Na Substitution Steering RuO6 Unit in Ruthenium Pyrochlores for Enhanced Oxygen Evolution in Acid.

Although Ruthenium-based pyrochlore oxides can function as promising catalysts for acidic water oxidation, their limitations in terms of stability and activity still need to be addressed for further application in practical conditions. In this work, the possibility to enhance both oxygen evolution reaction activity and durability of Gd2Ru2O7- δ through partial replacement with Na+ in Gd3+ sites is first offered, leading to the electronic and geometric regulation of active center RuO6. Na+ triggers the emergence of Ru<4+ and the electron rearrangement of active-centered RuO6. Specifically, Ru ions with a negative d-band center after Na+ doping exhibit weaker adsorption energies of *O and result in the conversion of the rate-limiting step from *O/*OOH to *OH/O*, reducing energy barriers for boosting activities. Therefore, the NaxGd2- xRu2O7- δ requires a low overpotential of 260 mV at 10 mA cm-2 in 0.1 m HClO4 electrolyte. Moreover, the higher formation energy of Ru vacancy and less distorted RuO6 enable the as-prepared NaxGd2- xRu2O7- δ to operate steadily at 10 mA cm-2 for 300 h and multi-current chronopotentiometry with current densities from 20 to 100 mA cm-2 for 60 h in acidic proton exchange membrane electrolyzer, respectively.

Evaluation of safety and efficacy of inhaled ambroxol in hospitalized adult patients with mucopurulent sputum and expectoration difficulty.

Background: Ambroxol is a widely used mucoactive drug in sputum clearance of respiratory diseases taken orally and by injection. However, there is a paucity of evidence for inhaled ambroxol in sputum clearance. Methods: This study performed a multicenter, randomized, double-blind, placebo-controlled, phase 3 trial at 19 centers in China. Hospitalized adult patients with mucopurulent sputum and expectoration difficulty were recruited. Patients were randomized by 1:1 to receive inhalation of either ambroxol hydrochloride solution 3 mL (22.5 mg) + 0.9% sodium chloride 3 mL or 0.9% sodium chloride 6 mL twice daily for 5 days, with an interval of more than 6 h. The primary efficacy endpoint was the absolute change in the sputum property score after treatment compared to the baseline in the intention-to-treat population. Results: Between 10 April 2018 and 23 November 2020, 316 patients were recruited and assessed for eligibility, of whom 138 who received inhaled ambroxol and 134 who received a placebo were included. Patients who received inhaled ambroxol had a significantly greater decrease in the sputum property score compared with patients who received inhalation of placebo (difference: -0.29; 95% CI: -0.53 to -0.05; p = 0.0215). Compared with the placebo, inhaled ambroxol also significantly reduced more expectoration volume in 24 h (difference: -0.18; 95% CI: -0.34 to -0.03; p = 0.0166). There was no significant difference in the proportion of adverse events between the two groups, and no deaths were reported. Discussion: In hospitalized adult patients with mucopurulent sputum and expectoration difficulty, inhaled ambroxol was safe and effective for sputum clearance compared with a placebo. Clinical trial registration: [https://www.chictr.org.cn/showproj.html?proj=184677], Chinese Clinical Trial Registry [ChiCTR2200066348].

PO6 geometric configuration unit enhanced electrocatalytic performance of Co3O4 in acidic oxygen evolution.

It is challenging to develop high-efficient and stable nonprecious metal-based electrocatalyst for oxygen evolution reaction (OER) in acid for proton exchange membrane (PEM) water splitting. Herein, P atoms were introduced into the lattice of spinel Co3O4 (P-Co3O4) to replace with octahedral coordinated Co3+ via a hydrothermal process following a thermal treatment. The formation of PO6 geometric configuration unit in Co3O4 can trigger electron rearrangement around Co ions, which resulted in the high-active Co2+ site on the surface, significantly decreasing the energy barrier of rate-determining step for OER. Moreover, the weaker covalency of the Co 3d-O 2p bond and higher formation energy of oxygen vacancy around Co2+ in P-Co3O4 inhibited the participation of lattice oxygen during OER process, enabling that P-Co3O4 can work stably in acidic media. The obtained P-Co3O4 afforded satisfying stability over 30 h in a PEM electrolysis device with an overpotential of 400 mV@10 mA/cm2 in 0.1 M HClO4.

