The relative importance of drought stress and neighbor richness on plant-plant interactions shifts over a short time.

Exploring how plant-plant interactions between species and their neighbors vary with biotic and abiotic factors is vital to understanding community assembly mechanisms in the context of global changes. In this study, using a dominant species (Leymus chinensis (Trin.) Tzvel.) in the semiarid Inner Mongolia steppe as the target species and ten other species as neighbors, we carried out a microcosm experiment to evaluate how drought stress, neighbor richness and season affected the relative neighbor effect (Cint) (the ability to reduce growth of target species). The factor of season interactively affected the effect of drought stress or neighbor richness on Cint. In the summer, drought stress decreased Cint directly and indirectly by decreasing SLA hierarchical distance and neighbor biomass. In the subsequent spring, drought stress increased Cint, and neighbor richness increased Cint directly and indirectly by increasing neighbor community functional dispersion (FDis) and neighbor biomass. Specifically, SLA hierarchical distance was positively associated with neighbor biomass, while height hierarchical distance was negatively associated with neighbor biomass in both seasons, which increased Cint. These findings show that the relative importance of drought stress and neighbor richness on Cint shifted over seasons, which provides strong empirical evidence of how plant-plant interactions respond to changes in biotic and abiotic factors in the semiarid Inner Mongolia steppe over a short-term time. Furthermore, this study provides novel insight into community assembly mechanisms in the context of climatic aridity and biodiversity loss in semiarid regions.

Polyoxometalate-based frameworks for photocatalysis and photothermal catalysis.

Polyoxometalate-based frameworks (POM-based frameworks) are extended structures assembled from metal-oxide cluster units and organic frameworks that simultaneously possess the virtues of POMs and frameworks. They have been attracting immense attention because of their diverse architectures and charming topologies and also due to their probable application prospects in the areas of catalysis, separation, and energy storage. In this review, the recent progress in POM-based frameworks including POM-based metal organic frameworks (PMOFs), POM-based covalent organic frameworks (PCOFs), and POM-based supramolecular frameworks (PSFs) is systematically summarized. The design and construction of a POM-based framework and its application in photocatalysis and photothermal catalysis are introduced, respectively. Finally, our brief outlooks on the current challenges and future development of POM-based frameworks for photocatalysis and photothermal catalysis are provided.

Infection by Endophytic Epichloë sibirica Was Associated with Activation of Defense Hormone Signal Transduction Pathways and Enhanced Pathogen Resistance in the Grass Achnatherum sibiricum.

Epichloë endophytes can improve the resistance of host grasses to pathogenic fungi, but the underlying mechanisms remain largely unknown. Here, we used phytohormone quantifications, gene expression analysis, and pathogenicity experiments to investigate the effect of Epichloë sibirica on the resistance of Achnatherum sibiricum to Curvularia lunata pathogens. Comparison of gene expression patterns between endophyte-infected and endophyte-free leaves revealed that endophyte infection was associated with significant induction of 1,758 and 765 differentially expressed genes in the host before and after pathogen inoculation, respectively. Functional analysis of the differentially expressed genes suggested that endophyte infection could activate the constitutive resistance of the host by increasing photosynthesis, enhancing the ability to scavenge reactive oxygen species, and actively regulating the expression of genes with function related to disease resistance. We found that endophyte infection was associated with induction of the expression of genes involved in the biosynthesis pathways of jasmonic acid, ethylene, and pipecolic acid and amplified the defense response of the jasmonic acid/ethylene co-regulated EIN/ERF1 transduction pathway and Pip-mediated TGA transduction pathway. Phytohormone quantifications showed that endophyte infection was associated with significant accumulation of jasmonic acid, ethylene, and pipecolic acid after pathogen inoculation. Exogenous phytohormone treatments confirmed that the disease index of plants was negatively related to both jasmonic acid and ethylene concentrations. Our results demonstrate that endophyte infection can not only improve the constitutive resistance of the host to phytopathogens before pathogen inoculation but also be associated with enhanced systemic resistance of the host to necrotrophs after C. lunata inoculation.

