Identification of microRNAs and their target genes associated with chasmogamous and cleistogamous flower development in Viola prionantha.

MAIN CONCLUSION: Differentially expressed microRNAs were found associated with the development of chasmogamous and cleistogamous flowers in Viola prionantha, revealing potential roles of microRNAs in the developmental evolution of dimorphic flowers. In Viola prionantha, chasmogamous (CH) flowers are induced by short daylight, while cleistogamous (CL) flowers are triggered by long daylight. How environmental factors and microRNAs (miRNAs) affect dimorphic flower formation remains unknown. In this study, small RNA sequencing was performed on CH and CL floral buds at different developmental stages in V. prionantha, differentially expressed miRNAs (DEmiRNAs) were identified, and their target genes were predicted. In CL flowers, Viola prionantha miR393 (vpr-miR393a/b) and vpr-miRN3366 were highly expressed, while in CH flowers, vpr-miRN2005, vpr-miR172e-2, vpr-miR166m-3, vpr-miR396f-2, and vpr-miR482d-2 were highly expressed. In the auxin-activated signaling pathway, vpr-miR393a/b and vpr-miRN2005 could target Vpr-TIR1/AFB and Vpr-ARF2, respectively, and other DEmiRNAs could target genes involved in the regulation of transcription, e.g., Vpr-AP2-7. Moreover, Vpr-UFO and Vpr-YAB5, the main regulators in petal and stamen development, were co-expressed with Vpr-TIR1/AFB and Vpr-ARF2 and showed lower expression in CL flowers than in CH flowers. Some V. prionantha genes relating to the stress/defense responses were co-expressed with Vpr-TIR1/AFB, Vpr-ARF2, and Vpr-AP2-7 and highly expressed in CL flowers. Therefore, in V. prionantha, CH-CL flower development may be regulated by the identified DEmiRNAs and their target genes, thus providing the first insight into the formation of dimorphic flowers in Viola.

Oxygen Vacancy and Heterostructure Modulation of Co2P/Fe2P Electrocatalysts for Improving Total Water Splitting.

Designing a stable and highly active catalyst for hydrogen evolution and oxygen evolution reactions (HER/OER) is essential for the industrialization of hydrogen energy but remains a major challenge. This work reports a simple approach to fabricating coupled Co2P/Fe2P nanorod array catalyst for overall water decomposition, demonstrating the source of excellent activity in the catalytic process. Under alkaline conditions, Co2P/Fe2P heterostructures exhibit an overpotential of 96 and 220 mV for HER and OER, respectively, at 10 mA cm-2. For total water splitting, a low voltage of 1.56 V is required to provide a current density of 10 mA cm-2. And the catalyst exhibits long-term durability for 30 h at a high current density of 250 mA cm-2. The analysis of the results revealed that the presence of interfacial oxygen vacancies and the strong interaction between Co2P/Fe2P provided the catalyst with more electrochemically active sites and a faster charge transfer capability, which improved the hydrolysis dissociation process. Electrochemically active metal (oxygen) hydroxide phases were produced after OER stability testing. The results of this study prove its great potential in practical industrial electrolysis and provide a reasonable and feasible strategy for the design of nonprecious metal phosphide electrocatalysts.

Electrodeposition-Assisted Crystal Growth Regulation of PdBi Clusters on Carbon Cloths for Ethanol Oxidation.

Carbon-supported Pd-based clusters are one of the most promising anodic catalysts for ethanol oxidation reaction (EOR) due to their encouraging activity and practical applications. However, unclear growth mechanism of Pd-based clusters on the carbon-based materials has hindered their extensive applications. Herein, we first introduce multi-void spherical PdBi cluster/carbon cloth (PdBi/CC) composites by an electrodeposition routine. The growth mechanism of PdBi clusters on the CC supports has been systemically investigated by evaluating the selected samples and tuning their compositions, which involve the big difference in standard redox potential between Pd2+/Pd and Bi3+/Bi and easy adsorption of Bi3+ on the surface of Pd-rich seeds. Benefitting from the ensembles of many nanocrystal subunits, multi-void spherical PdBi clusters can present collective properties and novel functionalities. In addition, the outstanding characteristics of CC supports enable PdBi clusters with stable nanostructures. Thanks to the unique structure, Pd20Bi/CC catalysts manifest higher EOR activity and better stability compared to Pd/CC. Systematic characterizations and a series of CO poisoning tests further confirm that the dramatically enhanced EOR activity and stability can be attributed to the incorporation of Bi species and the strong coupling of the structure between PdBi clusters and CC supports.

