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At least 253 records · Page 14

HOCO formation in astrochemical environments by radical-induced H-abstraction from formic acid

Rate constants for the radical-induced hydrogen abstraction from formic acid, HCOOH, are presented here. Only those reactions leading to the formation of HOCO were investigated. The astrochemically relevant radicals OH, NH 2 , and H were considered to induce the H-abstraction. Tunnelling was taken into account by using the instanton method for rate constant calculations. For reactions relevant on grain surfaces, the unimolecular rate constant is of particular importance. For the reactions with OH and NH 2 , a corresponding deep pre-reactive minimum can be found that contributes to the barrier height and thus slows down the reaction. In general though, abstraction induced by OH radicals is found to be the fastest. The reaction with the H atoms becomes increasingly important at low temperatures, because of the narrow barrier through which tunnelling is efficient. In conclusion, the reaction with NH 2 radicals has both a high and broad barrier and consequently shows significantly smaller low-temperature rate constants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transcription Factors Controlling the Rhizobium–Legume Symbiosis: Integrating Infection, Organogenesis and the Abiotic Environment

Abstract Legume roots engage in a symbiotic relationship with rhizobia, leading to the development of nitrogen-fixing nodules. Nodule development is a sophisticated process and is under the tight regulation of the plant. The symbiosis initiates with a signal exchange between the two partners, followed by the development of a new organ colonized by rhizobia. Over two decades of study have shed light on the transcriptional regulation of rhizobium–legume symbiosis. A large number of transcription factors (TFs) have been implicated in one or more stages of this symbiosis. Legumes must monitor nodule development amidst a dynamic physical environment. Some environmental factors are conducive to nodulation, whereas others are stressful. The modulation of rhizobium–legume symbiosis by the abiotic environment adds another layer of complexity and is also transcriptionally regulated. Several symbiotic TFs act as integrators between symbiosis and the response to the abiotic environment. In this review, we trace the role of various TFs involved in rhizobium–legume symbiosis along its developmental route and highlight the ones that also act as communicators between this symbiosis and the response to the abiotic environment. Finally, we discuss contemporary approaches to study TF-target interactions in plants and probe their potential utility in the field of rhizobium–legume symbiosis.

Cell Biology↗

Warming‐Induced Earlier Greenup Leads to Reduced Stream Discharge in a Temperate Mixed Forest Catchment

Abstract The phenological response of vegetation to ongoing climate change may have great implications for hydrological regimes in the eastern United States. However, there have been few studies that analyze its resultant effect on catchment discharge dynamics, separating from dominant climatic controls. In this study, we examined the net effect of phenological variations on the long‐term and interannual gross primary production (GPP) and evapotranspiration (ET) fluxes in a temperate deciduous forest, as well as on the catchment discharge behavior in a mixed deciduous‐conifer forest catchment. First, we calibrated the spring and autumn leaf phenology models for the Harvard Forest in the northeastern United States, where the onsets of greenup and senescence have been significantly advanced and delayed, 10.3 and 6.0 days respectively, over the past two decades (1992–2011). We then integrated the phenology models into a mechanistic watershed ecohydrological model (RHESSys), which improved the interannual and long‐term simulations of both the plot‐scale daily GPP and ET fluxes and the catchment discharge dynamics. We found that the phenological changes amplified the long‐term increases in GPP and ET driven by the climatic controls. In particular, the earlier greenup onsets resulted in increases in annual ET significantly, while the delayed senescence onsets had less influence. Consequently, the earlier greenup onsets reduced stream discharge not only during the growing season but also during the following dormant season due to soil water depletion. This study highlights the importance of understanding vegetation response to ongoing climate change in order to predict the future hydrological nonstationarity in this region.

Kim, Ji Hyun↗

Altered climate leads to positive density‐dependent feedbacks in a tropical wet forest

Abstract Climate change is predicted to result in warmer and drier Neotropical forests relative to current conditions. Negative density‐dependent feedbacks, mediated by natural enemies, are key to maintaining the high diversity of tree species found in the tropics, yet we have little understanding of how projected changes in climate are likely to affect these critical controls. Over 3 years, we evaluated the effects of a natural drought and in situ experimental warming on density‐dependent feedbacks on seedling demography in a wet tropical forest in Puerto Rico. In the +4°C warming treatment, we found that seedling survival increased with increasing density of the same species (conspecific). These positive density‐dependent feedbacks were not associated with a decrease in aboveground natural enemy pressure. If positive density‐dependent feedbacks are not transient, the diversity of tropical wet forests, which may rely on negative density dependence to drive diversity, could decline in a future warmer, drier world.

