Unlocking Efficient Alkaline Hydrogen Evolution Through Ru-Sn Dual Metal Sites and a Novel Hydroxyl Spillover Effect.

Alkaline hydrogen evolution reaction (HER) has great potential in practical hydrogen production but is still limited by the lack of active and stable electrocatalysts. Herein, the efficient water dissociation process, fast transfer of adsorbed hydroxyl and optimized hydrogen adsorption are first achieved on a cooperative electrocatalyst, named as Ru-Sn/SnO2 NS, in which the Ru-Sn dual metal sites and SnO2 heterojunction are constructed based on porous Ru nanosheet. The density functional theory (DFT) calculations and in situ infrared spectra suggest that Ru-Sn dual sites can optimize the water dissociation process and hydrogen adsorption, while the existence of SnO2 can induce the unique hydroxyl spillover effect, accelerating the hydroxyl transfer process and avoiding the poison of active sites. As results, Ru-Sn/SnO2 NS display remarkable alkaline HER performance with an extremely low overpotential (12 mV at 10 mA cm-2) and robust stability (650 h), much superior to those of Ru NS (27 mV at 10 mA cm-2 with 90 h stability) and Ru-Sn NS (16 mV at 10 mA cm-2 with 120 h stability). The work sheds new light on designing of efficient alkaline HER electrocatalyst.

Reversed Charge Transfer and Enhanced Hydrogen Spillover in Platinum Nanoclusters Anchored on Titanium Oxide with Rich Oxygen Vacancies Boost Hydrogen Evolution Reaction.

The catalytic activity of metal clusters is closely related with the support; however, knowledge on the influence of the support on the catalytic activity is scarce. We demonstrate that Pt nanoclusters (NCs) anchored on porous TiO2 nanosheets with rich oxygen vacancies (VO -rich Pt/TiO2 ) and deficient oxygen vacancies (VO -deficient Pt/TiO2 ), display significantly different catalytic activity for the hydrogen evolution reaction (HER), in which VO -rich Pt/TiO2 shows a mass activity of 45.28 A mgPt -1 at -0.1 V vs. RHE, which is 16.7 and 58.8 times higher than those of VO -deficient Pt/TiO2 and commercial Pt/C, respectively. DFT calculations and in situ Raman spectra suggest that porous TiO2 with rich oxygen vacancies can simultaneously achieve reversed charge transfer (electrons transfer from TiO2 to Pt NCs) and enhanced hydrogen spillover from Pt NCs to the TiO2 support, which leads to electron-rich Pt NCs being amenable to proton reduction of absorbed H*, as well as the acceleration of hydrogen desorption at Pt catalytic sites-both promoting the HER. Our work provides a new strategy for rational design of highly efficient HER catalysts.

A Network Pharmacology Study to Uncover the Multiple Molecular Mechanism of the Chinese Patent Medicine Toujiequwen Granules in the Treatment of Corona Virus Disease 2019 (COVID-19).

Since the outbreak of the novel corona virus disease 2019 (COVID-19) at the end of 2019, specific antiviral drugs have been lacking. A Chinese patent medicine Toujiequwen granules has been promoted in the treatment of COVID-19. The present study was designed to reveal the molecular mechanism of Toujiequwen granules against COVID-19. A network pharmacological method was applied to screen the main active ingredients of Toujiequwen granules. Network analysis of 149 active ingredients and 330 drug targets showed the most active ingredient interacting with many drug targets is quercetin. Drug targets most affected by the active ingredients were PTGS2, PTGS1, and DPP4. Drug target disease enrichment analysis showed drug targets were significantly enriched in cardiovascular diseases and digestive tract diseases. An "active ingredient-target-disease" network showed that 57 active ingredients from Toujiequwen granules interacted with 15 key targets of COVID-19. There were 53 ingredients that could act on DPP4, suggesting that DPP4 may become a potential new key target for the treatment of COVID-19. GO analysis results showed that key targets were mainly enriched in the cellular response to lipopolysaccharide, cytokine activity and other functions. KEGG analysis showed they were mainly concentrated in viral protein interaction with cytokine and cytokine receptors and endocrine resistance pathway. The evidence suggests that Toujiequwen granules might play an effective role by improving the symptoms of underlying diseases in patients with COVID-19 and multi-target interventions against multiple signaling pathways related to the pathogenesis of COVID-19.

Decorating graphdiyne on ultrathin bismuth subcarbonate nanosheets to promote CO2 electroreduction to formate.

