Dynamic transformation between bilayer islands and dinuclear clusters of Cr oxide on Au(111) through environment and interface effects.

SignificanceFor oxide catalysts, it is important to elucidate and further control their atomic structures. In this work, well-defined CrO2 bilayer islands and Cr2O7 dinuclear clusters have been grown on Au(111) and unambiguously identified by scanning tunneling microscopy and theoretical calculations. Upon cycled redox treatments, the two kinds of oxide nanostructures can be reversibly transformed. It is interesting to note that both Cr oxides do not exist in bulk but need to be stabilized by the metal surface and the specific environment. Our results suggest that both redox atmosphere and interface confinement effects can be used to construct an oxide nanostructure with the specific chemical state and structure.

Urodynamic analysis of the effect of electroacupuncture at different acupoints on the bladder after spinal cord injury.

OBJECTIVE: Guanyuan (CV4), Zhongji (CV3) and Sanyinjiao (SP6) are the most frequently used acupoints for treating neurogenic bladder after spinal cord injury (SCI). However, there has been no investigation to clarify the differences in effects of these acupoints in different types of neurogenic bladder. METHODS: The study was structured with a randomized, two-phase cross over design with a washout period. A routine urodynamic examination was performed first, then, in the order of grouping, electroacupuncture was performed on CV4, CV3, and SP6, respectively，and urodynamic examination was performed to observe the changes of urodynamic indexes in real time. RESULTS: When undergoing electroacupuncture at CV4, CV3, and SP6 in patients with neurogenic detrusor overactivity (DO), the bladder volume at the first occurrence of DO and maximum cystometric capacity increased (p < 0.05), but maximum detrusor pressure (Pdetmax) at DO decreased (p < 0.05), and the changes using CV4 and CV3 was more significantly than using SP6 (p < 0.05). And in patients with in neurogenic detrusor underactivity, there were no significant changes in maximum urinary flow rate and Pdetmax during urination (p > 0.05). CONCLUSION: The immediate relief effect of electroacupuncture at CV4, CV3 on DO was greater than at SP6.

Survival benefit of radical prostatectomy in patients with advanced TURP-diagnosed prostate cancer: a population-based real-world study.

OBJECTIVES: A considerable number of patients are diagnosed with prostate cancer (PCa) by transurethral resection of the prostate (TURP). We aimed to evaluate whether radical prostatectomy (RP) brings survival benefits for these patients, especially in the elderly with advanced PCa. PATIENTS AND METHODS: We used the Surveillance, Epidemiology, and End Results (SEER) database to obtain PCa cases diagnosed with TURP. After the propensity matching score (PSM) for case matching, univariate, multivariate, and subgroup analyses were performed to investigate whether RP impacts the survival benefit. RESULTS: 4,677 cases diagnosed with PCa by TURP from 2010 to 2019 were obtained, including 1,313 RP patients and 3,364 patients with no RP (nRP). 9.6% of RP patients had advanced PCa. With or without PSM, cancer-specific mortality (CSM) and overall mortality (OM) were significantly reduced in the RP patients compared to the nRP patients, even for older (> 75 ys.) patients with advanced stages (all p < 0.05). Except for RP, younger age (≤ 75 ys.), being married, and earlier stage (localized) contributed to a significant reduction of CSM risk (all p < 0.05). These survival benefits had no significant differences among patients of different ages, married or single, and at different stages (all p for interaction > 0.05). CONCLUSIONS: Based on this retrospective population-matched study, we first found that in patients diagnosed with PCa by TURP, RP treatment may lead to a survival benefit, especially a reduction in CSM, even in old aged patients (> 75 ys.) with advanced PCa.

Activating lattice oxygen of single-layer ZnO for the catalytic oxidation reaction.