Stable Crystalline Nanohoop Radical and Its Self-Association Promoted by van der Waals Interactions.

A stable nanohoop radical (OR3) combining the structures of cycloparaphenylene and an olympicenyl radical is synthesized and isolated in the crystalline state. X-ray crystallographic analysis reveals that OR3 forms a unique head-to-tail dimer that further aggregates into a one-dimensional chain in the solid state. Variable-temperature NMR and concentration-dependent absorption measurements indicate that the π-dimer is not formed in solution. An energy decomposition analysis indicates that van der Waals interactions are the driving force for the self-association process, in contrast with other olympicenyl derivatives that favor π-dimerization. The physical properties in solution phase have been studied, and the stable cationic species obtained by one-electron chemical oxidation. This study offers a new molecular design to modulate the self-association of organic radicals for overcoming the spin-Peierls transition, and to prepare novel nanohoop compounds with spin-related properties.

Heterogenization of Salen Metal Molecular Catalysts in Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution.

Integrating a molecular catalyst with a light harvester into a photocatalyst is an effective strategy for solar light conversion. However, it is challenging to establish a crystallized framework with well-organized connections that favour charge separation and transfer. Herein, we report the heterogenization of a Salen metal complex molecular catalyst into a rigid covalent organic framework (COF) through covalent linkage with the light-harvesting unit of pyrene for photocatalytic hydrogen evolution. The chemically conjugated bonds between the two units contribute to fast photogenerated electron transfer and thereby promote the proton reduction reaction. The Salen cobalt-based COF showed the best hydrogen evolution activity (1378 µmol g-1 h-1 ), which is superior to the previously reported nonnoble metal based COF photocatalysts. This work provides a strategy to construct atom-efficient photocatalysts by the heterogenization of molecular catalysts into covalent organic frameworks.

The Construction of Phosphorus-Doped g-C3N4/Rh-Doped SrTiO3 with Type-II Band Alignment for Efficient Photocatalytic Hydrogen Evolution.

It is of great importance to promote charge separation in photocatalysts for enhanced photocatalytic activity under visible light irradiation. In this work, a type-II heterostructured photocatalyst was constructed by compositing phosphorus-doped g-C3N4 (P-CN) and Rh-doped SrTiO3 (Rh-STO) via a thermal calcination treatment. A series of characterizations were conducted to investigate the structure of heterostructured P-CN/Rh-STO. It was found that Rh-STO interacted with in situ generated P atoms from the decomposition of P-CN during the calcination process, thus leading to the formation of heterojunction of P-CN/Rh-STO. Compared with the single component, i.e., P-CN or Rh-STO, the obtained P-CN/Rh-STO showed superior photocatalytic activity to that of both P-CN and Rh-STO due to the effective charge separation across the heterojunction between P-CN and Rh-STO.

Hypercrosslinking porous polymer layers on TiO2-graphene photocatalyst: Enhanced adsorption of water pollutants for efficient degradation.

Solar-driven photocatalysis offers an environmentally friendly and sustainable approach for the degradation of organic pollutants in water without chemical additives, but the low specific surface area and adsorption capacity of common photocatalysts restricts the surface reactions with the contaminants. Herein, we hypercrosslinked polymer layers on TiO2-graphene surface to enlarge the specific surface area from 136 to 988 m2/g, leading to a high adsorption capacity of sulfadiazine as 54.3 mg/g, which is 15.5 times that of TiO2-graphene (3.5 mg/g). The adsorption kinetics reveals the combination of physical and chemical adsorption by porous benzene-based polymer for sulfadiazine enrichment. Besides, the polymer layers with broad light absorption enable the composite to function efficiently as visible-light-driven photocatalysts. Thus, the as-designed composite exhibits excellent performance for sulfadiazine removal by integrating the adsorptive and photocatalytic processes, especially for the diluted sulfadiazine solution. More importantly, the porous polymer layer can function as a filter for weakening the interference of TiO2 surface with the natural matters from complex water matrices. Based on the identification of dominant reactive species, the possible attacking pathway and the sulfadiazine subsequent degradation are presented. Further, the enhanced adsorption and photodegradation efficiency can also be achieved for the removal of other typical pollutants such as 4-chlorophenol and methylene blue. This study highlights an adsorption-enhanced-degradation mechanism for water pollutants that can direct the design of high-performance photocatalysts under visible light.

