resilience to drought over the past century (1901–2015) with global tree ring data records from 2,935 sites, in conjunction with plant trait data. We found that gymnosperms and angiosperms showed different spatial patterns of drought resistance and resilience, driven by variations in eco-physiological traits. Resistance and resilience also varied with drought seasonal timing. Surprisingly, we found that the trade-off between resistance and resilience for gymnosperms, previously reported only spatially, also occurred at the temporal scale. In particular, drought resilience markedly increased, but resistance decreased, for gymnosperms between 1950–1969 and 1990–2009, indicating that previous model simulations assuming invariant resistance may have underestimated the impacts of drought on gymnosperm-dominated forests under future climate change. A study of global tree ring data records over the last century reveals a temporal trade-off between resistance and resilience to drought for gymnosperms.

Bacillus thuringiensis insecticidal proteins (Bt toxins) have been widely used in crops for agricultural pest management and to reduce the use of chemical insecticides. Here, we have engineered Bt toxin Cry2Ab30 and bioconjugated it with 4&rdquo, O-succinyl avermectin (AVM) to synthesize Cry2Ab&ndash, AVM bioconjugate. It was found that Cry2Ab&ndash, AVM showed higher insecticidal activity against Plutella xylostella, up to 154.4 times compared to Cry2Ab30. The binding results showed that Cry2Ab&ndash, AVM binds to the cadherin-like binding protein fragments, the 10th and 11th cadherin repeat domains in the P. xylostella cadherin (PxCR10&ndash, 11), with a much higher affinity (dissociation equilibrium constant KD = 3.44 nM) than Cry2Ab30 (KD = 28.7 nM). Molecular docking suggested that the macrolide lactone group of Cry2Ab&ndash, AVM ligand docking into the PxCR10&ndash, 11 is a potential mechanism to enhance the binding affinity of Cry2Ab&ndash, AVM to PxCR10&ndash, 11. These findings offer scope for the engineering of Bt toxins by bioconjugation for improved pest management.

There is an increasing demand to integrate land surface temperature (LST) into climate research due to its global coverage, which requires a comprehensive knowledge of its distinctive characteristics compared to near-surface air temperature (Tair). Using satellite observations and in situ station-based data sets, we conducted a global-scale assessment of the spatial and seasonal variations in the difference between daily maximum LST and daily maximum Tair (delta(T), LST - Tair) during 2003-2014. Spatially, LST is generally higher than Tair over arid and sparsely vegetated regions in the middle-low latitudes, but LST is lower than Tair in tropical rainforests due to strong evaporative cooling, and in the high-latitude regions due to snow-induced radiative cooling. Seasonally, delta(T) is negative in tropical regions throughout the year, while it displays a pronounced seasonality in both the midlatitudes and boreal regions. The seasonality in the midlatitudes is a result of the asynchronous responses of LST and Tair to the seasonal cycle of radiation and vegetation abundance, whereas in the boreal regions, seasonality is mainly caused by the change in snow cover. Our study identified substantial spatial heterogeneity and seasonality in delta(T), as well as its determinant environmental drivers, and thus provides a useful reference for monitoring near-surface air temperature changes using remote sensing, particularly in remote regions.

Markedly minimizing the platinum (Pt) loading and increasing its mass activity are significant to drive down the cost of H2 production from water splitting. Herein, a novel electrocatalyst, Pt nanoparticles (NPs) anchored on Ni/nitrogen-doped graphene nanotubes (Pt/Ni@NGNTs), was designed and its exceptional catalytic performance towards hydrogen evolution reaction was demonstrated. Ni@NGNTs itself showed poor catalytic activity. Unexpectedly, when employed as a support, it increased the mass activity of the Pt metal by 30.1 times in an acidic electrolyte and 15.3 times in an alkaline electrolyte relative to that of commercial 20 wt% Pt/C. Moreover, the durability of Pt/Ni@NGNTs reached up to 50 h. Impressively, Pt NPs preferentially distributed around the protective graphene shells of the enclosed metal Ni, due to the enriched electron density and structural defects induced by Ni and N dopants. The electronic interactions between Pt and Ni@NGNTs tuned the electronic properties and greatly boosted catalytic performances of the anchored Pt NPs. The present catalyst shows significant potential for the synthesis of low cost, high performance Pt-based catalysts.

A microwave-assisted N- fluorobenzenesulfonimide (NFSI)/Lewis acid-catalyzed Beckmann rearrangement was developed. The remarkable promotion to the electrophilicity of NFSI by Lewis acids was illustrated utilizing a series of readily available oxime substrates. The action model between NFSI and Lewis acids was probed by control experiments and theoretical calculations.

