A Dual-Active Covalent Triazine Framework Film for Efficient Visible-Light-Driven Hydrogen Peroxide Production.

Photocatalytic hydrogen peroxide production from water and oxygen offers a clean and sustainable alternative to the conventional energy-intensive anthraquinone oxidation method. Compared to powdered covalent triazine frameworks (CTFs), the film morphology of CTFs provides better connectivity in 2D, yielding several advantages: more efficient connections between active sites, reduced electron-hole pair recombination, increased resistance to superoxide radical induced corrosion, and decreased light scattering. Leveraging these benefits, it has incorporated dual active sites for both the oxygen reduction reaction (ORR) and the water oxidation reaction (WOR) into a CTF film system. This dual-active CTF film demonstrated an exceptional hydrogen peroxide production rate of 19 460 µmol h⁻¹ m⁻2 after 1 h and 17 830 µmol h⁻¹ m⁻2 after 5 h under visible light irradiation (≥420 nm) without the need for sacrificial agents.

Tandem Electro-Thermo-Catalysis for the Oxidative Aminocarbonylation of Arylboronic Acids to Amides from CO2 and Water.

Direct CO2 electroreduction to valuable chemicals is critical for carbon neutrality, while its main products are limited to simple C1 /C2 compounds, and traditionally, the anodic O2 byproduct is not utilized. We herein report a tandem electrothermo-catalytic system that fully utilizes both cathodic (i.e., CO) and anodic (i.e., O2 ) products during overall CO2 electrolysis to produce valuable organic amides from arylboronic acids and amines in a separate chemical reactor, following the Pd(II)-catalyzed oxidative aminocarbonylation mechanism. Hexamethylenetetramine (HMT)-incorporated silver and nickel hydroxide carbonate electrocatalysts were prepared for efficient coproduction of CO and O2 with Faradaic efficiencies of 99.3 % and 100 %, respectively. Systematic experiments, operando attenuated total reflection surface-enhanced Fourier transform infrared spectroscopy characterizations and theoretical studies reveal that HMT promotes *CO2 hydrogenation/*CO desorption for accelerated CO2 -to-CO conversion, and O2 inhibits reductive deactivation of the Pd(II) catalyst for enhanced oxidative aminocarbonylation, collectively leading to efficient synthesis of 10 organic amides with high yields of above 81 %. This work demonstrates the effectiveness of a tandem electrothermo-catalytic strategy for economically attractive CO2 conversion and amide synthesis, representing a new avenue to explore the full potential of CO2 utilization.

Unprecedented Photocatalytic Hydrogen Peroxide Production via Covalent Triazine Frameworks Constructed from Fused Building Blocks.

Covalent organic frameworks (COFs) have garnered attention for their potential in photocatalytic hydrogen peroxide (H2O2) production. However, their photocatalytic efficiency is impeded by insufficient exciton dissociation and charge carrier transport. Constructing COFs with superior planarity is an effective way to enhance the π-conjugation degree and facilitate electron-hole separation. Nonetheless, the conventional linear linkers of COFs inevitably introduce torsional strain that disrupts coplanarity. Herein, we address this issue by introducing inherently coplanar triazine rings as linkers and fused building blocks as monomers to create covalent triazine frameworks (CTFs) with superior coplanarity. Both experimental and theoretical calculations confirm that CTFs constructed from fused building blocks significantly enhance the electron-hole separation efficiency and improve the photocatalytic performance, compared to the CTFs constructed with non-fused building blocks. The frontier molecular orbitals and electrostatic potentials (ESP) revealed that the oxygen reduction reaction (ORR) is preferentially facilitated by the triazine rings, with the water oxidation reaction (WOR) likely occurring at the thiophene-containing moiety. Remarkably, CTF-BTT achieved an exceptional H2O2 production rate of 74956 µmol g-1 h-1 when employing 10 % benzyl alcohol (V/V) as a sacrificial agent in an O2-saturated atmosphere, surpassing existing photocatalysts by nearly an order of magnitude. Our findings provide valuable insights for designing highly coplanar polymer-based photocatalysts that enhance the solar-to-chemical energy conversion process.

Mixed-Linker Strategy for the Construction of Sulfone-Containing D-A-A Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Peroxide Production.

The solar-driven photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H2O2 production is often restricted by the low photo-generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed-linker strategy to build a donor-acceptor-acceptor (D-A-A) type covalent organic framework (COF) photocatalyst, FS-OHOMe-COF. The FS-OHOMe-COF structure features extended π-π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS-OHOMe-COF has a low exciton binding energy, long excited-state lifetime and high photo-stability that leads to high performance for photocatalytic H2O2 production (up to 1.0 mM h-1) with an H2O2 output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment.