Bachelot, Benedicte↗

Evaluation of an open forecasting challenge to assess skill of West Nile virus neuroinvasive disease prediction

Abstract Background West Nile virus (WNV) is the leading cause of mosquito-borne illness in the continental USA. WNV occurrence has high spatiotemporal variation, and current approaches to targeted control of the virus are limited, making forecasting a public health priority. However, little research has been done to compare strengths and weaknesses of WNV disease forecasting approaches on the national scale. We used forecasts submitted to the 2020 WNV Forecasting Challenge, an open challenge organized by the Centers for Disease Control and Prevention, to assess the status of WNV neuroinvasive disease (WNND) prediction and identify avenues for improvement. Methods We performed a multi-model comparative assessment of probabilistic forecasts submitted by 15 teams for annual WNND cases in US counties for 2020 and assessed forecast accuracy, calibration, and discriminatory power. In the evaluation, we included forecasts produced by comparison models of varying complexity as benchmarks of forecast performance. We also used regression analysis to identify modeling approaches and contextual factors that were associated with forecast skill. Results Simple models based on historical WNND cases generally scored better than more complex models and combined higher discriminatory power with better calibration of uncertainty. Forecast skill improved across updated forecast submissions submitted during the 2020 season. Among models using additional data, inclusion of climate or human demographic data was associated with higher skill, while inclusion of mosquito or land use data was associated with lower skill. We also identified population size, extreme minimum winter temperature, and interannual variation in WNND cases as county-level characteristics associated with variation in forecast skill. Conclusions Historical WNND cases were strong predictors of future cases with minimal increase in skill achieved by models that included other factors. Although opportunities might exist to specifically improve predictions for areas with large populations and low or high winter temperatures, areas with high case-count variability are intrinsically more difficult to predict. Also, the prediction of outbreaks, which are outliers relative to typical case numbers, remains difficult. Further improvements to prediction could be obtained with improved calibration of forecast uncertainty and access to real-time data streams (e.g. current weather and preliminary human cases). Graphical Abstract

54 ENVIRONMENTAL SCIENCES↗

An Ordered Ni 6 ‐Ring Superstructure Enables a Highly Stable Sodium Oxide Cathode

Abstract Sodium‐based layered oxides are among the leading cathode candidates for sodium‐ion batteries, toward potential grid energy storage, having large specific capacity, good ionic conductivity, and feasible synthesis. Despite their excellent prospects, the performance of layered intercalation materials is affected by both a phase transition induced by the gliding of the transition metal slabs and air‐exposure degradation within the Na layers. Here, this problem is significantly mitigated by selecting two ions with very different MO bond energies to construct a highly ordered Ni 6 ‐ring superstructure within the transition metal layers in a model compound (NaNi 2/3 Sb 1/3 O 2 ). By virtue of substitution of 1/3 nickel with antimony in NaNiO 2 , the existence of these ordered Ni 6 ‐rings with super‐exchange interaction to form a symmetric atomic configuration and degenerate electronic orbital in layered oxides can not only largely enhance their air stability and thermal stability, but also increase the redox potential and simplify the phase‐transition process during battery cycling. The findings reveal that the ordered Ni 6 ‐ring superstructure is beneficial for constructing highly stable layered cathodes and calls for new paradigms for better design of layered materials.

Wang, Peng‐Fei↗

Inhibition of Polyimide Photodegradation by Incorporation of Titanate Nanotubes into a Composite

The effect of UV light exposure on the properties of hexafluoroisopropylidene-diphthalic anhydride–oxydianiline (6FDA–ODA) polyimide (PI) and polyimide–titanate nanotube (TiNT/PI) composites has been studied using Raman spectroscopy, optical microscopy, nanoidentation and TEM. The degree of polymer photodegradation was estimated by measuring the change in affinity to a positively charged dye (methylene blue, MB). The mechanism of photoassisted transformations in polyimides usually involves scission of polymer chains accompanied by appearance of active radicals, which undergo further rapid transformations to more stable phenol, amine, and carboxylic functional groups. The accumulation of these groups can increase the degree of adsorption of charged dyes in the photodegraded polymer. It was found that neat PI showed a significantly increased capacity to adsorb MB after irradiation with UV, reaching a plateau after 1 h. In contrast, TiNT/PI composite demonstrated a much slower rise in concentration of adsorbed MB even after 4 h of UV exposure. Raman spectra indicated cleavage of C=O and C–F bonds in PI while only the C–F bond was damaged in TiNT/PI. Shorter cracks (≈ 40 µm long) appeared in TiNT/PI composites whereas macro cracks (> 100 µm) were visible in neat PI after 3 h of UV exposure. Brittleness was studied by comparing plasticity index which varied from 0 to 1 (0 corresponding to the most brittle material and 1 the most ductile one). Plasticity index reduced by 51% and 2% for PI and TiNT/PI, respectively after 3 h UV irradiation, indicating that TiNT can protect underlying PI from further damage. The hardness of neat PI decreased whereas, for TiNT/PI, it increased under UV, suggesting crosslinking of broken polymer chains with nanotubes. Graphical Abstract: Photodegradation of a titanate nanotubes/polyimide composite can lead to cross-linking of broken polymer chains by nanostructured material, resulting in increased hardness. .

