Vanadium-Containing Keggin-Type Polyoxometalates, [VM12O40]3- and [VVM11O40]4- (M = Mo, W): Structural Characterization and Voltammetric, NMR, and EPR Studies Related to Electrochemical Reduction at Framework and Central Vanadium Sites.

Vanadium is accommodated in both the framework (VoutV) and central positions (VinV) in the Keggin-type polyoxometalates (POMs) [VinVVoutVM11O40]4- (M = Mo, W; VinVVoutVM11) and in the central position in [VinVM12O40]3- (VinVM12). The structures of the VinVVoutVM11 class have been determined by X-ray crystallography and compared to those of VinVM12 reported previously. A major feature of interest with POMs is their capacity for very extensive reduction, particularly when protonation accompanies the electron transfer step. With VinVVoutVM11 and VinVM12 POMs, knowledge as to whether reduction occurs at V or M sites and the concomitant dependence on acidity has been obtained. Frozen solution EPR spectra obtained following bulk electrolysis showed that the one-electron reduction of VinVMo12 occurs at the molybdenum framework site to give VinVMoVMo11. In contrast, EPR spectra of one-electron reduced VinVW12 at <30 K are consistent with the electron being accommodated on the central V atom in a tetrahedral environment to give VinIVW12. In the case of VinVVoutVM11, the initial reduction occurs at the framework VoutV site to give VinVVoutIVM11. The second electron is delocalized over the Mo framework in two-electron reduced VinVVoutIVMoVMo10, whereas it is accommodated on the central V site in VinIVVoutIVW11. The distance between VinIV and VoutIV in VinIVVoutIVW11 estimated as 3.5 ± 0.2 Å from analysis of the EPR spectrum is consistent with that obtained in VinVVoutVW11 from crystallographic data. Simulations of the cyclic voltammograms as a function of CF3SO3H acid concentration for the initial reduction processes provide excellent agreement with experimental data obtained in acetonitrile (0.10 M [n-Bu4N][PF6]) and allowed acid association constants to be estimated and compared with the literature values available for [XVoutVM11O40]n- (X = S (n = 3), P and As (n= 4); M = Mo, W). The interpretation of the voltammetric data is supported by 51V NMR measurements on the oxidized VV forms of the POMs.

On Ternary Complex Stability in Protein Degradation: In Silico Molecular Glue Binding Affinity Calculations.

Molecular glues are small molecules that simultaneously bind to two proteins, creating a chemically induced protein-protein interface. CELMoDs (cereblon E3 ligase modulators) are a class of molecular glues that promote recruitment of neosubstrate proteins to the E3 ubiquitin ligase cereblon (CRBN) for poly-Lys48-ubiquitination and proteasomal degradation. Ternary complex structures of clinical CELMoDs CC-885 and CC-90009 bound to CRBN and neosubstrate G1 to S phase transition protein 1 (GSPT1) have been experimentally determined. Although cellular degradation is a downstream event, dependent not only on the affinity of the glue CELMoD in the ternary complex, we test the applicability of established structure-based drug design principles to predict binding affinity of CELMoDs to the protein-protein neointerface and correlation to measured cellular degradation for the neosubstrates GSPT1 and zinc finger Aiolos (IKZF3). For a congeneric series of CELMoDs, which have a similar sequence of binding events and resultant binding modes, we conclude that well-established structure-based methods that measure in silico ternary complex stabilities can predict relative degradation potency by CELMoDs.

Splenic Artery Steal Syndrome in Patients with Liver Cirrhosis: A Retrospective Clinical Study.

BACKGROUND Splenic artery steal syndrome (SASS) can aggravate liver damage in patients with cirrhosis. This study explored whether SASS could be an effective therapeutic target for improving hepatic artery perfusion and liver function in patients with decompensated cirrhosis. MATERIAL AND METHODS Based on inclusion and exclusion criteria, 87 patients with hepatitis B cirrhosis and portal hypertension hypersplenism admitted to our General Surgery Department for splenectomy and pericardial devascularization surgery were selected. A total of 35 cases met the diagnostic criteria of SASS and were assigned to the SASS group; the remaining 52 cases were assigned to the control group. The indicators before, during, and after surgery were compared between the 2 groups. RESULTS There were no significant differences in preoperative and intraoperative indicators between SASS group and control group (P>0.05). The MELD score 7 days after surgery and the hepatic artery diameter and hepatic artery velocity 14 days after surgery in both groups were significantly better than before surgery. The MELD score 7 days after surgery in the SASS group was significantly better than that in the control group, and the hepatic artery diameter and hepatic artery velocity 14 days after surgery in the SASS group were significantly better than those in the control group (P<0.05). CONCLUSIONS Splenectomy and pericardial devascularization surgery was an effective treatment to redirect blood flow to the hepatic artery for cirrhotic patients diagnosed with SASS. The introduction of cirrhotic SASS into clinical practice may benefit more patients with cirrhotic portal hypertension and hypersplenism.