Ultrahigh-Quality Infrared Polaritonic Resonators Based on Bottom-Up-Synthesized van der Waals Nanoribbons.

van der Waals nanomaterials supporting phonon polariton quasiparticles possess extraordinary light confinement capabilities, making them ideal systems for molecular sensing, thermal emission, and subwavelength imaging applications, but they require defect-free crystallinity and nanostructured form factors to fully showcase these capabilities. We introduce bottom-up-synthesized α-MoO3 structures as nanoscale phonon polaritonic systems that feature tailorable morphologies and crystal qualities consistent with bulk single crystals. α-MoO3 nanoribbons serve as low-loss hyperbolic Fabry-Pérot nanoresonators, and we experimentally map hyperbolic resonances over four Reststrahlen bands spanning the far- and mid-infrared spectral range, including resonance modes beyond the 10th order. The measured quality factors are the highest from phonon polaritonic van der Waals structures to date. We anticipate that bottom-up-synthesized polaritonic van der Waals nanostructures will serve as an enabling high-performance and low-loss platform for infrared optical and optoelectronic applications.

An oligomeric semiconducting nanozyme with ultrafast electron transfers alleviates acute brain injury.

Artificial enzymes have attracted wide interest in disease diagnosis and biotechnology due to high stability, easy synthesis, and cost effectiveness. Unfortunately, their catalytic rate is limited to surface electron transfer, affecting the catalytic and biological activity. Here, we report an oligomeric nanozyme (O-NZ) with ultrafast electron transfer, achieving ultrahigh catalytic activity. O-NZ shows electron transfer of 1.8 nanoseconds in internal cores and 1.2 picoseconds between core and ligand molecule, leading to ultrahigh superoxidase dismutase­like and glutathione peroxidase­like activity (comparable with natural enzyme, Michaelis constant = 0.87 millimolars). Excitingly, O-NZ can improve the 1-month survival rate of mice with acute brain trauma from 50 to 90% and promote the recovery of long-term neurocognition. Biochemical experiments show that O-NZ can decrease harmful peroxide and superoxide via in vivo catalytic chain reaction and reduce acute neuroinflammation via nuclear factor erythroid-2 related factor 2­mediated up-regulation of heme oxygenase-1 expression.

Endophytic Fungi Activated Similar Defense Strategies of Achnatherum sibiricum Host to Different Trophic Types of Pathogens.

It is well documented that Epichloë endophytes can enhance the resistance of grasses to herbivory. However, reports on resistance to pathogenic fungi are limited, and their conclusions are variable. In this study, we chose pathogenic fungi with different trophic types, namely, the biotrophic pathogen Erysiphales species and the necrotrophic pathogen Curvularia lunata, to test the effects of Epichloë on the pathogen resistance of Achnatherum sibiricum. The results showed that, compared to Erysiphales species, C. lunata caused a higher degree of damage and lower photochemical efficiency (Fv/Fm) in endophyte-free (E-) leaves. Endophytes significantly alleviated the damage caused by these two pathogens. The leaf damaged area and Fv/Fm of endophyte-infected (E+) leaves were similar between the two pathogen treatments, indicating that the beneficial effects of endophytes were more significant when hosts were exposed to C. lunata than when they were exposed to Erysiphales species. We found that A. sibiricum initiated jasmonic acid (JA)-related pathways to resist C. lunata but salicylic acid (SA)-related pathways to resist Erysiphales species. Endophytic fungi had no effect on the content of SA but increased the content of JA and total phenolic compounds, which suggest that endophyte infection might enhance the resistance of A. sibiricum to these two different trophic types of pathogens through similar pathways.

Removal of Soil Microbes Alters Interspecific Competitiveness of Epichloë Endophyte-Infected over Endophyte-Free Leymus chinensis.

Epichloë endophytes may not only affect the growth and resistances of host grasses, but may also affect soil environment including soil microbes. Can Epichloë endophyte-mediated modification of soil microbes affect the competitive ability of host grasses? In this study, we tested whether Epichloë endophytes and soil microbes alter intraspecific competition between Epichloë endophyte-colonized (EI) and endophyte-free (EF) Leymus chinensis and interspecific competition between L. chinensis and Stipa krylovii. The results demonstrated that Epichloë endophyte colonization significantly enhanced the intraspecific competitive ability of L. chinensis and that this beneficial effect was not affected by soil microbes. Under interspecific competition, however, significant interactions between Epichloë endophytes and soil microbes were observed. The effect of Epichloë endophytes on interspecific competitiveness of the host changed from positive to neutral with soil microbe removal. Here higher mycorrhizal colonization rates probably contributed to interspecific competitive advantages of EI over EF L. chinensis. Our result suggests that Epichloë endophytes can influence the competitive ability of the host through plant soil feedbacks from the currently competing plant species.

