Significance of Engineering the MnO6 Octahedral Units to Promote the Oxygen Reduction Reaction of Perovskite Oxides.

The electronic structure and geometric configuration of catalysts play a crucial role to design novel perovskite-type catalysts for oxygen reduction reaction (ORR). Nowadays, many studies are more concerned with the influence of electronic structure and ignore the geometric effect, which plays a nonnegligible role in enhancing catalytic performances. Herein, this work regulates the MnO6 octahedral tilting degree of LaMnO3 by modulating the concentration of Y3+, excluding the electronic effect from the valence state of manganese. Plotting the MnO6 octahedral tilting degree as a function of concentration of Y3+ produces a volcano-shaped plot. The octahedral tilting can reduce the Mn-O covalency, generating more highly active Mn3+ and oxygen vacancies during ORR process. The specific activity has a positive correlation with octahedral tilting degree. Meanwhile, the octahedral tilting stabilizes Mn-O interactions during ORR process and promote stability. Based on experimental results and DFT calculations, octahedral tilting alters the rate-determining step (RDS) and decrease the energy barrier. Subsequent extended experiment confirms that octahedral tilting is the key factor to affect the catalytic performances.

Triggered lattice-oxygen oxidation with active-site generation and self-termination of surface reconstruction during water oxidation.

To master the activation law and mechanism of surface lattice oxygen for the oxygen evolution reaction (OER) is critical for the development of efficient water electrolysis. Herein, we propose a strategy for triggering lattice-oxygen oxidation and enabling non-concerted proton-electron transfers during OER conditions by substituting Al in La0.3Sr0.7CoO3-δ. According to our experimental data and density functional theory calculations, the substitution of Al can have a dual effect of promoting surface reconstruction into active Co oxyhydroxides and activating deprotonation on the reconstructed oxyhydroxide, inducing negatively charged oxygen as an active site. This leads to a significant improvement in the OER activity. Additionally, Al dopants facilitate the preoxidation of active cobalt metal, which introduces great structural flexibility due to elevated O 2p levels. As OER progresses, the accumulation of oxygen vacancies and lattice-oxygen oxidation on the catalyst surface leads to the termination of Al3+ leaching, thereby preventing further reconstruction. We have demonstrated a promising approach to achieving tunable electrochemical reconstruction by optimizing the electronic structure and gained a fundamental understanding of the activation mechanism of surface oxygen sites.

Combined Use of Tumor Markers in Gastric Cancer: A Novel Method with Promising Prognostic Accuracy and Practicality.

BACKGROUND: The effect of a single tumor marker on the prognosis of gastric cancer patients is not ideal. This study explored a novel prognostic assessment method for gastric cancer (GC) patients using a combination of three important tumor markers (CEA, CA72-4, and CA19-9). METHOD: Data from 1966 GC patients who underwent curative gastrectomy at Sun Yat-Sen University Cancer Center (Guangzhou, China) were included. Hazard ratios (HR) for all factors for overall survival (OS) were analyzed by Cox regression. A nomogram and calibration curve were used to establish the survival prediction model. The prediction accuracy was evaluated with the concordance index (C-index). RESULTS: All patients were divided into four groups (C0-C3) according to the number of elevated tumor markers. The 5-year OS rates of the patients in preoperative groups C0-C3 were 83.8% (81.3-86.4%), 72.8% (68.5-77.4%), 58.9% (50.4-68.9%), and 18.5% (4.0-33.0%), respectively, and those in postoperative groups C0-C3 were 82.1% (79.4-84.8%), 76.1% (72.2-80.3%), 57.6% (48.4-68.5%), and 16.8% (5.1-28.5%), respectively, with significant differences between each C0-C3 subgroup in both preoperative and postoperative cohorts. Multivariate analysis showed that preoperative (HR: 6.001, 95% CI: 3.523-10.221) and postoperative (HR: 8.149, 95% CI: 4.962-13.528) elevated tumor markers were independent risk factors for GC patients. The C-index for the combined use of tumor markers was 0.65-0.66, which was higher than that for using a single tumor marker (0.53-0.56). CONCLUSION: The combined use of tumor markers significantly improved the prognostic value compared with using a single tumor marker. The survival prediction model including the combined tumor markers was accurate and effective.