Improving Alkaline Hydrogen Oxidation through Dynamic Lattice Hydrogen Migration in Pd@Pt Core-Shell Electrocatalysts.

Tracking the trajectory of hydrogen intermediates during hydrogen electro-catalysis is beneficial for designing synergetic multi-component catalysts with division of chemical labor. Herein, we demonstrate a novel dynamic lattice hydrogen (LH) migration mechanism that leads to two orders of magnitude increase in the alkaline hydrogen oxidation reaction (HOR) activity on Pd@Pt over pure Pd, even ≈31.8 times mass activity enhancement than commercial Pt. Specifically, the polarization-driven electrochemical hydrogenation process from Pd@Pt to PdHx @Pt by incorporating LH allows more surface vacancy Pt sites to increase the surface H coverage. The inverse dehydrogenation process makes PdHx as an H reservoir, providing LH migrates to the surface of Pt and participates in the HOR. Meanwhile, the formation of PdHx induces electronic effect, lowering the energy barrier of rate-determining Volmer step, thus resulting in the HOR kinetics on Pd@Pt being proportional to the LH concentration in the in situ formed PdHx @Pt. Moreover, this dynamic catalysis mechanism would open up the catalysts scope for hydrogen electro-catalysis.

Pseudo-Pt Monolayer for Robust Hydrogen Oxidation.

Heteroepitaxial core-shell structure is conducive to combining the advantages of the epilayer and the substrate, creating a novel multifunctionality for catalysis application. Herein, we report a pseudomorphic-Pt atomic layer (PmPt) epitaxially growing on an IrPd-core matrix (PmPt@IrPd/C) as an efficient and stable catalyst for alkaline hydrogen oxidation reaction that exhibits ∼29.2 times more mass activity enhancement than that of benchmark Pt/C. The PmPt@IrPd/C catalyst also gives rise to ∼25.0 times more enhancement than Pt/C during a 50,000-cycle accelerated stability test. This robust stability originates from the resistance to carbon corrosion owing to the stronger H2O interaction instead of carbon oxide (COx) poison species, and the modulated hydroxyl (OH*) adsorption could inhibit the OH* species from shuffling the surface Pt atoms away from the substrate. Moreover, the anion-exchange membrane fuel cells assembled by PmPt@IrPd/C with an ultralow Pt loading of 0.009 mgPt cm-2 in the anode can deliver a power density of 1.27 W cm-2.

Photocatalytic synthesis of alkynylsulfones and alkenylsulfones using sulfonylhydrazides and alkynes.

An efficient and energy saving photocatalytic coupling reaction of benzenesulfonyl hydrazide with bromoacetylene has been reported. A series of alkynylsulfones were obtained in up to 98% yield. In addition, changing the base from KHCO3 to KOAc can give the alkenylsulfone product. In addition, we tested the biological activity of some alkynylsulfone compounds and found that they exhibited excellent in vitro antioxidant activity by activating the Nrf2/ARE pathway, up to 8 fold.

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance.

Atomically dispersed metal catalysts show potential advantages in N2 reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N2 adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N2 adsorption, activation and NRR performance. The extended X-ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH3 yield (RNH3 ) of 28.3 µg h-1 mgcat -1 (7447 µg h-1 mgSn -1 ) at -0.3 V. Furthermore, the enhanced N2 Hx intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N2 fixation.

A Bismuth-Based Zeolitic Organic Framework with Coordination-Linked Metal Cages for Efficient Electrocatalytic CO2 Reduction to HCOOH.

Zeolitic metal-organic frameworks (ZMOFs) have emerged as one of the most promsing catalysts for energy conversion, but they suffer from either weak bonding between metal-organic cubes (MOCs) that decrease their stability during catalysis processes or low activity due to inadequate active sites. In this work, through ligand-directing strategy, we successfully obtain an unprecedented bismuth-based ZMOF (Bi-ZMOF) featuring a ACO topological crystal structure with strong coordination bonding between the Bi-based cages. As a result, it enables efficient reduction of CO2 to formic acid (HCOOH) with Faradaic efficiency as high as 91 %. A combination of in situ surface-enhanced infrared absorption spectroscopy and density functional theory calculation reveals that the Bi-N coordination contributes to facilitating charge transfer from N to Bi atoms, which stabilize the intermediate to boost the reduction efficiency of CO2 to HCOOH. This finding highlights the importance of the coordination environment of metal active sites on electrocatalytic CO2 reduction. We believe that this work will offer a new clue to rationally design zeolitic MOFs for catalytic reaction.