Tuning an oxide/metal interface is of critical importance for the performance enhancement of many heterogeneous catalytic reactions. However, catalytic oxidation occurring at the interface between non-reducible oxide and metal has been challenging, since non-reducible oxides hardly lose their lattice oxygen (OL) or dissociate O2 from the gas phase. In this work, a ZnO monolayer film on Au(111) is used as an inverse catalyst to investigate CO oxidation occurring at the ZnO/Au(111) interface via high pressure scanning tunneling microscopy. Surface science experiments indicate that oxygen intercalation under the ZnO monolayer film, termed ZnO/O/Au(111), can be achieved via a surface reaction with 1 × 10-6 mbar O3. Subsequent exposure of the formed ZnO/O/Au(111) surface to mbar CO at room temperature leads to the recovery of the pristine ZnO/Au(111) surface. Theoretical calculations reveal that OL adjacent to intercalated oxygen (Oint) is activated due to the OL-Zn-Oint bonding and surface corrugation, which can be directly involved in CO oxidation. Subsequently, Oint migrates to the formed oxygen vacancy from the subsurface resuming the pristine ZnO structure. These results thus reveal that oxygen intercalation underneath single-layer ZnO will strongly boost the oxidation reaction via activating adjacent lattice oxygen atoms.

DNA Methylation-Mediated Lowly Expressed AOX1 Promotes Cell Migration and Invasion of Prostate Cancer.

INTRODUCTION: DNA methylation regulates gene transcriptional functions in the pathogenesis of malignant diseases. In prostate cancer, several tumor suppressors are known to be tumor specifically methylated. METHODS: In this study, 450K methylation data and mRNA expression data were accessed from The Cancer Genome Atlas-Prostate Adenocarcinoma database and analyzed bioinformatically. Methylation-specific PCR was used to examine the methylation condition in AOX1 promoter. qRT-PCR was applied to measure the mRNA expression of AOX1. Western blot was employed to detect the expressions of AOX1 and the EMT associated proteins. Transwell and scratch healing assays were used to examine the invasive and migratory abilities of the prostate cancer cells respectively. RESULTS: AOX1 was lowly expressed and hypermethylated in the prostate cancer tissues and cells. Also, AOX1 was downregulated at protein level in prostate cancer cells. Knocking down AOX1 could promote cell migration and invasion in the prostate cancer cells. By using a DNA methylation inhibitor, 5-AzadC was found to promote the expression of AOX1 and reverse the promoting effects of short interfering RNA against AOX1 on cell migration and invasion. CONCLUSION: This study suggested that DNA methylation and low AOX1 level might be biomarkers for prostate cancer.

Overturning CO2 Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal-Support Interactions.

Encapsulation of metal nanoparticles by support-derived materials known as the classical strong metal-support interaction (SMSI) often happens upon thermal treatment of supported metal catalysts at high temperatures (≥500 °C) and consequently lowers the catalytic performance due to blockage of metal active sites. Here, we show that this SMSI state can be constructed in a Ru-MoO3 catalyst using CO2 hydrogenation reaction gas and at a low temperature of 250 °C, which favors the selective CO2 hydrogenation to CO. During the reaction, Ru nanoparticles facilitate reduction of MoO3 to generate active MoO3-x overlayers with oxygen vacancies, which migrate onto Ru nanoparticles' surface and form the encapsulated structure, that is, Ru@MoO3-x. The formed SMSI state changes 100% CH4 selectivity on fresh Ru particle surfaces to above 99.0% CO selectivity with excellent activity and long-term catalytic stability. The encapsulating oxide layers can be removed via O2 treatment, switching back completely to the methanation. This work suggests that the encapsulation of metal nanocatalysts can be dynamically generated in real reactions, which helps to gain the target products with high activity.

UBC Mediated by SEPT6 Inhibited the Progression of Prostate Cancer.

