Abstract Aim Pollination is an essential stage of angiosperm reproduction, and the mode of pollination plays a major role in driving evolutionary and ecological responses of plants to environmental changes. However, the effects of climate, evolutionary history and floral traits (i.e. plant sexual systems) on pollination mode variation remain unclear. Here, we explored the biogeographic patterns in pollination mode frequency and tested the hypothesis that insect pollination prevails in warm humid regions with old floras due to high pollinator dependence, whereas wind pollination is more frequent in arid regions with younger floras and is more strongly associated with dioecy. Location China. Time period Since the Last Glacial Maximum. Major taxa studied Angiosperms. Methods Using data on pollination modes and geographic ranges of 29,719 angiosperm species in China, we mapped the biogeographic pattern of pollination mode frequency. Phylogenetic logistic regressions and generalized linear mixed models were employed to evaluate the relative importance of climate, evolutionary history (represented by phylogenetic conservatism and grid-level mean genus age) and sexual systems on variations in pollination modes across species and space. Results Evolutionary history was the strongest correlate of pollination mode variation across species and space. The proportion of insect-pollinated species was higher in humid regions with old floras, but lower in arid regions with young floras. Evolutionary history and temperature dominated variations in pollination mode frequency in humid areas, while precipitation dominated in arid areas. Climate influenced geographic pattern in pollination mode frequency both directly and indirectly via its effects on species richness and plant sexual systems. Main Conclusions Our results showed that geographic pattern in angiosperm pollination mode frequency is dominated by evolutionary history followed by climate, which extended previous findings of climate-driven mechanisms. Our findings demonstrate the importance to incorporate evolutionary history in understanding the mechanisms underlying the functional biogeography of plant traits.
Abstract Aim Climate has been regarded as an important explanation for large-scale species richness patterns. However, the mechanisms underlying the significant variations in species richness?climate relationships across different clades remain to be tested. We explored how niche conservatism, diversification rates and time for speciation influenced species richness?climate relationships between clades. Location The globe. Time Period Present day. Major Taxa Studied Angiosperms. Methods Based on a newly complied database of the global distributions of 288,735 angiosperm species, we used generalized linear models to assess the relationships between species richness of different angiosperm families and climatic factors. We also conducted phylogenetic comparative analysis to test whether niche conservatism, diversification rates and time for speciation affect the variations in species richness?climate relationships. Results We found that temperature seasonality dominated the global angiosperm diversity patterns. Closely related families had more similar species richness?climate relationships than distantly related ones. The discrepancy between the current and ancestral niches of different clades had much stronger effects on variations in species richness?climate relationships than diversification rates and time for speciation. With the increase in the discrepancy between current and ancestral niches, the explanatory power (i.e., R2) of contemporary temperature and precipitation in explaining species richness patterns increased. Main Conclusions Overall, our findings strongly support that niche conservatism dominates the variations in species richness?climate relationships across taxonomic groups. These findings allow better understanding on how large-scale species diversity patterns are formed.
Organic aerosol particles are oxidized by atmospheric oxidants. These particles are occasionally internally mixed with solid materials such as soot and inorganic crystals. However, potential impacts of the particles' mixing states on chemical reactivity have rarely been investigated. This study investigated the influence of the existence of crystalline ammonium sulfate on chemical reactivity of oleic acid particles with ozone for the temperature range of −20°C to +35°C using an aerosol flow tube reactor. The chemical compositions of the resulting particles were monitored using online instruments for deriving the reactive uptake coefficients (γ) of ozone by oleic acid. The values of γ were not significantly influenced by the existence of ammonium sulfate when the temperature of the reactor was higher than the melting point of oleic acid (∼13°C). The values of γ were unmeasurably small for the lower temperature range when oleic acid particles were internally mixed with crystalline ammonium sulfate. No significant change in γ was observed for the temperature range down to −13°C when the inorganic salt was absent, likely due to the formation of supercooled liquid. The difference in chemical reactivity can be explained by the occurrence of heterogeneous nucleation induced by inorganic seed.
Abstract Organic aerosol particles are oxidized by atmospheric oxidants. These particles are occasionally internally mixed with solid materials such as soot and inorganic crystals. However, potential impacts of the particles' mixing states on chemical reactivity have rarely been investigated. This study investigated the influence of the existence of crystalline ammonium sulfate on chemical reactivity of oleic acid particles with ozone for the temperature range of −20°C to +35°C using an aerosol flow tube reactor. The chemical compositions of the resulting particles were monitored using online instruments for deriving the reactive uptake coefficients (γ) of ozone by oleic acid. The values of γ were not significantly influenced by the existence of ammonium sulfate when the temperature of the reactor was higher than the melting point of oleic acid (∼13°C). The values of γ were unmeasurably small for the lower temperature range when oleic acid particles were internally mixed with crystalline ammonium sulfate. No significant change in γ was observed for the temperature range down to −13°C when the inorganic salt was absent, likely due to the formation of supercooled liquid. The difference in chemical reactivity can be explained by the occurrence of heterogeneous nucleation induced by inorganic seed.