Integrated single-cell and bulk RNA sequencing analysis identifies a cancer-associated fibroblast-related gene signature for predicting survival and therapy in gastric cancer.

As the dominant component of the tumor microenvironment, cancer-associated fibroblasts (CAFs), play a vital role in tumor progression. An increasing number of studies have confirmed that CAFs are involved in almost every aspect of tumors including tumorigenesis, metabolism, invasion, metastasis and drug resistance, and CAFs provide an attractive therapeutic target. This study aimed to explore the feature genes of CAFs for potential therapeutic targets and reliable prediction of prognosis in patients with gastric cancer (GC). Bioinformatic analysis was utilized to identify the feature genes of CAFs in GC by performing an integrated analysis of single-cell and transcriptome RNA sequencing using R software. Based on these feature genes, a CAF-related gene signature was constructed for prognostic prediction by LASSO. Simultaneously, survival analysis and nomogram were performed to validate the prognostic predictive value of this gene signature, and qRT-PCR and immunohistochemical staining verified the expression of the feature genes of CAFs. In addition, small molecular drugs for gene therapy of CAF-related gene signatures in GC patients were identified using the connectivity map (CMAP) database. A combination of nine CAF-related genes was constructed to characterize the prognosis of GC, and the prognostic potential and differential expression of the gene signature were initially validated. Additionally, three small molecular drugs were deduced to have anticancer properties on GC progression. By integrating single-cell and bulk RNA sequencing analyses, a novel gene signature of CAFs was constructed. The results provide a positive impact on future research and clinical studies involving CAFs for GC.

Selective Electrochemical Hydrogenation of Phenol with Earth-abundant Ni-MoO2 Heterostructured Catalysts: Effect of Oxygen Vacancy on Product Selectivity.

Herein, we report highly efficient carbon supported Ni-MoO2 heterostructured catalysts for the electrochemical hydrogenation (ECH) of phenol in 0.10 M aqueous sulfuric acid (pH 0.7) at 60 °C. Highest yields for cyclohexanol and cyclohexanone of 95 % and 86 % with faradaic efficiencies of ∼50 % are obtained with catalysts bearing high and low densities of oxygen vacancy (Ov ) sites, respectively. In situ diffuse reflectance infrared spectroscopy and density functional theory calculations reveal that the enhanced phenol adsorption strength is responsible for the superior catalytic efficiency. Furthermore, 1-cyclohexene-1-ol is an important intermediate. Its hydrogenation route and hence the final product are affected by the Ov density. This work opens a promising avenue to the rational design of advanced electrocatalysts for the upgrading of phenolic compounds.

A novel biomarker NIFK-AS1 promotes hepatocellular carcinoma cell cycle progression through interaction with SRSF10.

Background: Hepatocellular carcinoma (HCC) is one of the most common carcinomas all over the world, with high mortality and low survival rate. Notably, many studies have showed that a variety of molecules play vital roles in the progression of HCC. Therefore, it is urgent to find reliable biomarkers to diagnose HCC and developing novel strategies are required for the effective treatment of patients with HCC. Methods: This study obtained an HCC cohort from The Cancer Genome Atlas (TCGA). For prognostic analysis, the TCGA cohort was grouped according to different median boundaries. The key module associated with HCC was adopted by Weighted Gene Co-expression Network analysis (WGCNA). We also analyzed the survival ability, functional enrichment, and potential binding proteins of key lncRNAs. The expression of hub lncRNAs in HCC tissues and cell lines was detected by reverse transcription-quantitative polymerase chain reaction (RT-qPCR). Cell Counting Kit-8 (CCK-8) and flow cytometry were applied to detect the cell proliferation, apoptosis, and cell cycle. The interaction between NIFK-AS1 and SRSF1 was examined using an RNA pull-down assay. Results: The green module is the key module in HCC. NIFK-AS1 was highly expressed in HCC tissues and correlated with a poor prognosis in HCC patients (P=0.008). NIFK-AS1 was also significantly associated with cell mitosis, the cell cycle, and other biological processes. NIFK-AS1 deletion prevented cell proliferation, induced apoptosis, caused G2/M arrest, and affected cell cycle progression. RNA pull-down validated the NIFK-AS1/SRSF10 interaction. The overexpression of NIFK-AS1 was sufficient to rescue the growth of SRSF10 knockdown HepG2 cells. Conclusions: This study suggested that NIFK-AS1 promotes HCC cell cycle progression through interaction with SRSF10 and its findings provide new insights into therapeutic targets for HCC.