BACKGROUND: Prostate cancer is one of the most common malignancies in men. Protein ubiquitination is an important mechanism for regulating protein activity and level in vivo. We aimed to study the mechanism of SEPT6 and UBC action in prostate cancer to identify new targets. METHODS: The ubiquitin-protein and the ubiquitin coding gene UBA52, UBA80, UBB, and UBC expressions were detected in clinical tissues and cells. Overexpression and knockdown of UBC were performed in prostate cancer DU145 cells. Cell Counting Kit 8 (CCK-8) assay was performed to detect cell proliferation. Cell cycle at 24 h was detected by flow cytometry. Clonal formation assay was used to measure cell clone number. Immunofluorescence (IF) was performed to detect the colocalization of SEPT6 and UBC in prostate cancer cells. Next, we overexpressed or knocked down SEPT6 expression in DU145 cells. Pearson correlation coefficient was applied to analyze the relationship between SEPT6 and UBC in prostate cancer tissue. oe-SEPT6+oe-UBC coexpressing cells were constructed to detect the upstream and downstream relationship between SEPT6 and UBC on prostate cancer cells. The tumor formation experiment was performed to explore SEPT6/UBC effect on prostate cancer. RESULTS: UBC was upregulated in prostate cancer tissues and cells. Overexpression of UBC promoted cell survival and proliferation. IF revealed the colocalization of SEPT6 and UBC in prostate cancer cells. UBC expression decreased after oe-SEPT6, while increased after sh-SEPT6, indicating that UBC was downstream of SEPT6. Pearson correlation coefficient analysis showed that SEPT6 was negatively correlated with UBC in prostate cancer tissues. SEPT6 as an upstream gene of UBC regulated prostate cancer cell behavior through UBC. The tumor formation experiment showed that SEPT6 could inhibit tumor growth. CONCLUSION: In general, SEPT6 inhibited UBC expression, thereby reducing the overall ubiquitination level, affecting the expression level of downstream cell proliferation-related genes, and then affecting the progression of prostate cancer.

AR12286 Alleviates TGF-ß-Related Myofibroblast Transdifferentiation and Reduces Fibrosis after Glaucoma Filtration Surgery.

Scar formation can cause the failure of glaucoma filtration surgery. We investigated the effect of AR12286, a selective Rho-associated kinase inhibitor, on myofibroblast transdifferentiation and intraocular pressure assessment in rabbit glaucoma filtration surgery models. Cell migration and collagen contraction were used to demonstrate the functionality of AR12286-modulated human conjunctival fibroblasts (HConFs). Polymerase chain reaction quantitative analysis was used to determine the effect of AR12286 on the production of collagen Type 1A1 and fibronectin 1. Cell migration and collagen contraction in HConFs were activated by TGF-ß1. However, compared with the control group, rabbit models treated with AR12286 exhibited higher reduction in intraocular pressure after filtration surgery, and decreased collagen levels at the wound site in vivo. Therefore, increased α-SMA expression in HConFs induced by TGF-ß1 could be inhibited by AR12286, and the production of Type 1A1 collagen and fibronectin 1 in TGF-ß1-treated HConFs was inhibited by AR12286. Overall, the stimulation of HConFs by TGF-ß1 was alleviated by AR12286, and this effect was mediated by the downregulation of TGF-ß receptor-related SMAD signaling pathways. In vivo results indicated that AR12286 thus improves the outcome of filtration surgery as a result of its antifibrotic action in the bleb tissue because AR12286 inhibited the TGF-ß receptor-related signaling pathway, suppressing several downstream reactions in myofibroblast transdifferentiation.

Super-Enhancer-Driven Long Non-Coding RNA LINC01503, Regulated by TP63, Is Over-Expressed and Oncogenic in Squamous Cell Carcinoma.