Curved Porous PdCu Metallene as a High-Efficiency Bifunctional Electrocatalyst for Oxygen Reduction and Formic Acid Oxidation.

Designing high-efficiency and newly developed Pd-based bifunctional catalytic materials still faces tremendous challenges for oxygen reduction reaction (ORR) and formic acid oxidation reaction (FAO). Metallene materials with unique structural features are considered strong candidates for enhancing the catalytic performance. In this work, we synthesized copper-doped two-dimensional curved porous Pd metallene nanomaterials via a simplistic one-pot solvothermal method. The updated catalysts served as sturdy bifunctional electrocatalysts for cathodal ORR and anodic FAO. In particular, the developed PdCu metallene exhibits excellent half-wave potential (0.943 V vs RHE) and mass activity (MA) (1.227 A mgPt-1) in alkaline solutions, which are 1.09 and 6.26 times higher than those of commercial Pt/C, respectively, indicating that the nanomaterials have abundant active sites, displaying surpassing catalytic performance for oxygen reduction. Furthermore, in an acidic formic acid electrolyte, PdCu metallene exhibits prominent MA with a value of 0.905 A mgPd-1, which is 2.76 times that of commercial Pd/C. The remarkable bifunctional catalytic performance of metallene materials can be attributed to the special structure and electronic effects. This work shows that metallene materials with curved and porous properties provide a scientific idea for the development and design of efficient and steady electrocatalysts.

Top-down manufacturing of efficient CO2 reduction catalysts from the gasification residue carbon.

Gram scale preparation of carbon-supported single-atom catalysts was achieved via a top-down approach starting from metallic and metalloid constituent-enriched gasification residual carbon, exhibiting superior electrocatalytic performance for CO2-to-CO conversion in both H-type and membrane electrode assembly electrolyzers.

Transcriptomic comparison sheds new light on regulatory networks for dimorphic flower development in response to photoperiod in Viola prionantha.

BACKGROUND: Chasmogamous (CH)-cleistogamous (CL) dimorphic flowers are developed in Viola prionantha. However, the environmental and genetic factors necessary for the CH-CL transition are unknown. RESULTS: In the present work, short-day (SD) conditions induced CH flowers, whereas long days (LDs) triggered CL flowers in V. prionantha. Compared to fully developed CH flowers, CL flowers had less mature stamens, no nectar glands, and immature petals. Comparative transcriptomics revealed differentially expressed genes (DEGs) during CL and CH development. Core genes in the photoperiod pathway, such as V. prionantha orthologs of GIGANTEA (GI), CONSTANS (CO), and SUPPRESSOR OF OVEREXPRESSION OF CONSTANS 1 (SOC1), which promote floral induction, were highly expressed in CL flowers, whereas UNUSUAL FLORAL ORGANS (UFO) and B-class MADS-box genes for floral organ identity and development showed an opposite alteration. Moreover, genes in the glycolytic process, sucrose metabolic process, and fatty acid biosynthetic process were all highly expressed in CH flowers. Interestingly, V. prionantha orthologs of the B-class MADS-box genes APETALA3 (AP3) and PISTILLATA (PI) might relate to these sugar-fatty acid processes and were co-expressed with GAIP-B-like and YABBY5 (YAB5), which regulate the development of the petal, stamen, and nectary. Compared to CH flowers, DEGs and hub genes in the most significantly correlated modules of the gene co-expression network, which are involved in abiotic and biotic responses, were upregulated in CL flowers. CONCLUSIONS: We proposed an integrative model for transcription regulation of genes in the photoperiod pathway, floral organ development, stress response, and sugar-fatty acid processes to determine CH-CL flower development in V. prionantha. Particularly, under LDs, activated GI may induce genes involved in the stress-response pathways, and then downregulated AP3 and PI or UFO to inhibit the sugar-fatty acid metabolic processes, together forming CL flowers. In contrast, CH flowers were produced under SDs. This work provides novel insights into the developmental evolution of dimorphic flowers in Viola.

