Defect Engineering Simultaneously Regulating Exciton Dissociation in Carbon Nitride and Local Electron Density in Pt Single Atoms Toward Highly Efficient Photocatalytic Hydrogen Production.

The high exciton binding energy (Eb) and sluggish surface reaction kinetics have severely limited the photocatalytic hydrogen production activity of carbon nitride (CN). Herein, a hybrid system consisting of nitrogen defects and Pt single atoms is constructed through a facile self-assembly and photodeposition strategy. Due to the acceleration of exciton dissociation and regulation of local electron density of Pt single atoms along with the introduction of nitrogen defects, the optimized Pt-MCT-3 exhibits a hydrogen production rate of 172.0 µmol h-1 (λ ≥ 420 nm), ≈41 times higher than pristine CN. The apparent quantum yield for the hydrogen production is determined to be 27.1% at 420 nm. The experimental characterizations and theoretical calculations demonstrate that the nitrogen defects act as the electron traps for the exciton dissociation, resulting in a decrease of Eb from 86.92 to 43.20 meV. Simultaneously, the stronger interaction between neighboring nitrogen defects and Pt single atoms directionally drives free electrons to aggregate around Pt single atoms, and tailors the d-band electrons of Pt, forming a moderate binding strength between Pt atoms and H* intermediates.

An Interface-cascading Silicon Photoanode with Strengthened Built-in Electric Field and Enriched Surface Oxygen Vacancies for Efficient Photoelectrochemical Water Splitting.

To promote interfacial charge transfer process and accelerate surface water oxidation reaction kinetics for photoelectrochemical (PEC) water splitting over n-type Silicon (n-Si) based photoanodes, herein, starting with surface stabilized n-Si/CoOx , a NiOx /NiFeOOH composite overlayer was coated by atomic layer deposition and spray coating to fabricate the multilayer structured n-Si/CoOx /NiOx /NiFeOOH photoanode. Encouragingly, the obtained n-Si/CoOx /NiOx /NiFeOOH photoanode exhibits much increased PEC activity for water splitting, with onset potential cathodically shifted to ~0.96 V vs. RHE and photocurrent density increased to 22.6 mA cm-2 at 1.23 V vs. RHE for OER, as compared to n-Si/CoOx , even significantly surpassing the counterpart n-Si/CoOx /NiOx /FeOOH and n-Si/CoOx /NiOx /NiOOH photoanodes. Photophysical and electrochemical characterizations evidence that the deposited CoOx /NiOx /NiFeOOH composite overlayer would create large band bending and strong built-in electric field at the introduced cascading interfaces, thereby producing a large photovoltage of 650 mV to efficiently accelerate charge transfer from the n-Si substrate to the electrolyte for water oxidation. Furthermore, the surface oxygen vacancy enriched NiFeOOH overlayer could effectively catalyze the water oxidation reaction by thermodynamically reducing the energy barrier of rate determining step for OER.

Primary mucinous adenocarcinoma of the urethra: A clinicopathological analysis of 35 cases.

AIM: Primary mucinous adenocarcinoma of the urethra represents an extremely rare entity. We sought to characterise further these tumours' clinicopathological, immunohistochemical and molecular features. METHODS AND RESULTS: Thirty-five cases were identified, occurring in 18 males and 17 females. The mean age at diagnosis was 65 years (28-89 years). The main presentation symptoms were haematuria and urinary outlet obstruction. Microscopic analysis revealed that all 35 tumours have stromal dissection by mucin. Ten tumours showed villoglandular dysplasia, nine showed mucinous metaplasia, two showed adenocarcinoma in situ and four showed signet ring cell features. All tumours were immunopositive for CEA, while immunonegative for nuclear ß-catenin; 19 of 23 (83%) expressed high molecular weight cytokeratin; 19 of 33 (58%) CK7; 28 of 34 (82%) CK20; 32 of 35 (91%) CDX2; 22 of 27 (81%) cadherin-17 (CDH-17); 26 of 29 (90%) SATB2; and one of 31 (3%) GATA3. Mismatch repair gene products, including MLH1, PMS2, MSH2 and MSH6, were immunopositive, suggesting the MSI-low genotype of mucinous adenocarcinoma of the urethra. BRAF V600E and ALK rearrangements were not detected. During the mean follow-up of 20 months, nine patients either developed distant metastasis or succumbed to the illness. CONCLUSION: Our study, encompassing the most extensive series of 35 cases of primary mucinous adenocarcinoma of the urethra, provides crucial insights into its precise diagnosis, management and potential targeted treatments. We found a greater CDX2, SATB2 and CDH17 sensitivity in these urethral tumours for the first time, to our knowledge. We identified characteristics such as an MSI-low profile, non-V600E BRAF mutations and an absence of ALK rearrangements.