Prognostic signature for hepatocellular carcinoma based on 4 pyroptosis-related genes.

BACKGROUND: Hepatocellular carcinoma (HCC) is a cancer with a poor prognosis. Many recent studies have suggested that pyroptosis is important in tumour progression. However, the role of pyroptosis-related genes (PRGs) in HCC remains unclear. MATERIALS AND METHODS: We identified differentially expressed PRGs in tumours versus normal tissues. Through univariate, LASSO, and multivariate Cox regression analyses, a prognostic PRG signature was established. The signature effectiveness was evaluated by time-dependent receiver operating characteristic (t-ROC) curve and Kaplan-Meier (KM) survival analysis. The signature was validated in the ICGC (LIRI-JP) cohort. In addition, single-sample gene enrichment analysis (ssGSEA) showed the infiltration of major immune cell types and the activity of common immune pathways in different subgroups. RESULTS: Twenty-nine pyroptosis-related DEGs from The Cancer Genome Atlas-Liver Hepatocellular Carcinoma (TCGA-LIHC) dataset were detected, and four genes (CTSV, CXCL8, MKI67 and PRF1) among them were selected to construct a prognostic signature. Then, the patients were divided into high- and low-risk groups. The pyroptosis-related signature was significantly associated with overall survival (OS). In addition, the patients in the high-risk group had lower levels of immune infiltration. CONCLUSION: The prognostic signature for HCC based on 4 pyroptosis-related genes has reliable prognostic and predictive value for HCC patients.

Formulations of selected Energy beverages promote pro-oxidant effects of ascorbic acid and long-term stability of hydrogen peroxide.

Recently, autoxidation mediated by ascorbic acid (AA) and other ingredients, has been implicated in generation of hydrogen peroxide (H2O2) in so-called Energy beverages. Here, we report the use of cyclic voltammetry and the FOX assay to monitor at short and long incubation times, respectively, the production and stability of H2O2 generated by AA and redox-active ingredients. Levels of H2O2 in Energy drinks (36.5 ± 4.0 µM at 4 °C and 64.2 ± 7.6 µM at 20 °C) were found to be stable or increased (p < 0.05) upon vessel opening. A predictive model for the production of H2O2 as a function of AA concentration, temperature and incubation time, and depending on ingredients present, indicated that H2O2 peaked at 91-726 µM after 1 day and declined to âˆ¼ 42-60 µM (4 °C) or zero after âˆ¼10 days. The research supports that levels of H2O2 in beverages containing anti-oxidant mixtures and dissolved oxygen should be monitored and formulations modified to avoid AA autoxidation.

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO2.