Target-induced silver nanocluster generation for highly sensitive electrochemical aptasensor towards cell-secreted interferon-γ.

Interferon-gamma (IFN-γ) is one kind of crucial inflammatory cytokines, and its expression level is closely associated with various disease progressions. This work addresses the development of a sensitive and specific electrochemical assay for detection of IFN-γ by combing the recognition unit of aptamer with the signal reporter of target-induced silver nanoclusters (AgNCs). For biosensor preparation, the gold nanoparticles (AuNPs) immobilized on the amine-terminated electrode surface provided electrochemical interfaces for the self-assembly of C-rich modified aptamers. Then, the aptamer recognized IFN-γ and the free aptamer hybridized with conjugated DNA sequences. After the nuclease-catalyzed cleavage of DNA duplex, in situ-generated AgNCs in the C-rich template was utilized as the electrochemical indicator for IFN-γ detection. The present method demonstrated a good performance for detection of IFN-γ with a low detection limit of 1.7 pg mL-1. This aptasensor was verified to be applied for the evaluation of IFN-γ secreted by cell.

Resveratrol protects human luteinised granulosa cells against hydrogen peroxide-induced oxidative injury through the Sirt1.

Granulosa cells (GCs) control follicular development and are important for female reproduction. Resveratrol (Res) was considered as an antioxidant and Sirt1 inducer. Hydrogen peroxide (H2O2) is the classical reagent to study oxidative stress. The study was conducted to investigate the role of Res against H2O2 in human luteinised granulosa cells (LGCs). The LGCs in the H2O2 group were treated with 100µmol/L H2O2 for 24h. The LGCs in the Res group were treated with 50µmol/L Res for 2h, followed by H2O2. The LGCs in the Sirt1 blockage group were treated with 2.5µmol/L EX527+50µmol/L Res for 2h, followed by H2O2. Results showed that Res significantly increased LGCs viability in H2O2-induced LGCs. The apoptotic rate and ROS in the H2O2 group was higher and the antioxidant enzyme activity was lower compared with other groups. Following the Res, the apoptotic rate and ROS level were reduced and the antioxidant enzyme activity were increased. In the Res blockage group, no significant alterations in the cell apoptosis, ROS and antioxidant enzyme activity were observed compared with the H2O2 group. The Res group had a Caspase-3 downregulation and Sirt1 upregulation compared with the other groups. In conclusion, Res had a protective effect against the H2O2-induced LGCs, and the mechanism may be associated with Sirt1.

Effect of Different Iron Sources on In-Situ Growth of Zeolitic Imidazolate Frameworks-8: For Efficient Oxygen Reduction Electrocatalysts.

Transition metal and nitrogen co-doped carbon-based catalysts (TM-N-C) have become the most promising catalysts for Pt/C due to their wide range of sources, low cost, high catalytic activity, excellent stability and strong resistance to poisoning, especially Fe-N-C metal-organic frameworks (MOFs), which are some of the most promising precursors for the preparation of Fe-N-C catalysts due to their inherent properties, such as their highly ordered three-dimensional framework structure, controlled porosity, and tuneable chemistry. Based on these, in this paper, different iron sources were added to synthesis a sort of zeolitic imidazole frameworks (ZIF-8). Then the imidazole salt in ZIF-8 was rearranged into high N-doped carbon by high-temperature pyrolysis to prepare the Fe-N-C catalyst. We studied the physical characteristics of the catalysts by different iron sources and their effects on the catalytic properties of the oxygen reduction reaction (ORR). From the point of morphology, various iron sources have a positive influence on maintaining the morphology of ZIF-8 polyhedron. Fe-N/C-Fe(NO3)3 has the same anion as zinc nitrate, and can maintain a polyhedral morphology after high-temperature calcination. It had the highest ORR catalytic activity compared to the other four catalyst materials, which proved that there is a certain relationship between morphology and performance. This paper will provide a useful reference and new models for the development of high-performance ORR catalysts without precious metals.