In situ photodeposition of platinum clusters on a covalent organic framework for photocatalytic hydrogen production.

Photocatalytic hydrogen production has been considered a promising approach to obtain green hydrogen energy. Crystalline porous materials have arisen as key photocatalysts for efficient hydrogen production. Here, we report a strategy to in situ photodeposit platinum clusters as cocatalyst on a covalent organic framework, which makes it an efficient photocatalyst for light-driven hydrogen evolution. Periodically dispersed adsorption sites of platinum species are constructed by introducing adjacent hydroxyl group and imine-N in the region of the covalent organic framework structural unit where photogenerated electrons converge, leading to the in situ reduction of the adsorbed platinum species into metal clusters by photogenerated electrons. The widespread platinum clusters on the covalent organic framework expose large active surface and greatly facilitate the electron transfer, finally contributing to a high photocatalytic hydrogen evolution rate of 42432 µmol g-1 h-1 at 1 wt% platinum loading. This work provides a direction for structural design on covalent organic frameworks to precisely manipulate cocatalyst morphologies and positions at the atomic level for developing efficient photocatalysts.

Stacking Engineering: A Boosting Strategy for 2D Photocatalysts.

Two-dimensional (2D) photocatalytic material is a vital project for modern solar energy conversion and storage. Despite a vast family of potential 2D photocatalysts that is demonstrated, their commercial applications are severely limited because of fast photogenerated electron-hole recombination. Here, based on first-principles, we propose a general paradigm to boost the separation of photoexcited charge carriers in 2D photocatalysts by stacking engineering. Taking the emerging water splitting photocatalyst MoSi2N4 as an example, we show that specific interlayer stacking-induced electric polarization plays a significant role in altering the electronic properties and thus the suppressed recombination rate of photoexcited carriers. Moreover, we find that the catalytic performance can be further controlled by vertical strain. These generalized findings not only highlight the importance of stacking-induced electric polarization but also offer new prospects for the design and application of 2D photocatalysts.

A Porphyrin-Based Covalent Organic Framework for Metal-Free Photocatalytic Aerobic Oxidative Coupling of Amines.

Imines are important intermediates in drug synthesis. Photocatalytic aerobic oxidative coupling of amines has been considered as a clean and promising way to produce imines and has attracted great attention. Herein, we designed and synthesized a novel two-dimensional porphyrin-based covalent organic framework (Por-BC-COF) which adopts an AA stacking mode with excellent crystallinity, high Brunauer-Emmett-Teller surface areas (1200 m2 g-1 ), wide light absorption range (200-1300 nm) and good stability in a variety of organic solvents. Por-BC-COF can be used as a metal-free heterogeneous photocatalyst for the photocatalytic oxidation of amines to imines under visible light and red light with a high yield (97 %). This work presents a novel and efficient COF photocatalyst in the application of light-driven organic synthesis.

[Effects of Cullin1 on the Biological Characteristics of Lung Adenocarcinoma
A549 and H1395 Cells].