BACKGROUND & AIMS: Long non-coding RNAs (lncRNAs) are expressed in tissue-specific pattern, but it is not clear how these are regulated. We aimed to identify squamous cell carcinoma (SCC)-specific lncRNAs and investigate mechanisms that control their expression and function. METHODS: We studied expression patterns and functions of 4 SCC-specific lncRNAs. We obtained 113 esophageal SCC (ESCC) and matched non-tumor esophageal tissues from a hospital in Shantou City, China, and performed quantitative reverse transcription polymerase chain reaction assays to measure expression levels of LINC01503. We collected clinical data from patients and compared expression levels with survival times. LINC01503 was knocked down using small interfering RNAs and oligonucleotides in TE7, TE5, and KYSE510 cell lines and overexpressed in KYSE30 cells. Cells were analyzed by chromatin immunoprecipitation sequencing, luciferase reporter assays, colony formation, migration and invasion, and mass spectrometry analyses. Cells were injected into nude mice and growth of xenograft tumors was measured. LINC01503 interaction with proteins was studied using fluorescence in situ hybridization, RNA pulldown, and RNA immunoprecipitation analyses. RESULTS: We identified a lncRNA, LINC01503, which is regulated by a super enhancer and is expressed at significantly higher levels in esophageal and head and neck SCCs than in non-tumor tissues. High levels in SCCs correlated with shorter survival times of patients. The transcription factor TP63 bound to the super enhancer at the LINC01503 locus and activated its transcription. Expression of LINC01503 in ESCC cell lines increased their proliferation, colony formation, migration, and invasion. Knockdown of LINC01503 in SCC cells reduced their proliferation, colony formation, migration, and invasion, and the growth of xenograft tumors in nude mice. Expression of LINC01503 in ESCC cell lines reduced ERK2 dephosphorylation by DUSP6, leading to activation of ERK signaling via MAPK. LINC01503 disrupted the interaction between EBP1 and the p85 subunit of PI3K, increasing AKT signaling. CONCLUSIONS: We identified an lncRNA, LINC01503, which is increased in SCC cells compared with non-tumor cells. Increased expression of LINC01503 promotes ESCC cell proliferation, migration, invasion, and growth of xenograft tumors. It might be developed as a biomarker of aggressive SCCs in patients.

Interfacial Enhancement by γ-Al2 O3 of Electrochemical Oxidative Dehydrogenation of Ethane to Ethylene in Solid Oxide Electrolysis Cells.

Oxidative dehydrogenation of ethane (ODE) is limited by the facile deep oxidation and potential safety hazards. Now, electrochemical ODE reaction is incorporated into the anode of a solid oxide electrolysis cell, utilizing the oxygen species generated at anode to catalytically convert ethane. By infiltrating γ-Al2 O3 onto the surface of La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ -Sm0.2 Ce0.8 O2-δ (LSCF-SDC) anode, the ethylene selectivity reaches as high as 92.5 %, while the highest ethane conversion is up to 29.1 % at 600 °C with optimized current and ethane flow rate. Density functional theory calculations and in situ X-ray photoelectron spectroscopy characterizations reveal that the Al2 O3 /LSCF interfaces effectively reduce the amount of adsorbed oxygen species, leading to improved ethylene selectivity and stability, and that the formation of Al-O-Fe alters the electronic structure of interfacial Fe center with increased density of state around Fermi level and downshift of the empty band, which enhances ethane adsorption and conversion.

Modulation of transcription of genes related to the hypothalamic-pituitary-gonadal and the hypothalamic-pituitary-adrenal axes in zebrafish (Danio rerio) embryos/larvae by androstenedione.

This study aimed to determine the effects of Androstenodione (AED) on the transcriptional expression of genes involved in the hypothalamic-pituitary-gonadal (HPG) and the hypothalamic-pituitary-adrenal (HPA) axes in the zebrafish embryos/larvae. Zebrafish embryos were exposed to 0, 4.0, 45.0, 487.0, and 980.0 ng/L of AED from the day of fertilization to 144 h post fertilization (hpf), during which the transcriptional profiles of key genes related to the HPG and HPA axes were examined daily using quantitative real-time PCR. The AED exposure significantly up-regulated several receptor signaling pathways and the key genes involved in various steps of the steroidogenic pathways were also affected. In addition, the AED exposure could significantly modulate the transcriptional profiles of the other target genes related to hypothalamic and pituitary hormones. The findings of this study suggest that AED, at environmentally relevant concentrations, affects the adrenal endocrine systems and the reproduction of zebrafish by interrupting the HPG and HPA axes.

Ovicidal and Insecticidal Activities of Pyriproxyfen Derivatives with an Oxime Ester Group.