Surface Adsorbed Hydroxyl: A Double-Edged Sword in Electrochemical CO2 Reduction over Oxide-Derived Copper.

Oxide-derived Cu (OD-Cu) featured with surface located sub-20 nm nanoparticles (NPs) created via surface structure reconstruction was developed for electrochemical CO2 reduction (ECO2 RR). With surface adsorbed hydroxyls (OHad ) identified during ECO2 RR, it is realized that OHad , sterically confined and adsorbed at OD-Cu by surface located sub-20 nm NPs, should be determinative to the multi-carbon (C2 ) product selectivity. In situ spectral investigations and theoretical calculations reveal that OHad favors the adsorption of low-frequency *CO with weak C≡O bonds and strengthens the *CO binding at OD-Cu surface, promoting *CO dimerization and then selective C2 production. However, excessive OHad would inhibit selective C2 production by occupying active sites and facilitating competitive H2 evolution. In a flow cell, stable C2 production with high selectivity of ∼60 % at -200 mA cm-2 could be achieved over OD-Cu, with adsorption of OHad well steered in the fast flowing electrolyte.

Decrypting the Controlled Product Selectivity over Ag-Cu Bimetallic Surface Alloys for Electrochemical CO2 Reduction.

Electrochemical CO2 reduction reaction (ECO2 RR) with controlled product selectivity is realized on Ag-Cu bimetallic surface alloys, with high selectivity towards C2 hydrocarbons/alcohols (≈60 % faradaic efficiency, FE), C1 hydrocarbons/alcohols (≈41 % FE) and CO (≈74 % FE) achieved by tuning surface compositions and applied potentials. In situ spectral investigations and theoretical calculations reveal that surface-composition-dependent d-band center could tune *CO binding strengths, regulating the *CO subsequent reaction pathways and then the product selectivity. Further adjusting the applied potentials will alter the energy of participated electrons, which leads to controlled ECO2 RR selectivity towards desired products. A predominant region map, with an indicator proposed to evaluate the thermodynamic predominance of the *CO subsequent reactions, is then provided as a reliable theoretical guidance for the controllable ECO2 RR product selectivity over bimetallic alloys.

LC3 and NLRC5 interaction inhibits NLRC5-mediated MHC class I antigen presentation pathway in endometrial cancer.

The major histocompatibility complex class I (MHC-I) transactivator, nucleotide binding oligomerization domain-like receptor family caspase recruitment domain containing 5 (NLRC5), serves as a target for immune evasion in many cancers, including endometrial cancer (EC). An inhibition of autophagy can contribute to immunotherapy by assisting the MHC-I-mediated antigen presentation in cancer. However, the underlying mechanism for autophagy-regulated MHC-I in EC remains unclear. In this study, we found that autophagy was upregulated in EC tissues when compared to that in normal endometrial tissues. MHC I and NLRC5 expressions were lower in EC endometrium than in normal endometrium. Autophagy inhibited the MHC-I genes expression in vitro. Furthermore, a negative correlation was found between NLRC5 and LC3 levels, and LC3 interacted with NLRC5 to inhibit NLRC5-mediated MHC-I antigen presentation pathway in vitro and in vivo. Thus, our findings demonstrated that an upregulation of LC3 in EC patients may contribute to tumor immune escape by restricting the NLRC5-mediated MHC-I antigen presentation pathway, signifying inhibiting LC3 and promoting NLRC5 may be a promising immunotherapy strategy in the management of EC.