Boosting the Proton-coupled Electron Transfer via Fe-P Atomic Pair for Enhanced Electrochemical CO2 Reduction.

Single-atom catalysts exhibit superior CO2 -to-CO catalytic activity, but poor kinetics of proton-coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe-P atom paired catalyst onto nitrogen doped graphitic layer (Fe1 /PNG) to accelerate PCET step. Fe1 /PNG delivers an industrial CO current of 1 A with FECO over 90 % at 2.5 V in a membrane-electrode assembly, overperforming the CO current of Fe1 /NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe-P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2 , and enhancing the activity of CO2 reduction. This atom-pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single-atom catalysts.

Independent and Interactive Effects of OPRM1 and DAT1 Polymorphisms on Alcohol Consumption and Subjective Responses in Social Drinkers.

BACKGROUND: The current study examined independent and interactive effects of polymorphisms of the mu opioid receptor gene (OPRM1, A118G) and variable number tandem repeats of the dopamine transporter gene (DAT1, SLC6A3) on alcohol consumption and subjective responses to alcohol in 127 young, healthy, social drinkers. METHODS: Participants completed an in-person assessment, which included self-reported alcohol drinking patterns and blood sampling for DNA, and in a second visit, a cumulative alcohol dosing procedure with subjective ratings across multiple time points and breath alcohol contents (0.03 to 0.1%). DNA was analyzed for OPRM1 AA versus AG/GG (*G) genotypes, DAT1 10-repeat allele (A10) versus 9 or lesser alleles (A9), and ancestral informative markers. RESULTS: There were significant epistatic interactions between OPRM1 and DAT1 genotypes. Subjective High Assessment Scale scores after alcohol consumption were highest in *G and A9 carriers, and lowest in *G and A10 carriers. Negative subjective effects were also highest in *G and A9 carriers. Effects were similar in a sensitivity analysis limited to Caucasian subjects. There were independent and epistatic interactions on drinking. The OPRM1 *G allele was independently associated with fewer heavy drinking days. The A9 allele was associated with a greater number of drinking days, which was attenuated in carriers of the *G allele. CONCLUSIONS: These findings highlight the biological importance of interactions between these 2 genes and interactions between brain opioid and dopamine systems.

Mechanistic insights into C-C coupling in electrochemical CO reduction using gold superlattices.

Developing in situ/operando spectroscopic techniques with high sensitivity and reproducibility is of great importance for mechanistic investigations of surface-mediated electrochemical reactions. Herein, we report the fabrication of highly ordered rhombic gold nanocube superlattices (GNSs) as substrates for surface-enhanced infrared absorption spectroscopy (SEIRAS) with significantly enhanced SEIRA effect, which can be controlled by manipulating the randomness of GNSs. Finite difference time domain simulations reveal that the electromagnetic effect accounts for the significantly improved spectroscopic vibrations on the GNSs. In situ SEIRAS results show that the vibrations of CO on the Cu2O surfaces have been enhanced by 2.4 ± 0.5 and 18.0 ± 1.3 times using GNSs as substrates compared to those on traditional chemically deposited gold films in acidic and neutral electrolytes, respectively. Combined with isotopic labeling experiments, the reaction mechanisms for C-C coupling of CO electroreduction on Cu-based catalysts are revealed using the GNSs substrates.

Influence of OPRM1 Asn40Asp variant (A118G) on [11C]carfentanil binding potential: preliminary findings in human subjects.

The Asn40Asp variant (A118G) of the µ opioid receptor (OPRM1) gene is thought to contribute to the development and treatment of alcohol dependence. Employing positron emission tomography (PET), we first examined whether the single nucleotide polymorphism (SNP) modifies binding potential (BP(ND)) of the µ-selective ligand [(11)C]carfentanil in healthy control (Con) and 5-d abstinent alcohol-dependent (AD) subjects (unblocked basal scan). Second, we examined whether the allelic variants were associated with differences in OPRM1 occupancy by naltrexone (50 mg) in AD subjects. Con and AD carriers of the G allele (AG) had lower global BP(ND) at the basal scan than subjects homozygous for the A allele (AA). In AD subjects, naltrexone occupancy was slightly higher in AG subjects (98.9%) compared to AA subjects (93.1%), but this was not significant. We are the first to demonstrate using PET in healthy normal and AD subjects that the A118G SNP alters OPRM1 availability.