ConspectusElectrochemical reduction of the greenhouse gas CO2 offers prospects for the sustainable generation of fuels and industrially useful chemicals when powered by renewable electricity. However, this electrochemical process requires the use of highly stable, selective, and active catalysts. The development of such catalysts should be based on a detailed kinetic and mechanistic understanding of the electrochemical CO2 reduction reaction (eCO2RR), ideally through the resolution of active catalytic sites in both time (i.e., temporally) and space (i.e., spatially). In this Account, we highlight two advanced spatiotemporal voltammetric techniques for electrocatalytic studies and describe the considerable insights they provide on the eCO2RR. First, Fourier transformed large-amplitude alternating current voltammetry (FT ac voltammetry), as applied by the Monash Electrochemistry Group, enables the resolution of rapid underlying electron-transfer processes in complex reactions, free from competing processes, such as the background double-layer charging current, slow catalytic reactions, and solvent/electrolyte electrolysis, which often mask conventional voltammetric measurements of the eCO2RR. Crucially, FT ac voltammetry allows details of the catalytically active sites or the rate-determining step to be revealed under catalytic turnover conditions. This is well illustrated in investigations of the eCO2RR catalyzed by Bi where formate is the main product. Second, developments in scanning electrochemical cell microscopy (SECCM) by the Warwick Electrochemistry and Interfaces Group provide powerful methods for obtaining high-resolution activity maps and potentiodynamic movies of the heterogeneous surface of a catalyst. For example, by coupling SECCM data with colocated microscopy from electron backscatter diffraction (EBSD) or atomic force microscopy, it is possible to develop compelling correlations of (precatalyst) structure-activity at the nanoscale level. This correlative electrochemical multimicroscopy strategy allows the catalytically more active region of a catalyst, such as the edge plane of two-dimensional materials and the grain boundaries between facets in a polycrystalline metal, to be highlighted. The attributes of SECCM-EBSD are well-illustrated by detailed studies of the eCO2RR on polycrystalline gold, where carbon monoxide is the main product. Comparing SECCM maps and movies with EBSD images of the same region reveals unambiguously that the eCO2RR is enhanced at surface-terminating dislocations, which accumulate at grain boundaries and slip bands. Both FT ac voltammetry and SECCM techniques greatly enhance our understanding of the eCO2RR, significantly boosting the electrochemical toolbox and the information available for the development and testing of theoretical models and rational catalyst design. In the future, it may be possible to further enhance insights provided by both techniques through their integration with in situ and in operando spectroscopy and microscopy methods.

CHMP4C regulates lung squamous carcinogenesis and progression through cell cycle pathway.

BACKGROUND: Lung cancer is a common kind of human malignancies. Lung squamous cell carcinoma (LUSC) is a key subtype of lung cancer. Cell cycle plays an important role in the development and occurrence of LUSC, however, there is still a lack of cell cycle-related genes in LUSC diagnosis and prediction of prognosis. METHODS: We identified differentially expressed genes (DEGs) with "limma" package in R software, and determined the biomarkers of LUSC in diagnosing by performing receiver operating characteristic (ROC) curve analysis, the biomarker effectiveness in diagnosing LUSC was assessed by performing five-fold cross-validation with logistic regression. Kaplan-Meier plot and the nomogram assessed the relationship between the biomarker and patient survival, and WB and qRT-PCR detected the biomarker expression in cells and tissues. Flow cytometry detects the role of the biomarker in the cell cycle. RESULTS: Integration analysis with The Cancer Genome Atlas (TCGA) database obtained a unique gene related to cell cycle in LUSC (Charged multivesicular body protein 4C, CHMP4C), and the protein of CHMP4C was highly expressed in LUSC tissues. ROC analysis indicated that CHMP4C was a biomarker for the diagnosis of LUSC. Bioinformatic analysis indicated that CHMP4C might be associated with cell cycle in LUSC. CHMP4C knockdown resulted in S-phase arrest of cells with LUSC. According to the survival rate analysis, CHMP4C overexpression indicated poor prognosis in patients with LUSC. CONCLUSIONS: CHMP4C regulates the proliferation process of tumor cells through the cell cycle. It can be used as a potential diagnostic and prognostic biomarker for LUSC.

Polysaccharide of Atractylodes macrocephala Koidz regulates LPS-mediated mouse hepatitis through the TLR4-MyD88-NFκB signaling pathway.

Feed corruption and poor breeding environment could cause widespread bacterial infection which could cause severe liver inflammation and lead to liver damage, even death. It has been proved that Polysaccharide of Atractylodes macrocephala Koidz (PAMK) could improve the immunity of animal, but the mechanism of its protective effect on hepatitis has been rarely reported. This study investigated the protective effect of PAMK on mouse liver through LPS-induced liver inflammatory. The results showed that LPS caused swelling of hepatocytes, disappearance of hepatic cord structure and infiltration of a large number of inflammatory cells, and LPS could up-regulated mRNA and protein expression levels of TLR4, MyD88, IKBα and NFκB, increased cytokines IL-1ß, IL-4, IL-6 and TNF-α levels, enhance the levels of antioxidant enzymes CAT, GSH-PX, SOD, iNOs and MDA. PAMK pretreatment could relieved histopathological damage caused by LPS, and could activate the TLR4-MyD88-NFκB signalling pathway, reduce the levels of IL-1ß, IL-6 and TNF-α, increase IL-4 levels, inhibit the levels of GSH-PX and MDA. These results indicate that PAMK could reduce inflammatory damage and oxidative stress in mice and play a protective role in the early stages of LPS invasion of the liver.