Electrocatalytic reduction of CO2 is one of the most attractive approaches for converting CO2 into valuable chemical feedstocks and fuels. This work reports a catalyst comprising graphdiyne-decorated bismuth subcarbonate (denoted as BOC@GDY) for efficient electroreduction of CO2 to formate. The BOC@GDY shows a stable current density of 200 mA cm-2 at -1.1 V in a flow cell configuration, with a faradaic efficiency of 93.5% for formate. Experimental results show that the synergistic effect in BOC@GDY is beneficial for the CO2 adsorption affinity, the reaction kinetics and the selectivity for formate. In addition, in-situ X-ray absorption and Raman spectroscopy indicate that the electron-rich GDY could facilitate the reduction from Bi(III) to Bi(0), thus leading to more active sites. We also demonstrate that the promoting effect of GDY in CO2 electroreduction can be further extended to other metal catalysts. To the best of our knowledge, such general promoting functions of GDY for CO2 electroreduction have not been documented thus far.

Controlled Synthesis of a Vacancy-Defect Single-Atom Catalyst for Boosting CO2 Electroreduction.

The reaction of precursors containing both nitrogen and oxygen atoms with NiII under 500 °C can generate a N/O mixing coordinated Ni-N3 O single-atom catalyst (SAC) in which the oxygen atom can be gradually removed under high temperature due to the weaker Ni-O interaction, resulting in a vacancy-defect Ni-N3 -V SAC at Ni site under 800 °C. For the reaction of NiII with the precursor simply containing nitrogen atoms, only a no-vacancy-defect Ni-N4 SAC was obtained. Experimental and DFT calculations reveal that the presence of a vacancy-defect in Ni-N3 -V SAC can dramatically boost the electrocatalytic activity for CO2 reduction, with extremely high CO2 reduction current density of 65 mA cm-2 and high Faradaic efficiency over 90 % at -0.9 V vs. RHE, as well as a record high turnover frequency of 1.35×105  h-1 , much higher than those of Ni-N4 SAC, and being one of the best reported electrocatalysts for CO2 -to-CO conversion to date.

In Situ Synthesis of CdS/Graphdiyne Heterojunction for Enhanced Photocatalytic Activity of Hydrogen Production.

Hydrogen production through artificial photosynthesis has been regarded as a promising strategy for dealing with energy shortage and environmental problems. In this work, graphdiyne (GD) was first introduced to the visible-light catalytic system for hydrogen production, in which a CdS/GD heterojunction was prepared through a simple in situ growth process by adding Cd(AcO)2 into a dimethyl sulfoxide (DMSO) solution containing GD substrate. The as-prepared CdS/GD heterojunction exhibits much higher performance for photocatalytic hydrogen evolution compared to that of pristine GD and CdS nanoparticles. The photocatalytic performance of CdS/GD heterostructure containing 2.5 wt % of GD (GD2.5) is 2.6 times higher than that of the pristine CdS nanoparticles. The enhanced catalytic performance can be ascribed to the formation of CdS/GD heterojunction, in which the presence of GD can not only stabilize CdS nanoparticles by preventing the agglomeration of CdS nanoparticles but also act as a photogenerated hole transfer material for efficiently separating photogenerated electron-hole pairs in CdS. Accordingly, this work provides the potential of GD-derived materials for solar energy conversion and storage.

Engineering the Coordination Environment of Single-Atom Platinum Anchored on Graphdiyne for Optimizing Electrocatalytic Hydrogen Evolution.

Two Pt single-atom catalysts (SACs) of Pt-GDY1 and Pt-GDY2 were prepared on graphdiyne (GDY)supports. The isolated Pt atoms are dispersed on GDY through the coordination interactions between Pt atoms and alkynyl C atoms in GDY, with the formation of five-coordinated C1 -Pt-Cl4 species in Pt-GDY1 and four-coordinated C2 -Pt-Cl2 species in Pt-GDY2. Pt-GDY2 shows exceptionally high catalytic activity for the hydrogen evolution reaction (HER), with a mass activity up to 3.3 and 26.9 times more active than Pt-GDY1 and the state-of-the-art commercial Pt/C catalysts, respectively. Pt-GDY2 possesses higher total unoccupied density of states of Pt 5d orbital and close to zero value of Gibbs free energy of the hydrogen adsorption (|ΔGPtH* |) at the Pt active sites, which are responsible for its excellent catalytic performance. This work can help better understand the structure-catalytic activity relationship in Pt SACs.

ANAPHASE PROMOTING COMPLEX/CYCLOSOME-mediated cyclin B1 degradation is critical for cell cycle synchronization in syncytial endosperms.