BACKGROUND: Cullin1 is a representative member of the Cullin family, and it plays an important role in the ubiquitination of cell cycle, transcription and signal transduction related proteins. Cullin1 is closely related to the occurrence and development of a variety of malignant tumors. The aim of this study is to investigate the effects of Cullin1 on biological function of lung adenocarcinoma A549 and H1395 Cells. METHODS: The expression of Cullin1 mRNA was detected by quantitative Real-time polymerase chain reaction in lung adenocarcinoma cells (A549, H358, H1395, H1650) and human normal lung epithelial cells BEAS-2B, siRNA technology was used to interfere with lung adenocarcinoma cells with relatively high expression of Cullin1 mRNA; cell proliferation, cell cycle distribution, early cell apoptosis, invasion and migration ability were detected by methyl thiazolyl tetrazolium assay (MTT), flow cytometry and Transwell experiment; Western blot was used to detect the expression levels of matrix metalloproteinase-2 (MMP-2), matrix metalloproteinase-9 (MMP-9), tissue inhibitor of metalloproteinase-1 (TIMP-1), Cyclin D1, Cyclin E2, p21 and p27. RESULTS: Compared with the BEAS-2B cell, Cullin1 mRNA was highly expressed in lung adenocarcinoma cells, especially in lung adenocarcinoma A549 and H1395 cells (P<0.05). The proliferation ability of lung adenocarcinoma cells was inhibited after interference with Cullin1, and the number of cells in G1 phase increased, the number of cells in S phase decreased, and the early apoptosis rate of lung adenocarcinoma cells is significantly increased (P<0.05); The invasion and migration ability of lung adenocarcinoma cells decreased (P<0.05). After interference with Cullin1, the protein expression of MMP-9, MMP-2, CyclinD1 and CyclinE2 decreased (P<0.05), while the expression of TIMP-1, p21 and p27 protein increased (P<0.05). CONCLUSIONS: Interference with Cullin1 inhibits the proliferation, invasion and migration of lung adenocarcinoma A549 and H1395 cells, Cullin1 plays a role in promoting cancer in lung adenocarcinoma.

Efficacy and Safety of Budesonide/Glycopyrrolate/Formoterol Fumarate Metered Dose Inhaler in Chinese Patients with COPD: A Subgroup Analysis of KRONOS.

INTRODUCTION: This pre-specified subgroup analysis evaluated the efficacy and safety of budesonide/glycopyrrolate/formoterol fumarate metered dose inhaler (BGF MDI) triple therapy versus corresponding dual therapies in the China subgroup of the phase III, double-blind KRONOS study in patients with moderate to very severe chronic obstructive pulmonary disease (COPD). METHODS: Patients were randomized 2:2:1:1 to BGF MDI 320/18/9.6 µg, glycopyrrolate/formoterol fumarate (GFF) MDI 18/9.6 µg, budesonide/formoterol fumarate (BFF) MDI 320/9.6 µg, or budesonide/formoterol fumarate dry powder inhaler (BUD/FORM DPI) 400/12 µg twice daily for 24 weeks. The primary endpoint was change from baseline in morning pre-dose trough forced expiratory volume in 1 s (FEV1) over weeks 12-24. Secondary endpoints included symptoms, health-related quality of life, and safety. Rate of moderate/severe COPD exacerbations was an additional efficacy endpoint. RESULTS: In the China subgroup (n = 432; 22.7% of the KRONOS population), BGF MDI demonstrated nominally significant improvements in the primary endpoint versus BFF MDI (least squares mean (LSM) difference 68 mL; P = 0.0035) and BUD/FORM DPI (LSM difference 78 mL; P = 0.0010) but not GFF MDI (LSM difference - 4 mL; P = 0.8316). BGF MDI demonstrated at least numerical improvements versus comparators in secondary lung function and symptom endpoints. BGF MDI reduced the rate of moderate/severe COPD exacerbations versus GFF MDI (rate ratio 0.41; P = 0.0030), with numerical benefits versus BFF MDI and BUD/FORM DPI. All treatments were well tolerated. CONCLUSIONS: Results demonstrated that BGF MDI showed benefits on lung function (vs inhaled corticosteroid/long-acting ß2-agonist), as well as symptoms and exacerbations relative to dual therapies. Findings support BGF MDI use in Chinese patients with moderate to very severe COPD. CLINICAL TRIAL REGISTRATION: ClinicalTrials.gov NCT02497001.

High Expression of Metallo-ß-Lactamase Contributed to the Resistance to Carbapenem in Clinical Isolates of Pseudomonas aeruginosa from Baotou, China.