A stable gene set for prediction of prognosis and efficacy of chemotherapy in gastric cancer.

BACKGROUND: Gastric cancer (GC) is a primary reason for cancer death in the world. At present, GC has become a public health issue urgently to be solved to. Prediction of prognosis is critical to the development of clinical treatment regimens. This work aimed to construct the stable gene set for guiding GC diagnosis and treatment in clinic. METHODS: A public microarray dataset of TCGA providing clinical information was obtained. Dimensionality reduction was carried out by selection operator regression on the stable prognostic genes discovered through the bootstrap approach as well as survival analysis. FINDINGS: A total of 2 prognostic models were built, respectively designated as stable gene risk scores of OS (SGRS-OS) and stable gene risk scores of PFI (SGRS-PFI) consisting of 18 and 21 genes. The SGRS set potently predicted the overall survival (OS) along with progression-free interval (PFI) by means of univariate as well as multivariate analysis, using the specific risk scores formula. Relative to the TNM classification system, the SGRS set exhibited apparently higher predicting ability. Moreover, it was suggested that, patients who had increased SGRS were associated with poor chemotherapeutic outcomes. INTERPRETATION: The SGRS set constructed in this study potentially serves as the efficient approach for predicting GC patient survival and guiding their treatment.

Recent advances and future perspectives for automated parameterisation, Bayesian inference and machine learning in voltammetry.

Advanced data analysis tools such as mathematical optimisation, Bayesian inference and machine learning have the capability to revolutionise the field of quantitative voltammetry. Nowadays such approaches can be implemented routinely with widely available, user-friendly modern computing languages, algorithms and high speed computing to provide accurate and robust methods for quantitative comparison of experimental data with extensive simulated data sets derived from models proposed to describe complex electrochemical reactions. While the methodology is generic to all forms of dynamic electrochemistry, including the widely used direct current cyclic voltammetry, this review highlights advances achievable in the parameterisation of large amplitude alternating current voltammetry. One significant advantage this technique offers in terms of data analysis is that Fourier transformation provides access to the higher order harmonics that are almost devoid of background current. Perspectives on the technical advances needed to develop intelligent data analysis strategies and make them generally available to users of voltammetry are provided.

Identification of a novel pyroptosis-related gene signature correlated with the prognosis of diffuse glioma patients.

BACKGROUND: Diffuse glioma is the most common primary tumor of the central nervous system and has a poor prognosis. Recently, a new type of programmed cell death (PCD), pyroptosis, has been found to be widely involved in the process of tumor diseases. However, the expression of pyroptosis-related genes (PRGs) in diffuse gliomas and their relationship with prognosis have rarely been evaluated. METHODS: In this study, we obtained RNA sequencing and clinical data from the Cancer Genome Atlas (TCGA) database and the Chinese Glioma Genome Atlas (CGGA) of diffuse glioma patients. Simultaneously, differentially expressed PRGs between TCGA-Glioma tumor samples and the normal brain samples from the Genome Tissue Expression (GTEx) were investigated. Besides, univariate and multivariate Cox regression analysis were performed to identify and construct the prognostic gene signature. Time-dependent receiver operating characteristic (ROC), Kaplan-Meier curve and principal component analysis (PCA) was undertaken to assess the prognostic capacity of the signature. Gene set enrichment analyses (GSEA) and single sample GSEA (ssGSEA) were used to further understand the molecular mechanisms and the difference of immune microenvironment. External validation of two separate cohorts from the CGGA database was then performed. RESULTS: Caspase 3 (CASP3) and interleukin-18 (IL18) were identified as potential prognostic biomarkers. A novel prognostic model was constructed to predict diffuse glioma patients' overall survival (OS) time. Patients in high-risk subgroup had shorter survival than those with high-risk with P<0.0001. GSEA and ssGSEA showed the activation of immune-related pathways and the extensive infiltration of immune cells [such as cytotoxic T cells, dendritic cells (DC), natural killer T cell (NKT), induced regulatory T cells (iTreg), naturally occurring regulatory T cells (nTreg)] in high-risk subgroup. CONCLUSIONS: A novel two-PRGs prognostic signature based on gene expression was identified, which could predict diffuse glioma patients' OS time. Pyroptosis may be involved in the establishment of immune microenvironment in diffuse glioma.