A SPEEK/PW 11 V/rGO hybrid film was prepared by a simple method through sulfonated polyether ether ketone (SPEEK), tungstovanadophosphoric acid (H 4 PW 11 VO 40 , abbreviated as PW 11 V) and reduced graphene oxide (rGO) in this work. The results indicate that the Keggin framework of PW 11 VO 40 4 − anion still remain in the hybrid film and confirm the homogeneous dispersion of PW 11 V on the surface of graphene sheet, which results in a better stability of PW 11 V. The electrochemical impedance spectroscopy shows that this film exhibits high proton conductivity of 2.22 × 10 − 2 S cm − 1 at 17 °C and 6.43 × 10 − 2 S cm − 1 at 65 °C (65% relative humidity). Its activation energy value for proton conduction is 18.9 kJ mol − 1 , suggesting that the conduction mechanism for this film is a mix of Vehicle mechanism and Grotthuss mechanism. It is an alternative film material which may be applied in the field of fuel cells.

Land surface albedo is a key parameter affecting energy balance and near-surface climate. In this study, we used satellite data to evaluate simulated surface albedo in 37 models participating in the Coupled Model Intercomparison Project Phase 5 (CMIP5). There was a systematic overestimation in the simulated seasonal cycle of albedo with the highest bias occurring during the Northern Hemisphere's winter months. The bias in surface albedo during the snow-covered season was classified into that in snow cover fraction (SCF) and albedo contrast (beta(1)). There was a general overestimation of beta(1) due to the simulated snow-covered albedo being brighter than the observed value; negative biases in SCF were not always related to negative albedo biases, highlighting the need for realistic representation of snow-covered albedo in models. In addition, models with a lower leaf area index (LAI) tend to produce a higher surface albedo over the boreal forests during the winter, which emphasizes the necessity of improving LAI simulations in CMIP5 models. Insolation weighting showed that spring albedo biases were of greater importance for climate. The removal of albedo biases is expected to improve temperature simulations particularly over high-elevation regions.

Organic semiconductor-based electrode materials are promising candidates for energy storage devices due to their high capacity, excellent flexibility, low cost and resource sustainability. The alkali metal storage mechanisms on various active functional groups of the organic materials, however, are still not clear at the molecular scale. It is essential to conduct systematic mechanism studies for the alkali storage behaviors in organic electrode materials. Here, the chemical and electronic structure evolutions upon the deposition of lithium (Li) and sodium (Na) on a model organic semiconductor electrode material of perylene-3,4,9,10-tetracarboxylicdianhydride (PTCDA), have been investigated by in-situ x-ray photoemission spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), near edge x-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory (DFT) calculations. It reveals that Li/Na can react with the carbonyl oxygen and increase the electron density within the PTCDA perylene. Moreover, the band-bending like features are observed on PTCDA film upon Li/Na interaction. Our experimental results and theoretical calculations indicate that reactions on carbonyl groups and charge redistribution are crucial for the Li/Na storage process, which shed light on comprehensive insights for the Li/Na storage behaviors on organic semiconductor-based electrode materials. Ministry of Education (MOE) Authors acknowledge the financial support from Singapore MOE grant R143-000-A29-112 and Academic Research Fund Tier 1 (RG104/ 18), as well as the computing resources from National Supercomputing Centre Singapore.

Evapotranspiration (ET) is one of the most important fluxes in terrestrial ecosystems that regulate atmosphere–hydrosphere–biosphere interactions. Several studies have suggested that global ET has significantly increased in the past several decades, and that such increase has exhibited big spatial variability, but there are few detailed studies on the spatio-temporal change in ET over China. Here, we developed a high-resolution data-oriented monthly ET product in China between 1982 and 2015 by integrating remote-sensing and the eddy covariance technique observed ET data in a machine learning approach (model tree ensemble, MTE). We showed that the mean annual ET over China is 552 ± 14 mm yr−1, which is comparable to the estimate from a MTE-derived product based on water balance, but is larger than that from both previous MTE-derived global product and process-based land surface models. ET in China significantly increased with a rate of 10.7 mm yr−1 per decade over the past 30 years (p 60 mm yr−1 per decade) occurred in the eastern periphery of Sichuan, southern Taiwan, and central China, which was attributed to the increases in temperature and solar radiation, as well as the enhanced vegetation productivity. About 22% of the area showed a decreasing trend in ET, mainly in parts of southeastern, southwestern, and northeastern China. The regional decrease in ET was likely due to decreasing precipitation and/or vegetation browning. Although our finding of the significant increase in China’s ET at the country scale is supported by five different ET products, there are still less agreement on the change in ET at the regional scale among different ET products.