Corrigendum: Endophytic Fungi Activated Similar Defense Strategies of Achnatherum sibiricum Host to Different Trophic Types of Pathogens.

[This corrects the article DOI: 10.3389/fmicb.2020.01607.].

Reactive Oxygen Species-Induced Aggregation of Nanozymes for Neuron Injury.

Nanozymes show excellent enzyme activity and robust catalytic properties, but the targeting capability to disease organs is limited because of lack of specificity. Herein, we developed an ultrasmall (∼3 nm) organic nanozyme that can gradually aggregate under a reactive oxygen species (ROS)-rich environment via a spontaneous reaction, namely, ROS-induced aggregation. The size of nanozymes is 75 and 100 times higher than the original size under •OH and H2O2 environments without losing enzyme activity. In vitro experiments confirm that nanozymes prefer to aggregate in mitochondria under ROS-rich conditions. Importantly, the nanozymes show in situ ROS-induced aggregation in the brain, ∼9 times higher uptake than ordinary nanozymes, indicating their potential for treating ROS-related diseases in the central nervous system.

Black phosphorene as a hole extraction layer boosting solar water splitting of oxygen evolution catalysts.

As the development of oxygen evolution co-catalysts (OECs) is being actively undertaken, the tailored integration of those OECs with photoanodes is expected to be a plausible avenue for achieving highly efficient solar-assisted water splitting. Here, we demonstrate that a black phosphorene (BP) layer, inserted between the OEC and BiVO4 can improve the photoelectrochemical performance of pre-optimized OEC/BiVO4 (OEC: NiOOH, MnOx, and CoOOH) systems by 1.2∼1.6-fold, while the OEC overlayer, in turn, can suppress BP self-oxidation to achieve a high durability. A photocurrent density of 4.48 mA·cm-2 at 1.23 V vs reversible hydrogen electrode (RHE) is achieved by the NiOOH/BP/BiVO4 photoanode. It is found that the intrinsic p-type BP can boost hole extraction from BiVO4 and prolong holes trapping lifetime on BiVO4 surface. This work sheds light on the design of BP-based devices for application in solar to fuel conversion, and also suggests a promising nexus between semiconductor and electrocatalyst.

N- and O-Doped Carbon Dots for Rapid and High-Throughput Dual Detection of Trace Amounts of Iron in Water and Organic Phases.

In this work, we report a dual use of highly fluorescent N- and O-doped carbon dots (CDs) for rapid and high-throughput trace analysis of iron in water and organic phases. The CDs are rapidly synthesized in a sealed vessel via microwave irradiation within 5 min, and they exhibit high quantum yields of 80% with sensitive quenching responses to iron contents. Combined with a microplate fluorescence reader, a rapid and high-throughput assay for ions is further developed. The whole process from the CD synthesis to the detection output can be accomplished within 15 min. The limits of detection for Fe3+ in aqueous solution and ferrocene in organic gasoline are determined down to 0.05 mM. Furthermore, this method has been successfully used to determine the level of irons in real gasoline for quality evaluation. The results have an excellent agreement with atomic absorption spectrophotometric measurements. The CD-based facile assay with lower cost, use of less sample, and higher-throughput holds great promise as a powerful tool for iron detection in water and organic phase samples.

A facile plasmonic silver needle for fluorescence-enhanced detection of tumor markers.

Tumor markers have been regularly detected for early cancer diagnosis in clinical oncology. The development of facile and low cost technology has become an important challenge for their diagnosis. We here report a low-cost plasmonic silver needle (PSN) for immunofluorescence detection of tumor biomarkers. The fluorescence signal is enhanced on the needle by up to 220-fold, allowing high-performance detection of tumor markers down to 0.08 ng mL-1. To assess the clinical potential of the proposed assay technique, PSN-based sandwich immunoassay for the detection of alpha-fetoprotein and carcinoembryonic antigen were performed for blood as well as for serum sample. The results from serum sample have an excellent agreement with an electrochemluminecence assay. The small relative error and a good linear correlation suggest that the accuracy and precision of this analytical technology are satisfactory. This assay technique with lower cost, use of less sample, higher sensitivity and easier procedure shows great promise for the facile and early cancer diagnosis.