Chrysin induces autophagy through the inactivation of the ROS­mediated Akt/mTOR signaling pathway in endometrial cancer.

Endometrial cancer (EC) is widely known as an aggressive malignancy. Due to the limited therapeutic options and poor prognosis of patients with advanced­stage EC, there is a need to identify effective alternative treatments. Chrysin is a naturally active flavonoid (5,7­dihydroxyflavone), which has been demonstrated to exert anticancer effects and may present a novel strategy for EC treatment. However, the role of chrysin in EC remains largely unclear. The aim of the present study was to examine the anticancer effects of chrysin on EC. The results revealed that, in addition to apoptosis, chrysin increased the LC3II expression levels and markedly accelerated the autophagic flux, suggesting that chrysin induced both the autophagy and apoptosis of EC cells. Furthermore, the inhibition of autophagy by chloroquine enhanced the inhibitory effect on cell proliferation and the promotion of the chrysin­induced apoptosis of EC cells, indicating that chrysin­induced autophagy was a cytoprotective mechanism. Additionally, chrysin led to the production of intracellular reactive oxygen species (ROS). N­acetylcysteine (NAC) pretreatment significantly inhibited chrysin­induced autophagy, suggesting that ROS activated autophagy induced by chrysin in EC cells. Furthermore, the phosphorylated (p­)Akt and p­mTOR levels were significantly decreased in a concentration­dependent manner following treatment with chrysin, while NAC blocked these effects. Taken together, these findings demonstrated that chrysin­induced autophagy via the inactivation of the ROS­mediated Akt/mTOR signaling pathway in EC cells.

Circular RNAs: Novel biomarkers for cervical, ovarian and endometrial cancer (Review).

Cervical, ovarian and endometrial cancer are the three most common types of malignant tumor and the leading causes of cancer­associated death in women. Tumor debulking surgery followed by platinum and paclitaxel chemotherapy is the current treatment regime of choice. However, as a result of late diagnosis and chemoresistance, the survival rates of patients with advanced gynecological cancers remains unsatisfactory. Circular RNAs (circRNAs) are stable noncoding RNAs that are present in a wide variety of tissue and cell types. With the enhancement of RNA sequencing methods, increasing numbers of circRNAs have been identified, and their functions are gradually being revealed. In recent years, circRNAs have received increasing attention for their regulatory roles in cervical, ovarian and endometrial cancer. The aim of the present review was to summarize the possible mechanisms of recently identified circRNAs; we hypothesize that a novel diagnostic and therapeutic biomarker may be identified to prolong the survival time of patients with gynecological malignancies.

Potential relationship between Sirt3 and autophagy in ovarian cancer.

Sirtuin 3 (Sirt3) is an important member of the sirtuin protein family. It is a deacetylase that was previously reported to modulate the level of reactive oxygen species (ROS) production and limit the extent of oxidative damage in cellular components. As an important member of the class III type of histone deacetylases, Sirt3 has also been documented to mediate nuclear gene expression, metabolic control, neuroprotection, cell cycle and proliferation. In ovarian cancer (OC), Sirt3 has been reported to regulate cellular metabolism, apoptosis and autophagy. Sirt3 can regulate autophagy through a variety of different molecular signaling pathways, including the p62, 5'AMP-activated protein kinase and mitochondrial ROS-superoxide dismutase pathways. However, autophagy downstream of Sirt3 and its association with OC remains poorly understood. In the present review, the known characteristics of Sirt3 and autophagy were outlined, and their potential functional roles were discussed. Following a comprehensive analysis of the current literature, Sirt3 and autophagy may either serve positive or negative roles in the regulation of OC. Therefore, it is important to identify the appropriate expression level of Sirt3 to control the activation of autophagy in OC cells. This strategy may prove to be a novel therapeutic method to reduce the mortality of patients with OC. Finally, potential research directions into the association between Sirt3 and other signaling pathways were provided.