Impact of the Lithium Cation on the Voltammetry and Spectroscopy of [XVM11O40]n- (X = P, As (n = 4), S (n = 3); M = Mo, W): Influence of Charge and Addenda and Hetero Atoms.

Polyoxometalates (POMs) have been proposed as electromaterials for lithium-based batteries because they provide access to multiple electron transfer reactions coupled to fast lithium ion transport processes and high stability over many redox cycles. Consequently, knowledge of reversible potentials and Li+ cation-POM anion interactions provides a strategic basis for their further development. In this study, detailed cyclic voltammetric studies of a series of [XVVM11O40]n- (XVM11n-) POMs (where X (heteroatom) = P (n = 4), As (n = 4), and S (n = 3) and M (addenda atom) = Mo, W) have been undertaken in CH3CN in the presence of LiClO4, with n-Bu4NPF6 also present when required to keep the ionic strength close to constant value of 0.1 M. An analysis of the data has allowed the impact of the POM charge, and addenda and hetero atoms on the reversible potentials and the interaction between Li+ and the oxidized XVVM11n- and reduced XVIVM11(n+1)- forms of the VV/IV redox couple to be determined. The SVV/IVM113-/4- process is independent of the Li+ concentration, implying the absence of the association of this cation with either SVVM113- or SVIVM114- redox levels. However, lithium-ion association constants for both VV and VIV redox levels were obtained from a comparison of simulated and experimental cyclic voltammograms for the reduction of the more negatively charged XVVM114- (X = P, As; M = Mo, W), since the Li+ interaction with these more negatively charged POMs is much stronger. The interaction between Li+ and the oxidized, XVVM11n-, and reduced, XVIVM11(n+1)-, forms was also investigated by 51V NMR and EPR spectroscopy, respectively, and it was confirmed that, due to their lower charge density, SVVM113- and SVIVM114- interact significantly less strongly with the lithium ion than XVVM114- and XVIVM115- (X = P, As). The lithium-POM association constants are substantially smaller than the corresponding proton association constants reported previously, which is attributed to a smaller surface charge density. The much stronger impact of Li+ on the WVI/V- and MoVI/V-based reductions that occur at more negative potentials than the VV/IV process also has been qualitatively evaluated.

Clinical and genomic landscape of hepatocellular carcinoma subtypes with various proportions of nonleukocyte stromal cells.

BACKGROUND: Hepatocellular carcinoma (HCC) is one of the most common malignancies and inflicts high mortality worldwide. The effect of tumor microenvironment components on HCC oncogenesis remains unknown. In particular, the nonleukocyte portion of the stromal fraction (SF) is poorly understood. METHODS: We comprehensively evaluated the proportional cell counts and gene expression data from The Cancer Genome Atlas (TCGA) to examine the contributions of cell components to the tumor microenvironment. Single-cell sequencing data from the Gene Expression Omnibus (GEO) were also analyzed to verify the association between the nonleukocyte SF and genes. We classified HCC using a hierarchical clustering method based on diversity of nonleukocyte SF-related gene expression among different components, and we used an appropriate GEO dataset to verify the clusters with a support vector machine (SVM) model. The prognosis of subtypes and their relationship with tumor microenvironmental cell proportions, clinicopathogenesis factors, and other indicators were evaluated. RESULTS: Based on linear regression, 711 genes related to nonleukocyte SF were selected from the TCGA dataset. We classified HCC into three subtypes using genes related to the nonleukocyte SF. Additionally, the GEO single-cell sequencing data confirmed the relationship between genes and the nonleukocyte SF. The tumor microenvironment of Type 2 contained the most significant mutually reinforcing interaction between the nonleukocyte SF and tumor cells. Meanwhile, Type 2 patients had the poorest prognosis and the most severe tumor-node-metastasis (TNM) stages, histological grades, etc. The analysis based on the GEO dataset verified the classification results with an SVM model. Type 2 was associated with worse clinicopathological characteristics, including tumor grading and staging, than the other types. In addition, the pathway analysis revealed that signals related to the SF and cell proliferation were significantly enhanced in Type 2 compared to the other group, which consisted of Types 1 and 3. CONCLUSION: The nonleukocyte SF in the tumor microenvironment contributed greatly to HCC oncogenesis. We can use these HCC classification criteria to stratify patients into subtypes for personalized treatment.