Based on the structural framework of a pyriproxyfen metabolite, nineteen oxime ester derivatives were synthesized via reaction of the carboxylic acids with 4-(2-(2-pyridinyloxy)ethoxy)benzaldehyde oxime. The corresponding structures were comprehensively characterized by ¹H-nuclear magnetic resonance (NMR), 13C-NMR, and electrospray ionization high-resolution mass spectrometry (ESI-HRMS). All of the compounds were screened for their insecticidal activities against Plutella xylostella and Myzus persicae, and for their ovicidal activities against Helicoverpa armigera eggs. The results obtained show that most of the oxime ester derivatives displayed moderate to high insecticidal activities and ovicidal activities at a concentration of 600 ug/mL. In particular, the ovicidal activity of compounds 5j, 5o, 5p, 5q, and 5s was determined to be 100%. Importantly, some of the compounds presented even higher biological activities than the reference compound pyriproxyfen. For example, compound 5j displayed an insecticidal activity value of 87.5% against Myzus persicae, whereas the activity value of pyriproxyfen was 68.3% at a concentration of 600 ug/mL. Among the synthesized compounds 5j and 5s exhibited broad biological activity spectra.

Reverse water gas-shift reaction product driven dynamic activation of molybdenum nitride catalyst surface.

In heterogeneous catalysis catalyst activation is often observed during the reaction process, which is mostly attributed to the induction by reactants. In this work we report that surface structure of molybdenum nitride (MoNx) catalyst exhibits a high dependency on the partial pressure or concentration of reaction products i.e., CO and H2O in reverse water gas-shift reaction (RWGS) (CO2:H2 = 1:3) but not reactants of CO2 and H2. Molybdenum oxide (MoOx) overlayers formed by oxidation with H2O are observed at reaction pressure below 10 mbar or with low partial pressure of CO/H2O products, while CO-induced surface carbonization happens at reaction pressure above 100 mbar and with high partial pressure of CO/H2O products. The reaction products induce restructuring of MoNx surface into more active molybdenum carbide (MoCx) to increase the reaction rate and make for higher partial pressure CO, which in turn promote further surface carbonization of MoNx. We refer to this as the positive feedback between catalytic activity and catalyst activation in RWGS, which should be widely present in heterogeneous catalysis.

Contrast-enhanced ultrasound evaluation of renal perfusion before angioplasty and its predictive value for hypertension.

BACKGROUND: Atherosclerotic renal artery stenosis (ARAS) is a common disease in the elderly population. OBJECTIVE: The aim was to develop a contrast-enhanced ultrasound (CEUS)-based model for predicting post-angioplasty improvement in hypertension in patients with severe ARAS. METHODS: Thirty-five patients with severe ARAS (⩾ 70%) were included in this study, and 42 renal arteries received percutaneous transluminal renal arterial stenting. An optimal integral formula was developed from pre-interventional color-coded duplex sonography (CCDS) and CEUS parameters using least absolute shrinkage and selection operator (LASSO) regression and receiver operating characteristic (ROC) curve analysis. A model for predicting short-term hypertension improvement was established using the integral formula and clinical risk factors. Bootstrapping was used for internal validation. RESULTS: Two integral formulas, LASSO.CCDS and LASSO.CEUS, were established. ROC curves of the two integral formulas showed that LASSO.CEUS was the better formula for predicting hypertension improvement (AUC 0.816, specificity 78.6%). Univariate and multivariate regression analyses showed that duration of hypertension (OR 0.841, P= 0.027), diabetes (OR = 0.019, P= 0.010), and LASSO.CEUS (OR 7.641, P= 0.052) were predictors of short-term hypertension improvement after interventional therapy. Using LASSO.CEUS combined with clinical risk factors, the following prediction model was established: logit (short-term improvement in hypertension) = 1.879-0.173 × hypertension duration - 3.961 × diabetes + 2.034 × LASSO.CEUS (AUC 0.939). CONCLUSIONS: The model established using CEUS parameters and clinical risk factors could predict hypertension improvement after interventional therapy, but further research and verification are needed.

Connecting Structural Characteristics and Material Properties in Phase-Separating Polymer Solutions: Phase-Field Modeling and Physics-Informed Neural Networks.