Recent Progress in Electrochemical Nitrogen Reduction on Transition Metal Nitrides.

Distributed electrochemical nitrogen reduction reaction (ENRR) powered by renewable energy for the on-site production of ammonia is an attractive alternative to the industrial Haber-Bosch process, which is responsible for roughly 2 % of global energy consumption. In this Review, we summarize recent progress in the ENRR catalyzed by transition metal nitrides (TMNs). The unique electronic structures of TMNs make them promising ENRR catalysts for active and selective ammonia production, which have been predicted theoretically and demonstrated experimentally. Reaction pathways and deactivation mechanisms of the ENRR on different TMNs are surveyed, and current understanding of structure-activity relations is discussed. To develop highly active, selective, and stable TMN catalysts for industrial-scale ENRR, membrane electrode assembly configuration is recommended in catalyst evaluation. Furthermore, we highlight the importance of developing mechanistic understanding on ENRR with different operando spectroscopic techniques.

Elucidating the structure-stability relationship of Cu single-atom catalysts using operando surface-enhanced infrared absorption spectroscopy.

Understanding the structure-stability relationship of catalysts is imperative for the development of high-performance electrocatalytic devices. Herein, we utilize operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) to quantitatively monitor the evolution of Cu single-atom catalysts (SACs) during the electrochemical reduction of CO2 (CO2RR). Cu SACs are converted into 2-nm Cu nanoparticles through a reconstruction process during CO2RR. The evolution rate of Cu SACs is highly dependent on the substrates of the catalysts due to the coordination difference. Density functional theory calculations demonstrate that the stability of Cu SACs is highly dependent on their formation energy, which can be manipulated by controlling the affinity between Cu sites and substrates. This work highlights the use of operando ATR-SEIRAS to achieve mechanistic understanding of structure-stability relationship for long-term applications.

Glucocorticoid-induced loss of DNA methylation in non-neuronal cells and potential involvement of DNMT1 in epigenetic regulation of Fkbp5.

Glucocorticoids may play a significant role in the etiology of neuropsychiatric illnesses. Abnormalities in plasma cortisol levels, glucocorticoid sensitivity, and HPA-axis function often accompany clinical symptoms of stress-related illnesses such as PTSD and depression. Of particular interest are genetic association studies that link single nucleotide polymorphisms of HPA-axis genes with illnesses only in the context of an early-life trauma exposure such as child abuse. These studies suggest that dysregulation of HPA-axis function can have lasting repercussions in shaping mood and anxiety, long after termination of the traumatic experience. As persistent glucocorticoid-induced loss of DNA methylation in FK506 binding protein 5 (Fkbp5) was previously observed in the hippocampus and blood and in the neuronal cell line HT-22, we asked whether these epigenetic alterations occur in non-neuronal, HPA-axis relevant cells. We used the pituitary adenoma cell line AtT-20 to demonstrate that the intronic enhancer region of Fkbp5 undergoes loss of DNA methylation in response to dexamethasone treatment in a dose-dependent manner. We also focused on the mouse hippocampal dentate gyrus to test whether these changes would be enriched in a region implicated in the HPA-axis stress response, neurogenesis, and synaptic plasticity. We observed an increase in enrichment of DNA methylation loss in the dentate gyrus, as compared to whole hippocampal tissues that were similarly treated with glucocorticoids. We then asked whether DNA methyltransferase 1 (Dnmt1), a methyltransferase enzyme involved in maintaining DNA methylation following cell division, is involved in the observed epigenetic alterations. We found a dose-dependent decrease of Dnmt1 expression in the AtT-20 cells following dexamethasone treatment, and a similar decrease in corticosterone-treated mouse hippocampus. Taken together, we provide evidence that these glucocorticoid-induced epigenetic alterations have a broader validity in non-neuronal cells and that they may involve the DNA methylation machinery.

Effects of internet-based cognitive behavioral therapy on postpartum depression: A protocol for systematic review and meta-analysis.