International audience; The ratio of plant transpiration to total terrestrial evapotranspiration (T/ET) captures the role of vegetation in surface–atmosphere interactions. However, its magnitude remains highly uncertain at the global scale. Here we apply an emergent constraint approach that integrates CMIP5 Earth system models (ESMs) with 33 field T/ET measurements to re-estimate the global T/ET value. Our observational constraint strongly increases the original ESM estimates (0.41 ± 0.11) and greatly alleviates intermodel discrepancy, which leads to a new global T/ET estimate of 0.62 ± 0.06. For all the ESMs, the leaf area index is identified as the primary driver of spatial variations of T/ET, but to correct its bias generates a larger T/ET underestimation than the original ESM output. We present evidence that the ESM underestimation of T/ET is, instead, attributable to inaccurate representation of canopy light use, interception loss and root water uptake processes in the ESMs. These processes should be prioritized to reduce model uncertainties in the global hydrological cycle.

Forzieri et al . (Reports, 16 June 2017, p. 1180) used satellite data to show that boreal greening caused regional warming. We show that this positive sensitivity of temperature to the greening can be derived from the positive response of vegetation to boreal warming, which indicates that results from a statistical regression with satellite data should be carefully interpreted.

We found high spatial heterogeneity in the hydrological response to 30-year afforestation and vegetation greening in China., China has experienced substantial changes in vegetation cover, with a 10% increase in the leaf area index and an ~41.5 million-hectare increase in forest area since the 1980s. Earlier studies have suggested that increases in leaf area and tree cover have led to a decline in soil moisture and runoff due to increased evapotranspiration (ET), especially in dry regions of China. However, those studies often ignored precipitation responses to vegetation increases, which could offset some of the negative impact on soil moisture by increased ET. We investigated 30-year vegetation impacts on regional hydrology by allowing for vegetation-induced changes in precipitation using a coupled land-atmosphere global climate model, with a higher spatial resolution zoomed grid over China. We found high spatial heterogeneity in the vegetation impacts on key hydrological variables across China. In North and Southeast China, the increased precipitation from vegetation greening and the increased forest area, although statistically insignificant, supplied enough water to cancel out enhanced ET, resulting in weak impact on soil moisture. In Southwest China, however, the increase in vegetation cover significantly reduced soil moisture while precipitation was suppressed by the weakened summer monsoon. In Northeast China, the only area where forest cover declined, soil moisture was significantly reduced, by −8.1 mm decade−1, likely because of an intensified anticyclonic circulation anomaly during summer. These results suggest that offline model simulations can overestimate the increase of soil dryness in response to afforestation in North China, if vegetation feedbacks lead to increased precipitation like in our study.

Leaf area index (LAI) is increasing throughout the globe, implying Earth greening. Global modeling studies support this contention, yet satellite observations and model simulations have never been directly compared. Here, for the first time, a coupled land–climate model was used to quantify the potential impact of the satellite-observed Earth greening over the past 30 years on the terrestrial water cycle. The global LAI enhancement of 8% between the early 1980s and the early 2010s is modeled to have caused increases of 12.0 ± 2.4 mm yr−1 in evapotranspiration and 12.1 ± 2.7 mm yr−1 in precipitation—about 55% ± 25% and 28% ± 6% of the observed increases in land evapotranspiration and precipitation, respectively. In wet regions, the greening did not significantly decrease runoff and soil moisture because it intensified moisture recycling through a coincident increase of evapotranspiration and precipitation. But in dry regions, including the Sahel, west Asia, northern India, the western United States, and the Mediterranean coast, the greening was modeled to significantly decrease soil moisture through its coupling with the atmospheric water cycle. This modeled soil moisture response, however, might have biases resulting from the precipitation biases in the model. For example, the model dry bias might have underestimated the soil moisture response in the observed dry area (e.g., the Sahel and northern India) given that the modeled soil moisture is near the wilting point. Thus, an accurate representation of precipitation and its feedbacks in Earth system models is essential for simulations and predictions of how soil moisture responds to LAI changes, and therefore how the terrestrial water cycle responds to climate change.