Quantitative Nanoscopy of Small Blinking Graphene Nanocarriers in Drug Delivery.

Nanotechnology-enhanced drug delivery via receptor-mediated endocytosis provides a promising and clinically translatable strategy to targeted diagnosis and precise therapy, yet an in-depth understanding of this process is technically limited by our inability to probe the nanocarrier distributions at the cell surface and inside the cell at nanoscale resolution. Here, we report small blinking single-layer graphene oxide nanosheet (GONS) that  serves both as a nanoscopy fluorophore and as a drug-bearing nanocarrier for addressing such a task. The GONS blinks spontaneously with a low duty cycle (∼0.003), high photon output (∼3000 photons per switching event), and higher photostability than organic dyes, thus affording well for single molecule localization-based super-resolution imaging. Applying the localization analysis, we reveal GONS clustering size, GONS number in each cluster, and the number fraction of GONSs that participate in clustering at the cell surface and in the cytoplasm, respectively, and track their evolutions over 24 h. The data suggest that the nanocarrier clustering and distribution at the cell surface control their endocytosis and accumulation inside the cell. This process is drug-independent during which drug transportation into the destination relies on its own loading and escaping capability. Thus, this work demonstrates the great potential of the dual-functional GONS in quantitative super-resolution imaging of drug carriers in cells, which is helpful for the rational design of a smart drug delivery system aiming at achieving full therapeutic capacity.

Understanding activity trends in electrochemical water oxidation to form hydrogen peroxide.

Electrochemical production of hydrogen peroxide (H2O2) from water oxidation could provide a very attractive route to locally produce a chemically valuable product from an abundant resource. Herein using density functional theory calculations, we predict trends in activity for water oxidation towards H2O2 evolution on four different metal oxides, i.e., WO3, SnO2, TiO2 and BiVO4. The density functional theory predicted trend for H2O2 evolution is further confirmed by our experimental measurements. Moreover, we identify that BiVO4 has the best H2O2 generation amount of those oxides and can achieve a Faraday efficiency of about 98% for H2O2 production.Producing hydrogen peroxide via electrochemical oxidation of water is an attractive route to this valuable product. Here the authors theoretically and experimentally investigate hydrogen peroxide production activity trends for a range of metal oxides and identify the optimal bias ranges for high Faraday efficiencies.

Encapsulation of Single Nanoparticle in Fast-Evaporating Micro-droplets Prevents Particle Agglomeration in Nanocomposites.

This work describes the use of fast-evaporating micro-droplets to finely disperse nanoparticles (NPs) in a polymer matrix for the fabrication of nanocomposites. Agglomeration of particles is a key obstacle for broad applications of nanocomposites. The classical approach to ensure the dispersibility of NPs is to modify the surface chemistry of NPs with ligands. The surface properties of NPs are inevitably altered, however. To overcome the trade-off between dispersibility and surface-functionality of NPs, we develop a new approach by dispersing NPs in a volatile solvent, followed by mixing with uncured polymer precursors to form micro-droplet emulsions. Most of these micro-droplets contain no more than one NP per drop, and they evaporate rapidly to prevent the agglomeration of NPs during the polymer curing process. As a proof of concept, we demonstrate the design and fabrication of TiO2 NP@PDMS nanocomposites for solar fuel generation reactions with high photocatalytic efficiency and recyclability arising from the fine dispersion of TiO2. Our simple method eliminates the need for surface functionalization of NPs. Our approach is applicable to prepare nanocomposites comprising a wide range of polymers embedded with NPs of different composition, sizes, and shapes. It has the potential for creating nanocomposites with novel functions.

Unassisted photoelectrochemical water splitting exceeding 7% solar-to-hydrogen conversion efficiency using photon recycling.