BACKGROUND: Bacterial resistance to antibiotics has become a major public health concern. This study aimed to determine the resistance mechanisms to carbapenem in clinical isolates of Pseudomonas aeruginosa. METHODS: A total of 62 clinical isolates of carbapenem-resistant P. aeruginosa (CRPA) were collected from 2015 to 2017. Imipenem (IPM)-EDTA disk synergy test was used to screen strains that produced metallo-ß-lactamase. In addition, the genes for outer membrane protein OprD2, metallo-ß-lactamase and mexR gene were amplified and sequenced. Expression of mexA was detected by real-time PCR. RESULTS: Disk synergy test showed that 51.6% (32/62) of the strains were positive for metallo-ß-lactamase. PCR showed that 84.4% of the strains were SIM-positive (27/32), 15.6% of the strains were IMP-positive (5/32), and 12.5% of the strains were VIM-positive (4/32). SPM-positive and GIM-positive strains were not detected. In addition, 5 of the 62 strains had small deletions and/or point mutations in OprD2. Three strains had a high expression of mexA, while eight strains were positive for the regulatory gene mexR with no mutations detected by DNA sequencing. CONCLUSION: Expression of metallo-ß-lactamase is the main resistance mechanism of P. aeruginosa to carbapenem. Mutations in OprD2 and/or the overexpression of efflux pump MexAB-OprM may contribute to P. aeruginosa resistance to carbapenem.

Interferon induced transmembrane protein 3 regulates the growth and invasion of human lung adenocarcinoma.

BACKGROUND: Interferon induced transmembrane protein 3 (IFITM3) plays an important role in the tumorigenesis and progression of multiple cancers. This study investigated the expression and function of IFITM3 in human lung adenocarcinoma. METHODS: Fifty human lung adenocarcinoma tissues were collected. IFITM3 expression was assessed by immunohistochemical staining. The clinicopathologic characteristics of all patients were analyzed. RESULTS: IFITM3 was mainly detected in the cytoplasm of advanced cancer tissues and its expression was correlated with tumor malignancy grade. Knockdown of IFITM3 in vitro markedly inhibited the proliferation and invasion of lung adenocarcinoma cells. CONCLUSION: IFITM3 represents a potential therapeutic target for the treatment of lung adenocarcinoma.

A multicenter, cross-sectional, observational study of budesonide/formoterol maintenance and reliever therapy in real-world settings.

BACKGROUND: To assess the level of asthma control achieved with budesonide/formoterol in Chinese patients with asthma, based on the Global Initiative for Asthma (GINA) definition and Asthma Control Test (ACT) score. METHODS: This multicenter, cross-sectional study (NCT01785901) evaluated asthma control levels in Chinese patients receiving physician-prescribed budesonide/formoterol treatment. Adults with a diagnosis of asthma ≥6 months and receiving budesonide/formoterol treatment ≥3 months before screening were consecutively enrolled. Data including medical and medication history were collected using face-to-face questionnaires and physical examinations during a single visit. RESULTS: A total of 1483 asthma out-patients from 27 medical centers were enrolled; 217 (14.6%) were treated with budesonide/formoterol using a fixed-dose strategy and 1266 (85.4%) with the SMART (Symbicort® Maintenance And Reliever Therapy) strategy. According to GINA criteria, asthma was controlled in 58.6% (95% CI: 56.1%-61.1%) of patients and was either controlled or partly controlled in 94.1% (95% CI: 92.8%-95.3%) of patients. According to ACT score, asthma was completely controlled in 22.4% (95% CI: 20.3%-24.6%) of patients and was either completely or well controlled in 83.3% (95% CI: 81.4%-85.2%) of patients. Multivariate logistic regression analysis revealed that a >5-year history of asthma and an age of >50 years were factors associated with lower levels of asthma control. CONCLUSIONS: This study demonstrated high levels of asthma control (GINA: controlled and partly controlled and ACT: completely and well controlled) in Chinese patients with asthma treated with budesonide/formoterol. Greater age and a longer disease history were associated with lower levels of asthma control. TRIAL REGISTRATION: ClinicalTrials.govNCT01785901. Registered February 5, 2013.