Most studies of the northern hemisphere carbon cycle based on atmospheric CO2 concentration have focused on spring and autumn, but the climate change impact on summer carbon cycle remains unclear. Here we used atmospheric CO2 record from Point Barrow (Alaska) to show that summer CO2 drawdown between July and August, a proxy of summer carbon uptake, is significantly negatively correlated with terrestrial temperature north of 50°N interannually during 1979–2012. However, a refined analysis at the decadal scale reveals strong differences between the earlier (1979–1995) and later (1996–2012) periods, with the significant negative correlation only in the later period. This emerging negative temperature response is due to the disappearance of the positive temperature response of summer vegetation activities that prevailed in the earlier period. Our finding, together with the reported weakening temperature control on spring carbon uptake, suggests a diminished positive effect of warming on high-latitude carbon uptake., The impacts of climate change on summer carbon cycling in the northern hemisphere remain poorly resolved. Here the authors use atmospheric CO2 records from Point Barrow (Alaska) to show that summer CO2 drawdown is significantly negatively correlated with terrestrial temperature north of 50°N between 1979–2012.

International audience; The surface air temperature response to vegetation changes has been studied for the extreme case of land-cover change; yet, it has never been quantified for the slow but persistent increase in leaf area index (LAI) observed over the past 30 years (Earth greening). Here we isolate the fingerprint of increasing LAI on surface air temperature using a coupled land–atmosphere global climate model prescribed with satellite LAI observations. We find that the global greening has slowed down the rise in global land-surface air temperature by 0.09 ± 0.02 °C since 1982. This net cooling effect is the sum of cooling from increased evapotranspiration (70%), changed atmospheric circulation (44%), decreased shortwave transmissivity (21%), and warming from increased longwave air emissivity (−29%) and decreased albedo (−6%). The global cooling originated from the regions where LAI has increased, including boreal Eurasia, Europe, India, northwest Amazonia, and the Sahel. Increasing LAI did not, however, significantly change surface air temperature in eastern North America and East Asia, where the effects of large-scale atmospheric circulation changes mask local vegetation feedbacks. Overall, the sum of biophysical feedbacks related to the greening of the Earth mitigated 12% of global land-surface warming for the past 30 years.

Two-dimensional (2D) black phosphorus (BP) has received great attention due to its anisotropic mechanical, optical and electronic properties. However, the air-instability of BP seriously limits its further applications. Various approaches have been explored to improve the device stability of BP, including the encapsulation by inert 2D counterparts, and surface passivation by AlOx via atomic layer deposition and by organic layers either van der Waals stacked or covalently bonded onto the surface. Here we systematically investigate the surface passivation effect of perylenetetracarboxylic dianhydride (PTCDA) on BP through a variety of in-situ characterization techniques. PTCDA molecule on BP adopts a lying down configuration with the molecular π-plane almost parallel to the BP surface, arising from the formation of multiple intermolecular hydrogen bonds. The evaporation of PTCDA on BP does not modify the intrinsic structure and electrical transport property of BP, as revealed by in-situ ultraviolet photoelectron spectroscopy (UPS)/x-ray photoelectron spectroscopy (XPS), and further corroborated by in-situ field-effect-transistor (FET) evaluation. After the air-exposure of PTCDA covered BP in dark, no obvious degradation on BP was observed by XPS. However, the electron mobility of the passivated BP FET significantly decreased by 80% after 20 h exposure despite lifetime of the passivated device was prolonged.

International audience; Rice is the staple food for more than 50% of the world's population1,​2,​3. Reliable prediction of changes in rice yield is thus central for maintaining global food security. This is an extraordinary challenge. Here, we compare the sensitivity of rice yield to temperature increase derived from field warming experiments and three modelling approaches: statistical models, local crop models and global gridded crop models. Field warming experiments produce a substantial rice yield loss under warming, with an average temperature sensitivity of −5.2 ± 1.4% K$^{−1}$. Local crop models give a similar sensitivity (−6.3 ± 0.4% K$^{−1}$), but statistical and global gridded crop models both suggest less negative impacts of warming on yields (−0.8 ± 0.3% and −2.4 ± 3.7% K$^{−1}$, respectively). Using data from field warming experiments, we further propose a conditional probability approach to constrain the large range of global gridded crop model results for the future yield changes in response to warming by the end of the century (from −1.3% to −9.3% K$^{−1}$). The constraint implies a more negative response to warming (−8.3 ± 1.4% K$^{−1}$) and reduces the spread of the model ensemble by 33%. This yield reduction exceeds that estimated by the International Food Policy Research Institute assessment (−4.2 to −6.4% K$^{−1}$) (ref. 4). Our study suggests that without CO$_2$ fertilization, effective adaptation and genetic improvement, severe rice yield losses are plausible under intensive climate warming scenarios.