Folic Acid Coordinated Cu-Co Site N-Doped Carbon Nanosheets for Oxygen Reduction Reaction.

The design and development of carbon materials with high-efficiency oxygen reduction activity is still a problem. Folic acid (FA) has unique structural characteristics, and it can provide multiple coordination sites for metal ions. Here, folic acid (FA) was used as a metal complex ligand, and Cu-Co-based N-doped porous carbon nanosheets (Cu-CoNCNs) were synthesized by the solvothermal method, the molten salt template-assisted calcination method, and the chemical etching method. The Cu-CoNCNs synthesized by this method have highly efficient oxygen reduction reaction (ORR) activity. In 0.1 mol/L KOH electrolytes, the catalyst exhibits excellent ORR activity and has a fairly high half-wave potential (0.905 V vs reversible hydrogen electrode (RHE)). X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, infrared spectroscopy, and X-ray diffraction (XRD) were used to investigate the reasons why the catalyst has excellent catalytic activity and long-life stability. It was proved that the impressive ORR activity of Cu-CoNCNs comes from Cu doping, which can regulate the surface electronic structure of the catalyst, thereby optimizing the binding ability between the intermediate and adsorbed species and improving the catalytic activity.

Gibberellins are required for dimorphic flower development in Viola philippica.

Photoperiod is a major determinant of chasmogamous (CH)-cleistogamous (CL) dimorphic flower development in Viola philippica, and only long-day (LD) conditions induce CL flowers. In this study, it was found that the active gibberellin (GA) content in CL floral buds was higher than in CH floral buds formed under short-day (SD) conditions, suggesting that the biosynthesis of active GAs is enhanced by a longer photoperiod and may be associated with dimorphic flower development. Thus, the next step was to molecularly characterize the key V. philippica GA synthesis genes GA 20-oxidase (VpGA20ox) and GA 3-oxidase (VpGA3ox). In terms of the expression of VpGA20ox and VpGA3ox, it was found that the active GAs could be upregulated in developing pistils under both LD and SD conditions to develop functional pistils, and GAs could also accumulate in the stamens under SD conditions. The anthers and the adjacent petals were well developed under SD conditions. In contrast, the above-mentioned floral organs displayed low GA contents under LD conditions and were poorly developed. Although the application of paclobutrazol, an inhibitor of GA synthesis, did not reverse CL development under LD conditions, exogenous GAs could partially trigger the transition from CH to CL flowers under relative SD conditions (≤12 h daylight). This was coupled with the downregulation of B-class MADS-box genes, thereby restraining stamen and petal development. Both VpGA20ox and VpGA3ox exhibited similar expression profiles with B-class MADS-box genes in the development of the stamens and petals. Therefore, in response to photoperiod, GA signaling could affect the expression of B-class homeotic genes and regulate dimorphic flower development in Viola. As a compensation for poorly-developed nectaries, anthers, and petals, filament elongation, style shortness, and inward bending could ensure self-pollination in CL flowers. This work provides new insights into the regulation of CH-CL floral development and the evolutionary significance of the formation of dimorphic flowers.

Molecular cloning, characterization and expression analysis of CbPLDδ gene from Chorispora bungeana in low temperature.