Upregulated miR-483-5p expression as a prognostic biomarker for esophageal squamous cell carcinoma.

BACKGROUND: Esophageal squamous cell carcinoma (ESCC) is one of the most common cause of cancer-associated mortality. Uncovering novel molecular biomarkers that can predict ESCC development will improve personalized therapy. OBJECTIVE: The goal of the current study was to investigate the expression pattern of miR-483-5p and determine its prognostic value in ESCC. METHODS: We first analyzed miRNA-seq data obtained from the Cancer Genome Atlas (TCGA) cohort to evaluate the prognostic value of miR-483-5p in ESCC. Then quantitative real-time RT-PCR (qRT-PCR) was carried out to compare the miR-483-5p levels in 80 pairs of ESCC tissues and adjacent non-cancerous tissues. The correlation between miR-483-5p levels and clinical features were determined. RESULTS: For the TCGA cohort, ESCC patients with higher miR-483-5p had significantly shorter overall survival time. The examined ESCC cancer tissues exhibited a remarkable increment in miR-483-5p expression compared with the adjacent normal tissues. miR-483-5p was positively correlated with TNM stage, lymph nodes metastasis and T stage. In addition, upregulate miR-483-5p expression was also found to be significantly associated with poor survival of ESCC patients. Furthermore, miR-483-5p expression was an independent prognostic factor for overall survival and disease free survival in ESCC patients. CONCLUSIONS: Our study demonstrates that miR-483-5p might be a tumor promoter of ESCC, which provide a promising prognostic biomarker and therapeutic target.

[Reproducibility of Gleason scores in prostate cancer].

OBJECTIVE: To investigate the reproducibility of Gleason scores for prostate cancer. METHODS: Based on the revised Gleason Scoring System of the International Society of Urological Pathology ( ISUP) , we analyzed the reproducibility and difference of Gleason scores in 49 cases of prostate cancer using the methods of combination and grouping. RESULTS: The total reproducibility of Gleason scores among 15 pathologists was good (κ = 0.642), 62.2% by the combination method, the highest in Gleason 5 + 5 (81.2%) and 5 +4 (73.3%), then in Gleason 4 + 4 (67.5%), 3 + 3 (64.0%), 4 +3 (61.3%), and 3 + 4 (44.0%), and the lowest in Gleason 4 + 5 (38.9%) and 3 + 5 (33.3%). The total reproducibility of Gleason scores by the grouping method was 71.4%, the highest in Gleason 9-10 (84.9%) , then in Gleason 7 (76.7%) and 6 (64.0%), and the lowest in Gleason 8 (60.7%). CONCLUSION: The reproducibility of Gleason scores remains to be further improved in prostate cancer, mainly concerning the understanding of Gleason 3 and 4 carcinoma.

Survival of hepatitis C virus in syringes: implication for transmission among injection drug users.

BACKGROUND: We hypothesized that the high prevalence of hepatitis C virus (HCV) among injection drug users might be due to prolonged virus survival in contaminated syringes. METHODS: We developed a microculture assay to examine the viability of HCV. Syringes were loaded with blood spiked with HCV reporter virus (Jc1/GLuc2A) to simulate 2 scenarios of residual volumes: low void volume (2 microL) for 1-mL insulin syringes and high void volume (32 microL) for 1-mL tuberculin syringes. Syringes were stored at 4 degrees C, 22 degrees C, and 37 degrees C for up to 63 days before testing for HCV infectivity by using luciferase activity. RESULTS: The virus decay rate was biphasic (t1/2alpha= 0.4 h and t1/2beta = 28 hh). Insulin syringes failed to yield viable HCV beyond day 1 at all storage temperatures except 4 degrees , in which 5% of syringes yielded viable virus on day 7. Tuberculin syringes yielded viable virus from 96%, 71%, and 52% of syringes after storage at 4 degrees, 22 degrees, and 37 degrees for 7 days, respectively, and yielded viable virus up to day 63. CONCLUSIONS: The high prevalence of HCV among injection drug users may be partly due to the resilience of the virus and the syringe type. Our findings may be used to guide prevention strategies.