In the presence of the difficulties pertinent to the selective oxidation of cyanide and the high-efficient hydrolysis of cyanate, the mineralization of cyanide into nitrogen could not be realized during the traditional processes. Herein, a novel system of electrocatalysis coupled with ultraviolet-based advanced oxidation processes (UV/EC/PS, PS: persulfate) is developed, exhibiting astonishingly high activity and selectivity for cyanide mineralization. The achieved results reveal that adequate active-chlorine species (ClO•/Cl2•−) are generated due to the synergistic effects of electrocatalysis and advanced oxidation processes and these are high-selective for cyanide mineralization. Concurrently, induced by the interconversion between active species, the pH value in the UV/EC/PS system vigorously lessens from 11.5 to 3.3 at a rate of 1.1 × 10-2 min−1, hugely speeding up the hydrolysis of cyanate intermediates. The results display that PS plays a pivotal role in the formation of ClO•/Cl2•− and the self-reduction of pH value in the UV/EC/PS system. Under the action of ClO•/Cl2•− and self-decreased pH value, 0.25 mM of ferricyanide is thoroughly mineralized into nitrogen within 80 min and no HCN evolves. Additionally, the UV/EC/PS system exhibits exceptional feasibility for the practical purifications of cyanide-containing wastewater (CCWW). This study aims to give new insights into developing technologies associated with the mineralization treatment of CCWW.
A novel PbO2 electrode modified with rare earth elements (La, Ce, Gd and Er) doping (named as Re-PbO2) was prepared by electrodeposition in the present study. The micro-morphology and crystal structure of Re-PbO2 were characterized by scanning electronic microscopy (SEM), energy dispersive spectroscope (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. Their electrochemical properties were determined by linear sweep voltammetry (LSV), cyclic voltammetry (CV), accelerated life test and hydroxyl radicals (•OH) formation analysis. Electrochemical oxidation of p-nitrophenol (p-NP) by Re-PbO2 compared with un-doped PbO2 has been investigated and the degradation rate followed the order of Er-PbO2 > Gd-PbO2 > La-PbO2 > Ce-PbO2 > PbO2. Especially for Er-PbO2, the pseudo-first order kinetic for p-NP (kp-NP) degradation was 0.41, which was only 0.19 for un-doped PbO2. Rare earths elements doping improved the oxidation ability of Re-PbO2 mainly through reducing grain size, increasing oxygen evolution potential, enlarging electrochemical active surface area and enhancing •OH formation ability. In addition, existing formation of oxygen species on PbO2 electrode surface was investigated by XPS. For Re-PbO2, percentage of lattice oxygen species (Oads) were higher than that on the un-doped one. These results demonstrated that rare earth elements can enhance the oxidation ability of PbO2 electrode significantly.
MnFe Prussian blue analogues (MnFe PBAs) were fabricated for acetamiprid degradation with peroxymonosulfate (PMS) as an oxidant. MnFe PBAs (200) are the most active facets for PMS activation due to the superior chemisorption affinity and electron-transfer ability. Density functional theory calculation verified that Mn(III) served as an electron donor and acceptor to adjust the electron density between Fe and Mn, which played a crucial role in the high activation performance of MnFe PBAs (200). PBA lattice (−C═N) did not exhibit direct PMS activation capability in this system, which differed from previously reported Fenton counterparts. Based on the electronic localization function calculation and probe experiments, the O–O of HSO5– was broken, and the bonds of PBA could be restored during the activation reaction, leading to the continuous generation of reactive oxygen species in the MnFe PBAs/PMS system. Transformation product studies indicated that the oxidized products were primarily the result of aromatic hydroxylation, N–C bond cleavage, azo reaction, and so forth, achieving the mineralization and ecotoxicity mitigation of acetamiprid efficiently. Findings in this study provided new insights into developing advanced facet-dependent catalysts to activate PMS for the efficient degradation of emerging contaminants in the aqueous environment.
Precisely identifying the atomic structures in single-atom sites and establishing authentic structure–activity relationships for single-atom catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted the underlying catalytic activity of Fe–NxC4–x sites with diverse first-shell coordination environments. Substituting N with C to coordinate with the central Fe atom induces an inferior Fenton-like catalytic efficiency. Then, Fe-SACs carrying three configurations (Fe–N2C2, Fe–N3C1, and Fe–N4) fabricate facilely and demonstrate that optimized coordination environments of Fe–NxC4–x significantly promote the Fenton-like catalytic activity. Specifically, the reaction rate constant increases from 0.064 to 0.318 min–1 as the coordination number of Fe–N increases from 2 to 4, slightly influencing the nonradical reaction mechanism dominated by 1O2. In-depth theoretical calculations unveil that the modulated coordination environments of Fe-SACs from Fe–N2C2 to Fe–N4 optimize the d-band electronic structures and regulate the binding strength of peroxymonosulfate on Fe–NxC4–x sites, resulting in a reduced energy barrier and enhanced Fenton-like catalytic activity. The catalytic stability and the actual hospital sewage treatment capacity also showed strong coordination dependency. This strategy of local coordination engineering offers a vivid example of modulating SACs with well-regulated coordination environments, ultimately maximizing their catalytic efficiency.