International audience; Seventeen Earth system models (ESMs) from phase 5 of the Coupled Model Intercomparison Project (CMIP5) were evaluated, focusing on the seasonal sensitivities of net biome production (NBP), net primary production (NPP), and heterotrophic respiration (Rh) to interannual variations in temperature and precipitation during 1982–2005 and their changes over the twenty-first century. Temperature sensitivity of NPP in ESMs was generally consistent across northern high-latitude biomes but significantly more negative for tropical and subtropical biomes relative to satellite-derived estimates. The temperature sensitivity of NBP in both inversion-based and ESM estimates was generally consistent in March–May (MAM) and September–November (SON) for tropical forests, semiarid ecosystems, and boreal forests. By contrast, for inversion-based NBP estimates, temperature sensitivity of NBP was nonsignificant for June–August (JJA) for all biomes except boreal forest; whereas, for ESM NBP estimates, the temperature sensitivity for JJA was significantly negative for all biomes except shrublands and subarctic ecosystems. Both satellite-derived NPP and inversion-based NBP are often decoupled from precipitation, whereas ESM NPP and NBP estimates are generally positively correlated with precipitation, suggesting that ESMs are oversensitive to precipitation. Over the twenty-first century, changes in temperature sensitivities of NPP, Rh, and NBP are consistent across all RCPs but stronger under more intensive scenarios. The temperature sensitivity of NBP was found to decrease in tropics and subtropics and increase in northern high latitudes in MAM due to an increased temperature sensitivity of NPP. Across all biomes, projected temperature sensitivity of NPP decreased in JJA and SON. Projected precipitation sensitivity of NBP did not change across biomes, except over grasslands in MAM.

Global environmental change is rapidly altering the dynamics of terrestrial vegetation, with consequences for the functioning of the Earth system and provision of ecosystem services(1,2). Yet how global vegetation is responding to the changing environment is not well established. Here we use three long-term satellite leaf area index (LAI) records and ten global ecosystem models to investigate four key drivers of LAI trends during 1982-2009. We show a persistent and widespread increase of growing season integrated LAI (greening) over 25% to 50% of the global vegetated area, whereas less than 4% of the globe shows decreasing LAI (browning). Factorial simulations with multiple global ecosystem models suggest that CO2 fertilization effects explain 70% of the observed greening trend, followed by nitrogen deposition (9%), climate change (8%) and land cover change (LCC) (4%). CO2 fertilization effects explain most of the greening trends in the tropics, whereas climate change resulted in greening of the high latitudes and the Tibetan Plateau. LCC contributed most to the regional greening observed in southeast China and the eastern United States. The regional effects of unexplained factors suggest that the next generation of ecosystem models will need to explore the impacts of forest demography, differences in regional management intensities for cropland and pastures, and other emerging productivity constraints such as phosphorus availability.

International audience; Satellite-observed Earth's greening has been reproduced by the latest generation of Earth System Models (ESMs) participating in the Coupled Model Intercomparison Project Phase 5 (CMIP5). Land evapotranspiration (ET) is expected to rise with increasing leaf area index (LAI, Earth's greening). The responses of ET play a key role in the land–climate interaction, but they have not been evaluated previously. Here, we assessed the responses of ET to Earth's greening in these CMIP5 ESMs. We verified a significant and positive response of ET to the modeled greening in each model. However, the responses were not comparable across the ESMs because of an inherent bias in the sensitivity of ET to LAI $(\partial {\rm{E}}{\rm{T}}/\partial {\rm{L}}{\rm{A}}{\rm{I}})$ in the models: $\partial {\rm{E}}{\rm{T}}/\partial {\rm{L}}{\rm{A}}{\rm{I}}$ is precisely and inversely proportional to the trend of LAI $(\partial {\rm{L}}{\rm{A}}{\rm{I}}/\partial t)$ across the ESMs. Constrained by this inversely proportional relationship with the satellite-observed $\partial {\rm{L}}{\rm{A}}{\rm{I}}/\partial t,$ the Earth's $\partial {\rm{E}}{\rm{T}}/\partial {\rm{\text{LAI}}}$ is 0.26 (0.21–0.34) mm d−1 per m2 m−2, equaling the independent estimates from satellite-derived reconstructions of ET and LAI. Thus, the Earth's greening-induced acceleration of ET is about 11.4 mm yr−1, accounting for more than 50% of the observed increase in land ET over the last 30 years. To better model the land–climate interaction, $\partial {\rm{E}}{\rm{T}}/\partial {\rm{L}}{\rm{A}}{\rm{I}}$ in these ESMs should be calibrated. A feasible means is to improve the representation of the magnitude of LAI in these CMIP5 ESMs.

Observed northern extratropical land greening is consistent with anthropogenic forcings, where greenhouse gases play a dominant role, but not with simulations that include only natural forcings and internal climate variability.