Chorispora bungeana (C. bungeana) is a rare alpine subnival species that is highly tolerant to low temperature stress. Phospholipase D (PLD) is a key enzyme involved in membrane phospholipid catabolism during plant growth and the stress response. In this study, one member of CbPLD gene family, CbPLDδ, was cloned from C. bungeana and was introduced into tobacco. This gene encodes an 864-amino acid protein with two catalytic HxKxxxxD motifs which are essential for phospholipase D activity. After the CbPLDδ gene is fused with the vector containing the GFP tag, subcellular localization showed that CbPLDδ was predominately located in the cell membrane. RT-qPCR and histochemical GUS assays showed that CbPLDδ gene was induced by low temperature and expressed predominantly in leaf and root. Compared with wild-type tobacco, CbPLDδ transgenic tobacco showed higher activities of antioxidant enzymes, and lower levels of malonidiadehyde and electrolyte leakage under low temperature stress. These results reflected that CbPLDδ is involved in the response to low temperature stress, and has the potential to improve the low temperature tolerance of plants.

C2 Alcohol Oxidation Boosted by Trimetallic PtPbBi Hexagonal Nanoplates.

The exploration of ternary Pt-based catalysts represents a new trend for the application of electrocatalysts in fuel cells. In the present study, intermetallic PtPbBi hexagonal nanoplates (HNPs) with a hexagonal close-packed structure have been successfully synthesized via a facile solvothermal synthesis approach. The optimized PtPbBi HNPs exhibited excellent mass activity in the ethanol oxidation reaction (8870 mA mg-1Pt) in an alkaline ethanol solution, which is 12.7 times higher than that of JM Pt/C. Meanwhile, the mass activity of PtPbBi HNPs in an ethylene glycol solution (10,225 mA mg-1Pt) is 1.85 times higher than that of JM Pt/C. In particular, its catalytic activity is better than that of most reported Pt-based catalysts. In addition, the optimized PtPbBi HNPs also show a better operational durability than commercial Pt/C. For the ethylene glycol oxidation reaction, a mass activity of 42.7% was retained even after a chronoamperometric test for 3600 s, which is rare among the reported Pt-based catalysts. By combining X-ray photoelectron spectroscopy and electrochemical characterization, we reveal the electron transfer between Pt, Pb, and Bi; this would lead to weakened CO adsorption and enhanced OH adsorption, thereby promoting the removal of toxic intermediates and ensuring that PtPbBi HNP samples have high activity and excellent stability. This work can inspire the design and synthesis of Pt-based nanocatalysts.

Atomic Dispersion and Surface Enrichment of Palladium in Nitrogen-Doped Porous Carbon Cages Lead to High-Performance Electrocatalytic Reduction of Oxygen.

Metal-nitrogen-carbon (MNC) nanocomposites have been hailed as promising and efficient electrocatalysts toward oxygen reduction reaction (ORR), due to the formation of MNx coordination moieties. However, MNC hybrids are mostly prepared by pyrolysis of organic precursors along with select metal salts, where part of the MNx sites are inevitably buried in the carbon matrix. This limited accessibility compromises the electrocatalytic performance. Herein, we describe a wet-impregnation procedure by facile thermal refluxing, whereby palladium is atomically dispersed and enriched onto the surface of hollow, nitrogen-doped carbon cages (HNC) forming Pd-N coordination bonds. The obtained Pd-HNC nanocomposites exhibit an ORR activity in alkaline media markedly higher than that of metallic Pd nanoparticles, and the best sample even outperforms commercial Pt/C and relevant Pd-based catalysts reported in the literature. The results suggest that atomic dispersion and surface enrichment of palladium in a carbon matrix may serve as an effective strategy in the fabrication of high-performance ORR electrocatalysts.

Alleviation of osmotic stress by H2S is related to regulated PLDα1 and suppressed ROS in Arabidopsis thaliana.