Various tandem cell configurations have been reported for highly efficient and spontaneous hydrogen production from photoelectrochemical solar water splitting. However, there is a contradiction between two main requirements of a front photoelectrode in a tandem cell configuration, namely, high transparency and high photocurrent density. Here we demonstrate a simple yet highly effective method to overcome this contradiction by incorporating a hybrid conductive distributed Bragg reflector on the back side of the transparent conducting substrate for the front photoelectrochemical electrode, which functions as both an optical filter and a conductive counter-electrode of the rear dye-sensitized solar cell. The hybrid conductive distributed Bragg reflectors were designed to be transparent to the long-wavelength part of the incident solar spectrum (λ>500 nm) for the rear solar cell, while reflecting the short-wavelength photons (λ<500 nm) which can then be absorbed by the front photoelectrochemical electrode for enhanced photocurrent generation.

Understanding the synergistic effect of WO3-BiVO4 heterostructures by impedance spectroscopy.

WO3-BiVO4 n-n heterostructures have demonstrated remarkable performance in photoelectrochemical water splitting due to the synergistic effect between the individual components. Although the enhanced functional capabilities of this system have been widely reported, in-depth mechanistic studies explaining the carrier dynamics of this heterostructure are limited. The main goal is to provide rational design strategies for further optimization as well as to extend these strategies to different candidate systems for solar fuel production. In the present study, we perform systematic optoelectronic and photoelectrochemical characterization to understand the carrier dynamics of the system and develop a simple physical model to highlight the importance of the selective contacts to minimize bulk recombination in this heterostructure. Our results collectively indicate that while BiVO4 is responsible for the enhanced optical properties, WO3 controls the transport properties of the heterostructured WO3-BiVO4 system, leading to reduced bulk recombination.

A 3D triple-deck photoanode with a strengthened structure integrality: enhanced photoelectrochemical water oxidation.

WO3/BiVO4 is one of the attractive Type II heterojunctions for photoelectrochemical (PEC) water splitting due to its well-matched band edge positions and visible light harvesting abilities. However, two light absorption components generally suffer from poor charge collection and cannot be efficiently utilized because of non-ideal interfaces. Herein, a triple-deck three-dimensional (3D) architecture was designed through a one-step shaping process with an additional stress relaxation WO3 underlayer. The final photoanodes showed a promising photocurrent density of 5.1 mA cm(-2) at 1.23 V vs. RHE under AM 1.5G illumination. Using the uniformly distributed oxygen evolution co-catalyst (OEC) layer as the outer most shell of the WO3/BiVO4/OEC triple-deck 3D structure with a dense WO3 underlayer, the water splitting efficiency was improved dramatically by facilitating the charge transfer process at the electrode/electrolyte interface.

General Characterization Methods for Photoelectrochemical Cells for Solar Water Splitting.

Photoelectrochemical (PEC) water splitting is a very promising technology that converts water into clean hydrogen fuel and oxygen by using solar light. However, the characterization methods for PEC cells are diverse and a systematic introduction to characterization methods for PEC cells has rarely been attempted. Unlike most other review articles that focus mainly on the material used for the working electrodes of PEC cells, this review introduces general characterization methods for PEC cells, including their basic configurations and methods for characterizing their performance under various conditions, regardless of the materials used. Detailed experimental operation procedures with theoretical information are provided for each characterization method. The PEC research area is rapidly expanding and more researchers are beginning to devote themselves to related work. Therefore, the content of this Minireview can provide entry-level knowledge to beginners in the area of PEC, which might accelerate progress in this area.

Efficient photoelectrochemical hydrogen production from bismuth vanadate-decorated tungsten trioxide helix nanostructures.

Tungsten trioxide/bismuth vanadate heterojunction is one of the best pairs for solar water splitting, but its photocurrent densities are insufficient. Here we investigate the advantages of using helical nanostructures in photoelectrochemical solar water splitting. A helical tungsten trioxide array is fabricated on a fluorine-doped tin oxide substrate, followed by subsequent coating with bismuth vanadate/catalyst. A maximum photocurrent density of ~5.35±0.15 mA cm(-2) is achieved at 1.23 V versus the reversible hydrogen electrode, and related hydrogen and oxygen evolution is also observed from this heterojunction. Theoretical simulations and analyses are performed to verify the advantages of this helical structure. The combination of effective light scattering, improved charge separation and transportation, and an enlarged contact surface area with electrolytes due to the use of the bismuth vanadate-decorated tungsten trioxide helical nanostructures leads to the highest reported photocurrent density to date at 1.23 V versus the reversible hydrogen electrode, to the best of our knowledge.