Selenium-Alleviated Hepatocyte Necrosis and DNA Damage in Cyclophosphamide-Treated Geese by Mitigating Oxidative Stress.

Selenium (Se) has been well recognized as an immune-enhancing agent with antioxidant and anti-tumor properties. The commonly used chemotherapy drug, cyclophosphamide (CTX), induces liver injury by increasing the reactive oxygen species (ROS) level. However, little is known about how Se alleviates CTX-induced liver injury in geese. In this study, 90 male Magang geese (3 days old) were randomly allocated into three groups (control, CTX, and Se + CTX group) with three replicates per group and ten geese per replicate. The control and CTX groups were fed a basal diet (Se content was 0.03 mg/kg). The Se + CTX group was fed a basal diet containing 0.44 mg/kg sodium selenite (Se content was 0.2 + 0.03 mg/kg). The control group was injected with 0.5 mL saline, while the CTX and Se + CTX groups were injected with CTX at 40 mg/kg body weight per day on days 21-23. The liver index, liver histology, and ultra-micromorphology detected antioxidant enzyme activity in the liver and serum. In addition, we detected the liver marker enzymes and protein levels in serum, and hepatocyte DNA damage. Se could alleviate liver development dysregulation, hepatocyte structural damage, the disturbances in antioxidant enzyme (GPx, CAT, and SOD) activity, and malondialdehyde (MDA) levels in the serum and liver. Besides, Se could alleviate the dysregulation of liver marker enzyme (ALT and AST) activity and protein (ALB and TP) levels in the serum, and DNA migration induced by CTX. In conclusion, Se may inhibit hepatocyte necrosis and DNA damage by inhibiting CTX-induced oxidative stress.

Two-Dimensional Electrocatalysts for Efficient Reduction of Carbon Dioxide.

Two-dimensional (2D) materials are attractive catalysts for the electrochemical reduction of carbon dioxide reaction (eCO2 RR) by virtue of their tunable atomic structures, abundant active sites, enhanced conductivity, suitable binding affinity to carbon dioxide and/or reaction intermediates, and intrinsic scalability. Herein, recent advances in 2D catalysts for the eCO2 RR are reviewed. Structural features and properties of 2D materials that contribute to their advanced electrocatalytic properties are summarized, and strategies for enhancing their activity and selectivity for the eCO2 RR are reviewed. Prospects and challenges of applications of 2D catalysts for the eCO2 RR on an industrial scale are highlighted.

Unprecedented Formation of a Binuclear Au(II)-Au(II) Complex through Redox State Cycling: Electrochemical Interconversion of Au(I)-Au(I), Au(II)-Au(II), and Au(I)-Au(III) in Binuclear Complexes Containing the Carbanionic Ligand C6F4PPh2.

The rational design of binuclear Au(I)-Au(I), Au(II)-Au(II), and Au(I)-Au(III) complexes requires an understanding of how the redox states interconvert. Herein, the electrochemical interconversion of the three oxidation states I, II, and III is reported on the voltammetric (cyclic and rotating disk electrode) time scales for binuclear gold complexes containing C6F4PPh2 as a ligand, to demonstrate for the first time formation of a binuclear Au(II)-Au(II) from a Au(I)-Au(III) complex. Results are supported by bulk electrolysis and coulometry with reaction products being identified by 31P NMR and UV-vis spectroscopy. All electrochemical processes involve an overall two-electron charge-transfer process with no one-electron intermediate being detected. Importantly, the kinetically rather than thermodynamically favored isomer [Au2IIX2(µ-2-C6F4PPh2)2] is formed on redox cycling of [XAuI(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuIIIX] (X = Cl, ONO2). Finally, a mechanism is proposed to explain the simultaneous change of coordination of the chelating carbanionic ligand to bridging mode and interconversion of oxidation states in binuclear gold complexes.