Hydrogen sulfide (H2S) is an important gaseous molecule responding to osmotic stress in plant. Phospholipase Dα1 (PLDα1) and reactive oxygen species (ROS) are involved in many biotic or abiotic stress responses. Using the seedlings of Arabidopsis thaliana ecotype (WT), PLDα1 deficient mutant (pldα1) and the L-cysteine desulfhydrase (L-DEs) deficient mutant (lcd) as materials, the effect of H2S responding to osmotic stress and the functions of PLDα1 and ROS in this response were investigated. The results showed that H2S, PLDα1 and ROS were involved in osmotic stress resistance. Exogenous sodium hydrosulfide (NaHS) promoted the endogenous H2S content and up-regulated the expression of LCD in WT, lcd and plda1. Exogenous phosphatidic acid (PA) enhanced the H2S content and up-regulated the expressions of LCD in WT and plda1 but had no significant effect on the H2S content and LCD expression in lcd under osmotic stress. This suggested that H2S was located downstream of PLDα1 to participate in the osmotic stress signal response. Exogenous NaHS treatment regulated the antioxidant enzymes (SOD, POD, and CAT). The activities and the gene relative expressions of antioxidant enzymes in pldα1 and lcd were higher than those in WT under osmotic stress. This indicated that H2S and PLD regulated the antioxidant enzyme system under osmotic stress. The ROS level, electrolyte leakage (EL), malondialdehyde (MDA) were decreased by NaHS under osmotic stress, demonstrating H2S maintained the membrane integrity. All of these results revealed that H2S alleviated the osmotic stress by elevating PLD and suppressing ROS in A. thaliana.

Nanocomposites Based on Ruthenium Nanoparticles Supported on Cobalt and Nitrogen-Codoped Graphene Nanosheets as Bifunctional Catalysts for Electrochemical Water Splitting.

Rational design and engineering of high-efficiency electrocatalysts toward overall water splitting is crucial for the development of hydrogen energy technology. Herein, a facile procedure is described for the preparation of effective bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), where ruthenium nanoparticles are supported on graphene nanosheets that are codoped with atomic cobalt and nitrogen by controlled pyrolysis of melamine-functionalized graphene oxide and metal ion precursors. The obtained nanocomposites (CoNG/Ru) exhibit a remarkable electrocatalytic activity toward both HER and OER in alkaline media, with a respective overpotential of only -15 and +350 mV to reach the current density of 10 mA cm-2, which is much better than the monometallic counterparts and relevant catalysts in the literature. With CoNG/Ru as bifunctional catalysts for overall water splitting in a two-electrode system, a low potential of 1.58 V is needed to reach the current density of 10 mA cm-2, which is even better than that with commercial Pt/C and RuO2 catalysts. This is ascribed to the synergistic interactions between the metal species by metal-metal charge transfer. These results highlight the significance of exploiting the electronic interactions between metal species in carbon-based nanocomposites to develop bifunctional catalysts for electrochemical energy technologies.

Ethanol Electrooxidation Catalyzed by Tungsten Core@Palladium Shell Nanoparticles.

Bimetallic nanostructures represent effective electrocatalysts toward a number of important reactions. In the present study, carbon-supported palladium-tungsten alloy nanoparticles with a quasi-tungsten core@palladium shell structure (W@Pd/C) were synthesized by a galvanic replacement reaction of amorphous tungsten nanoparticles with Pd(II) at different temperatures (0, 25, and 50 °C), and exhibited apparent electrocatalytic activity toward ethanol oxidation reaction (EOR). When the sample was prepared at 0 °C, large amorphous tungsten nanoparticles were etched off and much smaller W@Pd nanoparticles were formed and dispersed rather evenly on the carbon surface whereas at higher reaction temperatures (25 and 50 °C), the W@Pd nanoparticles became agglomerated. The structures of the obtained samples were characterized by a range of experimental tools, including (scanning) transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical methods. Among the series, the W@Pd/C sample prepared at 0 °C was observed to exhibit the best EOR performance, with a mass activity (9535.5 mA mgPd-1) over three times better than that of commercial Pd/C and markedly enhanced stability.

Nickel Nitride Particles Supported on 2D Activated Graphene-Black Phosphorus Heterostructure: An Efficient Electrocatalyst for the Oxygen Evolution Reaction.