The formed morphology during phase separation is crucial for determining the properties of the resulting product, e.g., a functional membrane. However, an accurate morphology prediction is challenging due to the inherent complexity of molecular interactions. In this study, the phase separation of a two-dimensional model polymer solution is investigated. The spinodal decomposition during the formation of polymer-rich domains is described by the Cahn-Hilliard equation incorporating the Flory-Huggins free energy description between the polymer and solvent. We circumvent the heavy burden of precise morphology prediction through two aspects. First, we systematically analyze the degree of impact of the parameters (initial polymer volume fraction, polymer mobility, degree of polymerization, surface tension parameter, and Flory-Huggins interaction parameter) in a phase-separating system on morphological evolution characterized by geometrical fingerprints to determine the most influential factor. The sensitivity analysis provides an estimate for the error tolerance of each parameter in determining the transition time, the spinodal decomposition length, and the domain growth rate. Secondly, we devise a set of physics-informed neural networks (PINN) comprising two coupled feedforward neural networks to represent the phase-field equations and inversely discover the value of the embedded parameter for a given morphological evolution. Among the five parameters considered, the polymer-solvent affinity is key in determining the phase transition time and the growth law of the polymer-rich domains. We demonstrate that the unknown parameter can be accurately determined by renormalizing the PINN-predicted parameter by the change of characteristic domain size in time. Our results suggest that certain degrees of error are tolerable and do not significantly affect the morphology properties during the domain growth. Moreover, reliable inverse prediction of the unknown parameter can be pursued by merely two separate snapshots during morphological evolution. The latter largely reduces the computational load in the standard data-driven predictive methods, and the approach may prove beneficial to the inverse design for specific needs.

Oxide-Metal Interaction Probed by Scanning Tunneling Microscope Manipulation of Cr2O7 Clusters on Au(111).

Interfacial interaction plays a crucial rule in catalysis over supported catalysts, and the catalyst-support interaction needs to be explored at microscopic scale. Here, we use the scanning tunneling microscope (STM) tip to manipulate Cr2O7 dinuclear clusters on Au(111) and find that the Cr2O7-Au interaction can be weakened by an electric field in the STM junction, facilitating rotation and translation of the individual clusters at the imaging temperature (78 K). Surface alloying with Cu makes the manipulation of the Cr2O7 clusters hard due to the enhanced Cr2O7-substrate interaction. Density functional theory calculations reveal that barrier for translation of a Cr2O7 cluster on the surface can be increased by surface alloying, influencing the tip manipulation. Our study demonstrates that the oxide-metal interfacial interaction can be probed by STM tip manipulation of supported oxide clusters, which provides a new method to investigate the interfacial interaction.

Spatially Separated Active Sites Enable Selective CO Oxidation Reaction on Oxide Catalyst.

The search for efficient non-noble-metal catalysts able to perform selective oxidation reactions is of great importance, with relevance to many catalytic processes. However, this is often hampered because the origin of the selectivity remains controversial, particularly for reactions catalyzed by oxides. Here, combining high-pressure surface imaging techniques and theoretical calculations, we identify that spatially separated active sites for O2 activation and H2 adsorption on an ultrathin Mn3O4 surface enable selective oxidation of CO over H2. Theoretical calculations reveal that Mn-O pairs for H2 dissociation are separated from Mn-Mn pairs for the formation of adsorbed O2* so that H2 has to surmount much higher barriers for both H2 dissociation and H diffusion while CO can directly react with O2* following the Eley-Rideal process. Our study sheds light on the atomic-level understanding of the surface structure-dependent selective oxidation reaction on oxide catalysts.

Periodic Arrays of Metal Nanoclusters on Ultrathin Fe-Oxide Films Modulated by Metal-Oxide Interactions.

Rational design of highly stable and active metal catalysts requires a deep understanding of metal-support interactions at the atomic scale. Here, ultrathin films of FeO and FeO2-x grown on Pt(111) are used as templates for the construction of well-defined metal nanoclusters. Periodic arrays of Cu clusters in the form of monomers and trimers are preferentially located at FCC domains of FeO/Pt(111) surface, while the selective location of Cu clusters at FeO2 domains is observed on FeO2-x /Pt(111) surface. The preferential nucleation and formation of well-ordered Cu clusters are driven by different interactions of Cu with the Fe oxide domains in the sequence of FeO2-FCC > FeO-FCC > FeO-HCP > FeO-TOP, which is further validated by density functional theory calculations. It has been revealed that the p-band center as a reactivity descriptor of surface O atoms determines the interaction between metal adatoms and Fe oxides. The modulated metal-oxide interaction provides guidance for the rational design of supported single-atom and nanocluster catalysts.