The relationship between social acknowledgment and prolonged grief symptoms: a multiple mediation effect of beliefs about the goodness and controllability of grief-related emotions.

Background: Social acknowledgment is a protective factor for survivors of trauma. However, the role of social acknowledgment in association with prolonged grief symptoms has not yet been established.Objectives: The current study aims to explore the relationship between social acknowledgment and prolonged grief via two beliefs foundational to how people think about grief-related emotions (1) goodness (i.e. whether emotions are desirable, useful, or unwanted and harmful), and (2) controllability (i.e. whether emotions are regulated according to our will or involuntary, arising of their own accord). These effects were explored in two different cultural samples of bereaved people.Methods: One hundred and fifty-four German-speaking and two hundred and sixty-two Chinese bereaved people who lost their loved ones completed questionnaires assessing social acknowledgment, beliefs about the goodness and controllability of grief-related emotions, and prolonged grief symptoms.Results: Correlation analyses showed that social acknowledgment was positively linked with stronger beliefs about the goodness and controllability of grief-related emotions and negatively related to prolonged grief symptoms. Beliefs about the goodness and controllability of grief-related emotions correlated negatively with prolonged grief symptoms. Multiple mediation analyses suggested that beliefs about the controllability and goodness of grief-related emotions mediated the link between social acknowledgment and prolonged grief symptoms. Cultural groups did not moderate the above model.Conclusion: Social acknowledgment may be related to bereavement adjustment consequences via the roles of beliefs about the goodness and controllability of grief-related emotions. These effects seem to be consistent cross-culturally.

Social acknowledgment correlated positively with stronger beliefs about the goodness and controllability of grief-related emotions and negatively with prolonged grief symptoms.Beliefs about the goodness and controllability of grief-related emotions were negatively linked with prolonged grief symptoms.Beliefs about the controllability and goodness of grief-related emotions mediated the relationship between social acknowledgment and prolonged grief symptoms. The model presented cross-cultural consistency.

Synthesis of Bandgap-tunable Transition Metal Sulfides through Gas-phase Cation Exchange-induced Topological Transformation.

Oriented synthesis of transition metal sulfides (TMSs) with controlled compositions and crystal structures has long been promising for electronic devices and energy applications. Liquid-phase cation exchange (LCE) is a well-studied route by varying the compositions. However, achieving crystal structure selectivity is still a great challenge. Here, we demonstrate gas-phase cation exchange (GCE), which can induce a specific topological transformation (TT), for the synthesis of versatile TMSs with identified cubic or hexagonal crystal structures. The parallel six-sided subunit (PSS), a new descriptor, is defined to describe the substitution of cations and the transition of the anion sublattice. Under this principle, the band gap of targeted TMSs can be tailored. Using the photocatalytic hydrogen evolution as an example, the optimal hydrogen evolution rate of a zinc-cadmium sulfide (ZCS4) is determined to be 11.59 mmol h-1 g-1 , showing a 36.2-fold improvement over CdS.

Comprehensively Understanding the Role of Anion Vacancies on K-Ion Storage: A Case Study of Se-Vacancy-Engineered VSe2.