he simultaneous precipitation of (Fe, Cr)(OH)3 nanoparticles in solution (homogeneous) and on soil surfaces (heterogeneous), which controls Cr transport in soil and aquatic systems, was quantified for the first time in the presence of model surfaces, i.e., bare and natural organic matter (NOM)-coated SiO2 and Al2O3. Various characterization techniques were combined to explore the surface-ion-precipitate interactions and the controlling mechanisms. (Fe, Cr)(OH)3 accumulation on negatively charged SiO2 was mainly governed by electrostatic interactions between hydrolyzed ion species or homogeneous (Fe, Cr)(OH)3 and surfaces. The elevated pH through protonation of Al2O3 surface hydroxyls resulted in higher Cr/Fe ratios in both homogeneous and heterogeneous coprecipitates. Due to ignorable NOM adsorption onto SiO2, the amounts of (Fe, Cr)(OH)3 precipitates on bare/NOM-SiO2 were similar; contrarily, attributed to favored NOM adsorption onto Al2O3 and consequently carboxyl association with metal ions or (Fe, Cr)(OH)3 nanoparticles, remarkably more heterogeneous precipitates harvested on NOM-Al2O3 than bare-Al2O3. With the same solution supersaturation, the total amounts of homogeneous and heterogeneous precipitates were similar irrespective of the substrate type. With lower pH, decreased electrostatic forces between substrates and precipitates shifted (Fe, Cr)(OH)3 distribution from heterogeneous to homogeneous phases. The quantitative knowledge of (Fe, Cr)(OH)3 distribution and the controlling mechanisms can assist in better Cr sequestration in natural and engineered settings.
This study investigates the effect of firm performance on corporate social responsibility (CSR) in a specific spatial context. The results for a sample of 1,557 listed companies in China suggest that a firm’s CSR performance level is influenced by that of nearby firms. This study also confirms the indirect link between financial and CSR performance through the mediating role of institutional and executive shareholding rates. In addition, the empirical evidence in this study not only supports the spatial context-sensitive thesis but, more importantly, proposes a spatiotemporal context-sensitive thesis. It provides strong empirical support for the true relative value of the spatiotemporal context affecting CSR performance, which yields important theoretical, methodological, and policy implications.
The wake-up and fatigue effects exhibited by ferroelectric hafnium oxide (HfO2) during electrical cycling are two of the most significant obstacles limiting its development and application. Despite a mainstream theory relating these phenomena to the migration of oxygen vacancies and the evolution of the built-in field, no supportive experimental observations from a nanoscale perspective have been reported so far. By combining differential phase contrast scanning transmission electron microscopy (DPC-STEM) and energy dispersive spectroscopy (EDS) analysis, we directly observe the migration of oxygen vacancies and the evolution of the built-in field in ferroelectric HfO2 for the first time. These solid results indicate that the wake-up effect is caused by the homogenization of oxygen vacancy distribution and weakening of the vertical built-in field whereas the fatigue effect is related to charge injection and transverse local electric field enhancement. In addition, using a low-amplitude electrical cycling scheme, we exclude field-induced phase transition from the root cause of the wake-up and fatigue in Hf0.5Zr0.5O2. With direct experimental evidence, this work clarifies the core mechanism of the wake-up and fatigue effects, which is important for the optimization of ferroelectric memory devices.
Abstract The detection of surface electromyography (sEMG) signals on the skin has attracted increasing attention because of its ability to monitor muscle conditions in a noninvasive manner and thus possesses great application potential to assess athletic status and training efficiency in real time or to evaluate postoperative muscle rehabilitation conveniently. Here, a flexible wireless sEMG monitoring system that consists of a stretchable sEMG epidermal patch and a flexible printed circuit board to provide real-time evaluation of muscle strength and fatigue is reported. The epidermal patch is designed to have good stretchability and permeability and optimized to ensure a low contact impedance with the skin and minimized background noise for sEMG signal acquisition with high fidelity. Six commonly used time-domain and two frequency-domain features extracted from sEMG signals are systematically analyzed, and a strategy for feature selection and pattern identification is proposed that eventually enables the real-time assessment of muscle strength and fatigue by using an integrated system in a wearable form.
Tight and shale reservoirs are forming important components of the global hydrocarbon landscape, which impede the free thermal movement of fluid molecules, with numerous nanoscale pores. The confined hydrocarbons in the nanopores cannot be industrially produced from conventional exploration and development methods, with deviated fluid phase behavior under nano-confinement effects. Most commonly important fluid phase behavior in nanopores has been simulated and compared with the bulk cases previously, including phase coexistence, critical properties, and density distribution of confined fluids. This paper focuses on the deviated fluid phase behavior under nano-confinement effects by Monte Carlo modeling. The Monte Carlo simulation is still limited to modeling the macroscopic pore-related behavior like capillarity and complex fluid and solid materials. Moreover, the Monte Carlo simulation is usually scale-restricted and the pore-size range where the nano-confinement effect fails to work needs to be quantitatively determined. Overall, for the tight and shale fluid phase behavior, a functional Monte Carlo model, coupled with the long-range correction and configuration bias techniques, is suggested to include both the multi-component fluids and skeleton.