36 MATERIALS SCIENCE↗

Effect of Y/Ti atomic ratio on microstructure of oxide dispersion strengthened alloys

Highlights: • Controlling nano oxide distributions in ODS alloys by tuning Y/Ti ratio. • Advanced characterization techniques have been conducted to comprehensively study the various nano oxides. • A recipe with a Y/Ti ratio of 0.4 was found and the intrinsic oxide formation mechanism was explained. - Abstract: Oxide dispersion strengthened (ODS) alloys are the leading candidate materials for advanced fission and fusion reactor components because of their excellent high temperature creep strength and radiation tolerance. The promising performance of ODS alloys relies on a high-density population of nano oxides. Here, four 9Cr-ODS alloys with varying initial Y/Ti atomic ratio were processed using a combined route of mechanical alloying (MA) and hot isostatic pressing (HIP). Microstructural characterizations of the consolidated alloys were examined by advanced transmission electron microscopy (TEM). Great differences in oxide distribution behavior were observed. 9Cr-ODS alloy with a Y/Ti ratio of 0.4 presented the finest and the highest number density of nano oxides among the four alloys. The effects of Y/Ti ratio on oxide formation were explored, and the precipitated mechanisms of the nano oxides were interpreted.

36 MATERIALS SCIENCE↗

Development of nano-Y2O3 dispersed Zr alloys synthesized by mechanical alloying and consolidated by pulse plasma sintering

Highlights: • Zr-Fe-Cr-Cu-Ti-1.0wt% nano-Y{sub 2}O{sub 3} dispersed alloys are fabricated by mechanical alloying and pulse plasma sintering. • These alloys record extremely high compressive strength, Young’s modulus, and hardness. • These mechanical properties are superior as compared to other commercially available Zr based alloys. • Dispersion of nanometric FeZr{sub 2}, Y{sub 2}Ti{sub 2}O{sub 7}, Fe{sub 2}Ti, ZrCu, Cr{sub 2}Zr, Y{sub 2}O{sub 3} leads to grain boundary pinning at elevated temperature. - Abstract: In this paper, Zr alloys are synthesized with nominal compositions: 50Zr-30Fe-10Cr-5Cu-5Ti (alloy A), and 49Zr-30Fe-10Cr-5Cu-5Ti-1Y{sub 2}O{sub 3} (alloy B), 45Zr-30Fe-10Cr-10Cu-5Ti (alloy C), 44Zr-30Fe-10Cr-10Cu-5Ti-1Y{sub 2}O{sub 3} (alloy D) (all in wt%) by mechanical alloying and consolidated by pulse plasma sintering at 1173 K (900 °C), 1223 K (950 °C) and 1273 K (1000 °C) using 75 MPa uniaxial pressure applied for 5 min and 70 kA pulsed current at 3 Hz pulse frequency. The microstructure and phase evolution during mechanical alloying and sintering has been characterized by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM & TEM) and energy dispersive spectroscopy (EDS). Mechanical properties i.e. hardness and compressive strength were determined by using nano-indentation unit and universal testing machine. The produced alloys recorded very high levels of compressive strength (1359–2456 MPa), and hardness (7.05–10.05 GPa) which measures 1.5–2.0 times more than that of other Zr alloys (2 O{sub 3}) particles which can contribute to grain boundary pinning, and improved creep and oxidation resistance at elevated temperature.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Generation and healing of porosity in high purity copper by high-pressure torsion