Anion vacancy engineering (AVE) is widely used to improve the Li-ion and Na-ion storage of conversion-type anode materials. However, AVE is still an emerging strategy in K-ion batteries, which are promising for large-scale energy storage. In addition, the role of anion vacancies on ion storage is far from clear, despite several proposed explanations. Herein, by employing VSe2 as a model conversion-type anode material, Se vacancies are intentionally introduced (labeled as P-VSe2-x ) to investigate their effect on K+ storage. The P-VSe2-x shows excellent cyclability in half cells (143 mA h g-1 at 3.0 A g-1 after 1000 cycles) and high energy density in coin-type full cells (206.8 Wh kg-1 ). By applying various electrochemical techniques, the effects of Se vacancies on the redox potentials of K-ion insertion/extraction and the K-ion diffusion in electrodes upon cycling are uncovered. In addition, the structural evolution of Se vacancies during potassiation/de-potassiation using various operando and ex characterizations is revealed. Moreover, it is demonstrated that Se vacancies can facilitate the breaking of VSe bonds upon the P-VSe2-x conversion using theoretical calculations. This work comprehensively explains the role of anion vacancies in ion storage for developing high-performance conversion-type anode materials.

Adjuvant Chemotherapy for Patients with Adenocarcinoma of the Esophagogastric Junction: A Retrospective, Multicenter, Observational Study.

BACKGROUND: Although the incidence of adenocarcinoma of the esophagogastric junction (AEG) has been increasing since the past decade, the proportion of AEG cases in two previous clinical trials (ACTS-GC and CLASSIC) that investigated the efficacy of adjuvant chemotherapy was relatively small. Therefore, whether AEG patients can benefit from adjuvant chemotherapy remains unclear. METHODS: Patients who were diagnosed with pathological stage II/III, Siewert II/III AEG, and underwent curative surgery at three high-volume institutions were assessed. Clinical outcomes were analyzed by using Kaplan-Meier curves, log-rank test, and Cox regression model. Propensity score matching (PSM) was used to reduce the selection bias. RESULTS: A total of 927 patients were included (the chemotherapy group: 696 patients; the surgery-only group: 231 patients). The median follow-up was 39.0 months. The 5-year overall survival was 63.1% (95% confidence interval [CI]: 59.0-67.6%) for the chemotherapy group and 50.2% in the surgery-only group (hazard ratio [HR] = 0.69, 95% CI: 0.54-0.88; p = 0.003). The 5-year, disease-free survival was 35.4% for the chemotherapy group and 16.6% for the surgery-only group (HR = 0.66, 95% CI: 0.53-0.83; p < 0.001). After PSM, the survival benefit of adjuvant chemotherapy for AEG was maintained. Multivariate analysis for overall survival and disease-free survival further demonstrated the survival benefit of adjuvant chemotherapy, with HRs of 0.63 (p < 0.001) and 0.52 (p < 0.001), respectively. CONCLUSIONS: Postoperative adjuvant chemotherapy was associated with improved overall survival and disease-free survival in patients with operable stage II or III AEG after D2 gastrectomy.

A bibliometric review on latent topics and research trends in the growth mindset literature for mathematics education.

Embracing a growth mindset is essential to students' academic improvement. This manuscript aims to better understand the existing literature on the role and effects of the growth mindset in mathematics teaching and learning. It provides an updated perspective on the research regarding the growth mindset in mathematics education. The dataset comprises 85 journal articles published from 2012 to 2022 retrieved from the Web of Science (WOS) and Scopus databases. The current study applies a methodology based on bibliometric analysis techniques. The analysis reveals and corroborates several patterns from the research trends, journals, countries, and authors that have significant impacts on the research field. The findings show that USA, UK, and Norway are the most productive countries in publishing research on the topic. Moreover, the results of the thematic analysis indicate that the topics discussed among most of the articles in the dataset include engagement, implementation, persistence, children, fluid intelligence, and skills. The longitudinal trends in research themes based on study keywords illustrate an evolution in the research from the concept of mindsets to implicit theories on the growth mindset alongside academic achievement. Lastly, this study also provides an overview of the conceptual structure underlying studies on the growth mindset, which offers valuable insights into potential research topics for academics and practitioners seeking to explore the growth mindset in the future.

Function and therapeutic potential of transient receptor potential ankyrin 1 in fibrosis.