Hydrogen is regarded as the most promising green clean energy in the 21st century. Developing the highly efficient and low-cost electrocatalysts for oxygen evolution reaction (OER) is of great concern for the hydrogen industry. In the water electrolyzed reaction, the overpotential and the kinetics are the main hurdles for OER. Therefore, an efficient and durable oxygen evolution reaction electrocatalyst is required. In this study, an activated graphene (AG)-black phosphorus (BP) nanosheets hybrid is fabricated for supporting Ni3 N particles (Ni3 N/BP-AG) in the application of OER. The Ni3 N particles are combined with the BP-AG heterostructure via facile mechanical ball milling under argon protection. The synthesized Ni3 N/BP-AG shows excellent catalytic performance toward the OER, demanding the overpotential of 233 mV for a current density of 10 mA cm-2 with a Tafel slope of 42 mV dec-1 . The Ni3 N/BP-AG catalysts also show remarkable stability with a retention rate of the current density of about 86.4% after measuring for 10 000 s in potentiostatic mode.

Various Morphology of WO3 Modified Activated Carbon Supported Pd Catalysts with Enhanced Formic Acid Electrooxidation.

Activated carbon support Pd nanoparticles (NPs) modified by various WO3-shaped catalysts were prepared and applied as an efficient anode catalyst for direct formic acid fuel cells. Three forms of WO3 (nanosheets, nanoparticles, nanobars) modified activated carbon hybrids were first prepared via different syntheses, and then used as supports to synthesize three types of Pd-WO3/C catalysts by a NaBH4 reduction method. The morphology, structure, and electrochemical performances of the as-prepared Pd-WO3/C catalysts were characterized and analyzed. We can see that the noble metal particles loaded with activated carbon modified by WO3 exhibit small particle size and uniform dispersion from the transmission electron microscope image. The synthesized composite catalysts was used for the formic acid electrooxidation and showed excellent catalytic performance. The oxidation peak current density of the Pd/WO3-Nanosheets/C (40.04 mA·cm-2 was the highest, approximately 1.2 times that of Pd/C (33.00 mA·cm-2. Additionally, the long-term stability (i-t) test results show that the Pd/WO3-Nanosheets/C catalyst exhibits superior stability during formic acid electrooxidation. The reason for the increase in performance can be attributed to the following: the large specific surface area of WO3 decreases the adsorption strength of intermediates such as COad on Pd and prevents the accumulation of poisonous intermediates, thereby promoting the oxidation reaction of formic acid in the direct pathway; the catalyst-support interaction between precious metal Pd and WO3, substantially improving the catalytic performance of Pd-WO3/C catalysts.

Urbanization threaten the pollination of Gentiana dahurica.

With rapid spread of the urbanization, many environmental factors, such as climate, soil pH and nutrients have been changed. However, the plant pollination affected by urbanization was seldom conducted. Here, we studied the flower visitation rates, seed production, pollen limitation and flower morphological characters of Gentiana dahurica at 3 populations along an urban-peri-urban gradient around Xi'ning over 4 consecutive years, aiming to test the effects of urbanization on plant pollination service. Our results showed that the pollinator visit frequencies, interannual stability of pollinator assemblages and visit frequencies declined with the intensification of urbanization. As urbanization intensified, plant borne more flowers and the flower morphological sizes became "longer" (the length of flowers, filaments and styles were increased, but the width of flowers kept stable at the 3 populations); the flower duration, especially the female phase duration prolonged. The seed-set ratio of G. dahurica in natural condition decreased and more severe pollen limitation occurred in more urbanized populations. Also, an interannual variation of seed-set ratio and index of pollen limitation (IPL), which related with the variation of pollinator visit frequencies, were found in this study. These results suggest that the pollination service can be threatened by urbanization over a long-time interval for G. dahurica. This finding highlights the importance of pollinator affections acting on plant pollination system. Additionally, as pollinator assemblages and visit frequencies interannually changed, a long-time scale observation is needed to understand the plant-pollinator relationships.