Highlights: • Direct characterization of severe plastic deformation induced and healed porosities. • HPT process of disk with pre-fabricated holes reveals healing of porosity. • Ultrafine grains coexisting with shear bands and pores exhibit high stability. • Excess vacancies and pores cause drag effect on the grain boundary motion. • Accelerated vacancy diffusion leads to the generation and growth of pores. - Abstract: Generation and healing of pores in metals under loading or during processing have long been important research topics, and their mechanisms are still debatable. In recent years, unexpected percolating networks of pores acting as ultra-fast diffusion paths were found in ultrafine-grained metals processed by severe plastic deformation. Herein, we conducted a systematic study of the mechanisms of generation and healing of pores in ultrahigh-purity copper (99.9995 wt%) during high-pressure torsion (HPT). In addition to a solid Cu disk, the disk with holes that were drilled before processing, resulting in nominal initial porosity of 4.48%, was processed by HPT. After HPT, the percolating porosities of 0.07 ± 0.01% and 0.04 ± 0.01% were found in the solid disk, and in the disk with pre-fabricated holes, respectively. Thus, higher initial porosity resulted in lower percolating porosity in the HPT-processed disk. Systemic characterization using scanning electron microscopy revealed that in both cases shear bands and ultra-fine grains are located in the regions with induced and healed pores. We discussed the mechanisms of porosity evolution in both cases. In the end, to verify the possibility of pores nucleation and growth by vacancy agglomeration, vacancy diffusivity during HPT processing was estimated. This work sheds a new light on the mechanisms of pores nucleation and evolution during severe plastic deformation.

36 MATERIALS SCIENCE↗

Reactions of hydrazine with the amidogen radical and atomic hydrogen

The rate coefficient k 1 for NH 2 + N 2 H 4 was measured to be (5.4 ± 0.4) × 10 –14 cm 3 molecule –1 s –1 at 296 K. NH 2 was generated by pulsed laser photolysis of NH 3 at 193 nm, and monitored as a function of time by pulsed laser-induced fluorescence excited at 570.3 nm under pseudo-first order conditions in the presence of excess N 2 H 4 in an Ar bath gas. This reaction was also investigated computationally, with geometries and scaled frequencies obtained with M06-2X/6-311+G(2df,2p) theory, and single-point energies from CCSD(T)-F12b/cc-pVTZ-F12 theory, plus a term to correct approximately for electron correlation through CCSDT(Q). Three connected transition states are involved and rate constants were obtained via Multistructural Improved Canonical Variational Transition State Theory with Small Curvature Tunneling. Combination of experiment and theory leads to a recommended rate coefficient for hydrogen abstraction of k 1 = 6.3 × 10 –23 T 3.44 exp(+289 K/T) cm 3 molecule –1 s –1 . The minor channel for H + N 2 H 4 forming NH 2 + NH 3 was characterized computationally as well, to yield 5.0 × 10 –19 T 2.07 exp(-4032 K/T) cm 3 molecule –1 s –1 . Finally, these results are compared to several discordant prior estimates, and are employed in an overall mechanism to compare with measurements of half-lives of hydrazine in a shock tube.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Layered-rocksalt intergrown cathode for high-capacity zero-strain battery operation

Abstract The dependence on lithium-ion batteries leads to a pressing demand for advanced cathode materials. We demonstrate a new concept of layered-rocksalt intergrown structure that harnesses the combined figures of merit from each phase, including high capacity of layered and rocksalt phases, good kinetics of layered oxide and structural advantage of rocksalt. Based on this concept, lithium nickel ruthenium oxide of a main layered structure ( R $$\bar{3}$$ 3 ¯ m ) with intergrown rocksalt ( Fm $$\bar{3}$$ 3 ¯ m ) is developed, which delivers a high capacity with good rate performance. The interwoven rocksalt structure successfully prevents the anisotropic structural change that is typical for layered oxide, enabling a nearly zero-strain operation upon high-capacity cycling. Furthermore, a design principle is successfully extrapolated and experimentally verified in a series of compositions. Here, we show the success of such layered-rocksalt intergrown structure exemplifies a new battery electrode design concept and opens up a vast space of compositions to develop high-performance intergrown cathode materials.

25 ENERGY STORAGE↗

Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries

Abstract Confining molecules in the nanoscale environment can lead to dramatic changes of their physical and chemical properties, which opens possibilities for new applications. There is a growing interest in liquefied gas electrolytes for electrochemical devices operating at low temperatures due to their low melting point. However, their high vapor pressure still poses potential safety concerns for practical usages. Herein, we report facile capillary condensation of gas electrolyte by strong confinement in sub-nanometer pores of metal-organic framework (MOF). By designing MOF-polymer membranes (MPMs) that present dense and continuous micropore (~0.8 nm) networks, we show significant uptake of hydrofluorocarbon molecules in MOF pores at pressure lower than the bulk counterpart. This unique property enables lithium/fluorinated graphite batteries with MPM-based electrolytes to deliver a significantly higher capacity than those with commercial separator membranes (~500 mAh g −1 vs. <0.03 mAh g −1 ) at −40 °C under reduced pressure of the electrolyte.

25 ENERGY STORAGE↗