The transient receptor potential (TRP) protein superfamily is a special group of cation channels expressed in different cell types and signaling pathways. In this review, we focus on TRPA1 (transient receptor potential ankyrin 1), an ion channel in this family that exists in the cell membrane and shows a different function from other TRP channels. TRPA1 usually has a special activation effect that can induce cation ions, especially calcium ions, to flow into activated cells. In this paper, we review the role of TRPA1 in fibroblasts. To clarify the relationship between fibroblasts and TRPA1, we have also paid special attention to the interactions between TRPA1 and inflammatory factors leading to fibroblast activation. TRPA1 has different functions in the fibrosis process in different organs, and there have also been interesting discussions of the mechanism of TRPA1 in fibroblasts. Therefore, this review aims to describe the function of TRP channels in controlling fibrosis through fibroblasts in different organ inflammatory and immune-mediated diseases. We attempt to prove that TRPA1 is a target for fibrosis. In fact, some clinical trials have already proven that TRPA1 is a potential adjuvant therapy for treating fibrosis.

Caregivers' burden and schizophrenia patients' quality of life: Sequential mediating effects of expressed emotion and perceived expressed emotion.

Background: Increasing attention has been paid to the role of caregivers' burden in affecting quality of life (QoL) of schizophrenic patients. However, less is known about potential mediation mechanisms underlying this relationship. The current study aimed to explore the sequential mediating effect of expressed emotion and perceived expressed emotion on the relationship between care burden and QoL among people with schizophrenia. Methods: 135 Chinese families (one patient and one caregiver) participated in this study. Caregivers reported their care burden and expressed emotion, patients reported their perceived expressed emotion and QoL. Results: The results of the correlation analysis showed that care burden was negatively related to patients' QoL, including physical, psychological, and social relationships domains, with patients' sex, age, educational level, employment status, and medication-taking as covariates. The sequential mediating effects of criticism and perceived criticism between care burden and QoL were not significant. However, the sequential mediating effects of emotional over-involvement and perceived emotional over-involvement (EOI) between care burden and QoL (including physical and psychological domain) were significant. Conclusion: The results indicated that reducing the burden and expressed emotion of caregivers could be helpful to improve schizophrenia patients' QoL.

Controlling the Cation Exsolution of Perovskite to Customize Heterostructure Active Site for Oxygen Evolution Reaction.

Perovskite oxides are an important class of oxygen evolution reaction (OER) catalysts offering an ordered atomic arrangement and a highly flexible electronic structure. Currently, understanding and adjusting the dynamic reconstruction of perovskite during the OER process remains a formidable challenge. Here, we report the artificial construction of a heterostructure by the cation exsolution of perovskite to control the active site formation and reconstruction. The deliberately made La deficiency in LaNiO3 perovskite facilitates the original segregation of NiO from the parent matrix and forms a well-defined interface between perovskite parent and NiO exsolution phase. The dynamic formation process of such heterojunction was studied by density functional theory computation and high quality imaging characterization. Due to the valence redistribution of Ni ions caused by the interfacial electron transfer, the in situ formed LaNiO3/NiO heterostructure displays high electroactivity. Therefore, the LaNiO3/NiO heterostructure exhibits a dynamic surface evolution feature with the generation of the highly active NiOOH layer under a low anodic potential (∼1.35 V vs RHE) during the OER process, which is very different from the conventional LaNiO3 with a stoichiometry and NiO catalysts. With the newly formed heterostructure, the reconstructed catalysts impart a 4.5-fold increase in OER activity and a 3-fold improvement in stability against La and Ni dissolution during the OER process. This work provides a feasible interface engineering strategy for artificially controlling the reconstruction of the active phase in high-performance perovskite-based electrocatalytic materials.

Activation Strategies of Perovskite-Type Structure for Applications in Oxygen-Related Electrocatalysts.