NLRC5 promotes cell migration and invasion by activating the PI3K/AKT signaling pathway in endometrial cancer.

OBJECTIVE: NOD-like receptor family caspase recruitment domain family domain-containing 5 (NLRC5) is involved in the development of cancer. Our objective was to explore the role of NLRC5 in the progression of endometrial cancer (EC). METHODS: The roles of NLRC5 in migration and invasion of AN3CA EC cells were examined by cell wound-healing assay, Transwell migration, and invasion analysis. Overexpression of NLRC5 was achieved with NLRC5 plasmid, and knockdown of NLRC5 was achieved using small interfering (si)RNA-NLRC5 in AN3CA cells. The expression of NLRC5 was detected by immunohistochemical, western blot, and quantitative real-time PCR. LY294002 was used to inhibit the phosphatidylinositol 3-kinase (PI3K)/AKT signaling pathway. RESULTS: NLRC5 was downregulated in EC tissue compared with normal endometrium. Overexpression of NLRC5 led to upregulation of cell migration and invasion in AN3CA cells and expression of matrix metallopeptidase (MMP)-9. Inhibition of NLRC5 restricted migration and invasion of AN3CA cells and expression of MMP9. Overexpression of NLRC5 promoted the activation of PI3K/AKT signaling pathway. Inhibiting PI3K/AKT signaling pathway by using LY294002 blocked the positive role of NLRC5 in migration and invasion of AN3CA cells and expression of MMP9. CONCLUSIONS: These results demonstrate that NLRC5 promotes EC progression by activating the PI3K/AKT signaling pathway.

An Overview and Future Perspectives of Rechargeable Zinc Batteries.

Aqueous rechargeable zinc-based batteries have sparked a lot of enthusiasm in the energy storage field recently due to their inherent safety, low cost, and environmental friendliness. Although remarkable progress has been made in the exploration of performance so far, there are still many challenges such as low working voltage and dissolution of electrode materials at the material and system level. Herein, the central tenet is to establish a systematic summary for the construction and mechanism of different aqueous zinc-based batteries. Details for three major zinc-based battery systems, including alkaline rechargeable Zn-based batteries (ARZBs), aqueous Zn ion batteries (AZIBs), and dual-ion hybrid Zn batteries (DHZBs) are given. First, the electrode materials and energy storage mechanism of the three types of zinc-based batteries are discussed to provide universal guidance for these batteries. Then, the electrode behavior of zinc anodes and strategies to deal with problems such as dendrite and passivation are recommended. Finally, some challenge-oriented solutions are provided to facilitate the next development of zinc-based batteries. Combining the characteristics of zinc-based batteries with good use of concepts and ideas from other disciplines will surely pave the way for its commercialization.

Ionic liquid assisted electrochemical coating zinc nanoparticles on carbon cloth as lithium dendrite suppressing host.

The application of lithium metal anode with high specific capacity and energy density is limited by the volume expansion and pulverization caused by dendrite growth during cycle process. We propose a composite lithium anode by immersing molten lithium on the flexible three-dimensional (3D) carbon cloth scaffold with the zinc nanoparticles. The lithiophilic zinc nanoparticles layer of framework is synthesized by fast and easy electrochemical deposition from ionic liquid avoiding high temperature, high pressure and toxic reagent. The lithium is infused into the 3D lithiophilic framework, the composite anode is obtained. The steady network structure can confine the lithium and lead to Li dendrite restraining and reducing volume change due to the low interfacial resistance and reduce the effective current density, which induced the homogeneous Li growth. Benefiting from this, the Li infused 3D carbon cloth-Zn symmetric battery exhibits a low stripping/plating overpotential (~30 mV) and can be stable over 900 h at 1 mA cm-2. The Li//LiFePO4 battery delivers higher reversible capacity (140 mAh g-1 at 2 C and 120 mAh g-1 at 5 C) and stable cycling for 1500 and 2000 cycles than bare Li.