Although it is known that in most angiosperms mitosis in early endosperm development is syncytial and synchronized, it is unclear how the synchronization is regulated. We showed previously that APC11, also named ZYG1, in Arabidopsis activates zygote division by interaction and degradation of cyclin B1. Here, we report that the mutation in APC11/ZYG1 led to unsynchronized mitosis and over-accumulation of cyclin B1-GUS in the endosperm. Mutations in two other APC subunits showed similar defects. Transgenic expression of stable cyclin B1 in the endosperm also caused unsynchronized mitosis. Further, downregulation of APC11 generated multi-nucleate somatic cells with unsynchronized mitotic division. Together, our results suggest that APC/C-mediated cyclin B1 degradation is critical for cell cycle synchronization.

The anaphase-promoting complex initiates zygote division in Arabidopsis through degradation of cyclin B1.

As the start of a new life cycle, activation of the first division of the zygote is a critical event in both plants and animals. Because the zygote in plants is difficult to access, our understanding of how this process is achieved remains poor. Here we report genetic and cell biological analyses of the zygote-arrest 1 (zyg1) mutant in Arabidopsis, which showed zygote-lethal and over-accumulation of cyclin B1 D-box-GUS in ovules. Map-based cloning showed that ZYG1 encodes the anaphase-promoting complex/cyclosome (APC/C) subunit 11 (APC11). Live-cell imaging studies showed that APC11 is expressed in both egg and sperm cells, in zygotes and during early embryogenesis. Using a GFP-APC11 fusion construct that fully complements zyg1, we showed that GFP-APC11 expression persisted throughout the mitotic cell cycle, and localized to cell plates during cytokinesis. Expression of non-degradable cyclin B1 in the zygote, or mutations of either APC1 or APC4, also led to a zyg1-like phenotype. Biochemical studies showed that APC11 has self-ubiquitination activity and is able to ubiquitinate cyclin B1 and promote degradation of cyclin B1. These results together suggest that APC/C-mediated degradation of cyclin B1 in Arabidopsis is critical for initiating the first division of the zygote.

RNAi knockdown of acetyl-CoA carboxylase gene eliminates jinggangmycin-enhanced reproduction and population growth in the brown planthopper, Nilaparvata lugens.

A major challenge in ecology lies in understanding the coexistence of intraguild species, well documented at the organismal level, but not at the molecular level. This study focused on the effects of the antibiotic, jinggangmycin (JGM), a fungicide widely used in Asian rice agroecosystems, on reproduction of insects within the planthopper guild, including the brown planthopper (BPH) Nilaparvata lugens and the white-backed planthopper (WBPH) Sogatella furcifera, both serious resurgence rice pests. JGM exposure significantly increased BPH fecundity and population growth, but suppressed both parameters in laboratory and field WBPH populations. We used digital gene expression and transcriptomic analyses to identify a panel of differentially expressed genes, including a set of up-regulated genes in JGM-treated BPH, which were down-regulated in JGM-treated WBPH. RNAi silencing of Acetyl Co-A carboxylase (ACC), highly expressed in JGM-treated BPH, reduced ACC expression (by > 60%) and eliminated JGM-induced fecundity increases in BPH. These findings support our hypothesis that differences in ACC expression separates intraguild species at the molecular level.

Silencing a sugar transporter gene reduces growth and fecundity in the brown planthopper, Nilaparvata lugens (Stål) (Hemiptera: Delphacidae).

The brown planthopper (BPH), Nilaparvata lugens, sugar transporter gene 6 (Nlst6) is a facilitative glucose/fructose transporter (often called a passive carrier) expressed in midgut that mediates sugar transport from the midgut lumen to hemolymph. The influence of down regulating expression of sugar transporter genes on insect growth, development, and fecundity is unknown. Nonetheless, it is reasonable to suspect that transporter-mediated uptake of dietary sugar is essential to the biology of phloem-feeding insects. Based on this reasoning, we posed the hypothesis that silencing, or reducing expression, of a BPH sugar transporter gene would be deleterious to the insects. To test our hypothesis, we examined the effects of Nlst6 knockdown on BPH biology. Reducing expression of Nlst6 led to profound effects on BPHs. It significantly prolonged the pre-oviposition period, shortened the oviposition period, decreased the number of eggs deposited and reduced body weight, compared to controls. Nlst6 knockdown also significantly decreased fat body and ovarian (particularly vitellogenin) protein content as well as vitellogenin gene expression. Experimental BPHs accumulated less fat body glucose compared to controls. We infer that Nlst6 acts in BPH growth and fecundity, and has potential as a novel target gene for control of phloem-feeding pest insects.

Effects of two pesticides, TZP and JGM, on reproduction of three planthopper species, Nilaparvata lugens Stål, Sogatella furcifera Horvath, and Laodelphax striatella Fallén.