The oxygen-related electrochemical process, including the oxygen evolution reaction and oxygen reduction reaction, is usually a kinetically sluggish reaction and thus dominates the whole efficiency of energy storage and conversion devices. Owing to the dominant role of the oxygen-related electrochemical process in the development of electrochemical energy, an abundance of oxygen-related electrocatalysts is discovered. Among them, perovskite-type materials with flexible crystal and electronic structures have been researched for a long time. However, most perovskite materials still show low intrinsic activity, which highlights the importance of activation strategies for perovskite-type structures to improve their intrinsic activity. In this review, the recent progress of the activation strategies for perovskite-type structures is summarized and their related applications in oxygen-related electrocatalysis reactions, including electrochemistry water splitting, metal-air batteries, and solid oxide fuel cells are discussed. Furthermore, the existing challenges and the future perspectives for the designing of ideal perovskite-type structure catalysts are proposed and discussed.

Palliative Gastrectomy versus Gastrojejunostomy for advanced Gastric cancer with outlet obstruction: a propensity score matching analysis.

BACKGROUND: Gastric outlet obstruction (GOO) is a late complication of advanced gastric cancer, and it is controversial how to select the therapeutic strategies: gastrojejunostomy and palliative gastrectomy? Therefore, this study was to compare the surgical and survival outcomes of gastrojejunostomy and palliative gastrectomy. METHODS: In total, 199 gastric cancer patients with outlet obstruction treated by surgery between January 2000 and December 2015 at Sun Yat-sen University Cancer Center were retrospectively reviewed. Patients were divided into gastrojejunostomy group and palliative gastrectomy group. Propensity score matching (PSM) was performed to balance the selection bias. RESULTS: After 1:1 PSM, a total of 104 patients were included for final analysis. The median overall survival (OS) times in the gastrojejunostomy group and palliative gastrectomy group were 8.50 and 11.87 months, respectively (P = 0.243). The postoperative complication rates in the gastrojejunostomy group and palliative gastrectomy group were 19.23% (10/52) and 17.31% (9/52), respectively (P = 0.800), and no treatment-related death was observed. Multivariate analysis showed that periton0eal seeding (P = 0.014) and chemotherapy (P < 0.001) were independent prognostic factors. Among them, peritoneal seeding was a risk factor and postoperative chemotherapy was a protective factor. CONCLUSIONS: Our results indicated that although the surgical complications of palliative gastrectomy were manageable, it showed no survival benefit. Therefore, relieving obstruction symptom, improving patients' quality of life and creating better conditions for chemotherapy appear to be the main therapeutic strategies for advanced gastric cancer with GOO.

Human Cartilage Homogenates Influence the Crystallization of Monosodium Urate and Inflammatory Response to Monosodium Urate Crystals: A Potential Link Between Osteoarthritis and Gout.

OBJECTIVE: Monosodium urate (MSU) crystal deposition and gout flares frequently affect osteoarthritic joints. This study was undertaken to examine the effects of human cartilage homogenates on MSU crystallization and MSU crystal-induced inflammation. METHODS: Human cartilage homogenates were prepared from macroscopically healthy and macroscopically diseased knee joint samples. Crystallization assays were used to test the effects of cartilage homogenates or individual cartilage factors on MSU crystallization. Changes in urate solubility, crystal nucleation, crystal growth, and total crystal mass were determined. THP-1 cell assays were used to assess cytokine release following culture with MSU crystals grown in the presence or absence of cartilage homogenates or individual proteins. RESULTS: Addition of either 5% or 10% healthy cartilage homogenate increased the total mass of MSU crystals formed and resulted in formation of shorter MSU crystals compared to controls without cartilage homogenate. MSU crystal bows were observed in both the presence and absence of cartilage homogenate; however, bows formed in the presence of cartilage homogenates were significantly shorter than bows formed in their absence. There were no effect differences between macroscopically healthy and macroscopically diseased cartilage homogenates in all assessments. Addition of either type II collagen or albumin also led to the formation of shorter MSU crystals. In THP-1 cell assays, MSU crystals grown with healthy cartilage homogenate increased the release of interleukin-8, whereas MSU crystals grown with type II collagen or albumin had no effect on inflammatory cytokine release. CONCLUSION: In the presence of elevated urate levels, human cartilage homogenates increase MSU crystal formation and promote the formation of smaller crystals, which have greater inflammatory potential. These processes may contribute to the predilection of osteoarthritic joints to develop gout.

Co(OH)2 Nanoparticle-Encapsulating Conductive Nanowires Array: Room-Temperature Electrochemical Preparation for High-Performance Water Oxidation Electrocatalysis.

It is highly desired but still remains challenging to design and develop a Co-based nanoparticle-encapsulated conductive nanoarray at room temperature for high-performance water oxidation electrocatalysis. Here, it is reported that room-temperature anodization of a Co(TCNQ)2 (TCNQ = tetracyanoquinodimethane) nanowire array on copper foam at alkaline pH leads to in situ electrochemcial oxidation of TCNQ- into water-insoluable TCNQ nanoarray embedding Co(OH)2 nanoparticles. Such Co(OH)2 -TCNQ/CF shows superior catalytic activity for water oxidation and demands only a low overpotential of 276 mV to drive a geometrical current density of 25 mA cm-2 in 1.0 m KOH. Notably, it also demonstrates strong long-term electrochemical durability with its activity being retrained for at least 25 h, a high turnover frequency of 0.97 s-1 at an overpotential of 450 mV and 100% Faradic efficiency. This study provides an exciting new method for the rational design and development of a conductive TCNQ-based nanoarray as an interesting 3D material for advanced electrochemical applications.

In situ Formed Co(TCNQ)2 Metal-Organic Framework Array as a High-Efficiency Catalyst for Oxygen Evolution Reactions.

Energy conversion and storage systems such as water splitting devices and metal-air batteries need excellent and energy-efficiency oxygen evolution reaction (OER) catalysts. This work reports the in situ development of sawtooth-like Co(TCNQ)2 (TCNQ=tetracyanoquinodimethane) metal-organic framework array on Co foil (Co(TCNQ)2 /Co) by means of a solution immersion method at room temperature. As an oxygen-evolving catalyst, the resulting Co(TCNQ)2 /Co demonstrates superior OER activity with overpotential of 310 mV to drive a geometrical catalytic current density of 15 mA cm-2 in 1.0 M KOH. Notably, it also shows good long-term electrochemical durability with its activity being retained for at least 20 h and achieves a high turnover frequency of 0.66 mol O2 s-1 at overpotential of 380 mV.

CoC2O4·2H2O derived Co3O4 nanorods array: a high-efficiency 1D electrocatalyst for alkaline oxygen evolution reaction.

Energy conversion and storage systems such as water splitting metal-air batteries require high-performance and durable oxygen evolution reaction (OER) catalysts. Herein, we report the in situ development of self-standing Co3O4 nanorods array on Co foil (Co3O4 NA/CF) as a 1D OER catalyst electrode. Such Co3O4 NA/CF only needs overpotential of 308 mV to drive a geometrical catalytic current density of 15 mA cm-2 in 1.0 M KOH with good long-term electrochemical durability. In addition, this catalyst achieves a high turnover frequency of 0.646 mol O2 s-1 at overpotential of 410 mV.

In situ electrochemical development of copper oxide nanocatalysts within a TCNQ nanowire array: a highly conductive electrocatalyst for the oxygen evolution reaction.

It is highly desired to develop efficient earth-abundant electrocatalysts for the oxygen evolution reaction (OER) in alkaline media. In this communication, we report the in situ electrochemical conversion of a nanoarray of Cu(tetracyanoquinodimethane), Cu(TCNQ), an inorganic-organic hybrid, on Cu foam into CuO nanocrystals confined in a highly conductive nanoarray via anode oxidation. As a 3D catalyst electrode, the resulting CuO-TCNQ/CF shows high OER activity and demands an overpotential of only 317 mV to drive a geometrical catalytic current density of 25 mA cm-2. Notably, this catalyst also demonstrates strong long-term electrochemical durability. This study provides us with a universal strategy toward topotactic room-temperature preparation of conductive nanoarrays with confined transition metal nanocatalysts for practical applications.