Three planthopper species, the brown planthopper (BPH), Nilaparvata lugens Stål, the white-backed planthopper (WBPH), Sogatella furcifera Horvath, and the small brown planthopper (SBPH), Laodelphax striatella Fallén, often co-occur in rice grown regions of China. The present investigation examined effects of two pesticides, triazophos (TZP) and jinggangmycin (JGM) (a fungicide), on reproduction of BPH, WBPH, and SBPH. The results showed that TZP stimulated the fecundity of the three planthopper species. Interestingly, JGM stimulated the fecundity of BPH but suppressed the fecundity of WBPH. In addition, TZP and JGM had a significant effect on the preoviposition period (PVD), the oviposition period (OPD), and the longevity of adult females (LAF) of BPH and WBPH. Based on these findings, to avoid resurgence occurrence of planthoppers, we suggest that the application of TZP should be banned in rice fields, that JGM should be used to control rice sheath blight at the early growth stages of rice (with WBPH occurrence and without BPH occurrence).

Comparisons of topical and spray applications of two pesticides, triazophos and jinggangmycin, on the protein content in the ovaries and fat bodies of the brown planthopper Nilaparvata lugens Stål (Hemiptera:Delphacidae).

The pesticide-induced stimulation of reproduction in pests is one of the most important mechanisms of pest resurgence. There have been numerous reports on the insecticide-induced stimulation of reproduction. However, the relationship between pesticide application method and pest resurgence (stimulation of reproduction) has received little attention. Here, we studied the effect of two treatment methods, triazophos (TZP) and jinggangmycin (JGM), on the protein content in the ovaries and fat bodies of the brown planthopper (BPH) Nilaparvata lugens Stål. The results showed that pesticide treatment methods significantly affected the protein content in the ovaries and fat bodies of BPH. In addition, grand means (means of main effect) of the protein content at 2 and 3 days after emergence (2 and 3 DAE) for foliar sprays was significantly higher than that observed after topical treatments, which increased by 23.9% (from 1.42 to 1.76) and 8.82% (from 4.42 to 4.81), respectively. No significant differences on the protein content in the ovaries and fat bodies for the JGM topical treatment were observed compared with controls. However, the protein content for JGM foliar sprays was significantly higher than that for the controls. The protein contents in both topical and spray treatments of TZP were significantly higher than those of the controls. Ovarian protein is mainly yolk protein. There is a positive correlation between ovarian protein content and the number of eggs laid. These findings show that foliar spray of the pesticides promotes the resurgence of BPH. Therefore, the foliar spray of some pesticides, such as JGM, should be avoided for the control of pests, which is the sideeffects of the fungicide on non-target insect pests' occurrence.

NF-κB induces abnormal centrosome amplification by upregulation of CDK2 in laryngeal squamous cell cancer.

Centrosome amplification can drive chromosomal instability (CIN) which is a major source of tumor initiation. The present study aimed to investigate the impact of nuclear factor kappa B (NF-κB) on centrosome amplification of Hep-2 cells. Immunofluorescence was performed to display centrosomes. BAY11-7082 was used as an inhibitor of NF-κB to assess the inhibition of centrosome amplification, and cyclin-dependent kinase 2 (CDK2), ensuring cell cycle cycle coordination with centrosome cycle was detected by Western blotting. Furthermore, a 1556-bp fragment of the CDK2 promoter was analyzed using the TRANSFAC-TESS software. Luciferase assay, including a series of truncated CDK2 promoters and site mutations, was carried out to determine NF-κB binding sites in the CDK2 promoter. Electrophoresis mobility shift and chromatin immunoprecipitation assays were applied to confirm whether NF-κB indeed binds to the 5'-promoter region of the CDK2 gene. To reveal the clinical significance of CDK2 expression in laryngeal squamous cell cancer, mRNA and protein levels were assessed by RT-PCR and Western blotting, respectively. We found that the transcription factor NF-κB plays a role in centrosome amplification in Hep-2 cells. Centrosome amplification is reduced by inhibition of the NF-κB pathway. Moreover, expression of the p65 subunit of NF-κB is sufficient to promote centrosome amplification and increase in CDK2 protein levels. We further identified a functional NF-κB binding site located in the CDK2 promoter. Single mutation of the NF-κB site III (construct mutIII) however resulted in 76±5% (p<0.01) luciferase activity reduction. Electromobility shift assays and chromatin immunoprecipitaton results suggest that NF-κB indeed binds to this responsive element associating with CDK2 expression and centrosome amplification. RT-PCR and Western blotting results revealed that both mRNA and protein levels of CDK2 were significantly higher in tumor tissues than those in paired adjacent normal laryngeal tissues.