BACKGROUND: Postpartum depression is one of the most common complications during the postpartum period. In recent years, internet-based psychological interventions have made significant progress and provided a new psychotherapy model. Internet-based cognitive behavioral therapy (ICBT) for postpartum depression has achieved good results. However, the effectiveness of ICBT for postpartum depression reported by different studies still remains inconsistent. Therefore, a meta-analysis was used to further evaluate the efficacy of ICBT for postpartum depression, aiming to provide evidence to support nonpharmacological intervention strategies in the clinic. METHODS: The databases of PubMed, Web of Science, Scopus, Cochrane Library, Embase, China Scientific Journal Database, China National Knowledge Infrastructure, Chinese Biomedical Literature Database, and Wanfang Data will be searched. The randomized controlled trials of ICBT will be included for postpartum depression published before February 2022. Two independent researchers will independently complete literature selection, risk of bias assessment and data extraction. The disagreements will be discussed with a third party for the final decision. Cochrane Risk of Bias Assessment Tool will be used for literature quality assessment. Data processing will be conducted by RevMan 5.4 software. RESULTS: The results of this meta-analysis will be submitted to a peer-reviewed journal for publication. CONCLUSIONS: For the question whether ICBT for postpartum depression is efficacy, this study can provide more comprehensive and strong evidence. ETHICS AND DISSEMINATION: The ethical approval was not required for this study. The systematic review will be published in a peer-reviewed journal, presented at conferences, and shared on social media platforms. OSF REGISTRATION NUMBER: DOI 10.17605/OSF.IO/EQJDH.

The effectiveness of mindfulness-based stress reduction intervention on alleviating anxiety and depression in postoperative patients with cervical cancer: A protocol for systematic review and meta-analysis.

BACKGROUND: Surgical treatment for cervical cancer, as a stressor, largely leads to strong psychological reactions to stress like anxiety and depression. Whether mindfulness-based stress reduction (MBSR) can alleviate anxiety and depression in patients after cervical cancer surgery is controversial. Therefore, we aim to perform a meta-analysis involving randomized controlled trials analyzing the effect of MBSR on alleviating anxiety and depression in patients after cervical cancer surgery, thus providing evidence-based medical evidences for nonpharmacological interventions. METHODS: Randomized controlled trials analyzing the effect of MBSR on alleviating anxiety and depression in patients after cervical cancer surgery will be searched in online databases, including Cochrane Central Register of Controlled Trials Repositories, PubMed, Embase, Web of Science, Chinese Science Citation Database, China National Knowledge Infrastructure, Chinese Biomedical Literature Database, Chinese Scientific Journal Database, and Wan Fang Data. After screening eligible studies, we will perform a meta-analysis on the effect of MBSR on alleviating anxiety and depression in patients after cervical cancer surgery. RESULTS: The results of this meta-analysis will be submitted to a peer-reviewed journal for publication. CONCLUSION: This study will provide reliable evidence-based evidences for the effects of MBSR on alleviating anxiety and depression in patients after cervical cancer surgery. ETHICS AND DISSEMINATION: Ethical approval was not required for this study. The systematic review will be published in a peer-reviewed journal, presented at conferences, and shared on social media platforms. OSF REGISTRATION NUMBER: DOI 10.17605/OSF.IO/EXUM3.

Downregulation of LEMD1-AS1 and Its Influences on the Diagnosis, Prognosis, and Immune Infiltrates of Epithelial Ovarian Cancer.

Previous studies have confirmed long noncoding RNA LEMD1-AS1 (LEMD1-AS1) as a functional factor in several tumors. The present work is aimed at exploring the prognostic and diagnostic values of LEMD1-AS1 in patients with epithelial ovarian cancer (EOC). We examined the expressions of LEMD1-AS1 in pan-cancer from TCGA microarray datasets and GTEx Project. The expressions of LEMD1-AS1 were detected by qRT-PCR in EOC specimens and normal ovarian specimens from 30 EOC patients. The χ 2 test was applied to compare the clinicopathological characteristics of different groups. ROC curves were established to determine the diagnostic values of LEMD1-AS1 in screening EOC tissues. The association of LEMD1-AS1 expression with clinical outcome was determined by the Kaplan-Meier methods and COX assays. A decreased expression of LEMD1-AS1 was observed in EOC tissues compared to matched normal specimens (p < 0.01). Low LEMD1-AS1 expression could be used to distinguish EOC from adjacent normal specimens. A clinical study revealed that patients with low LEMD1-AS1 expression have a shorter overall survival (p = 0.035) and progress-free interval (p = 0.041) than those with high LEMD1-AS1 expression. The Spearman correlation test revealed that LEMD1-AS1 expressions were negatively associated with the expressions of neutrophil and myeloid dendritic cell. Overall, our finding suggested that LEMD1-AS1 may have potential roles as a potential biomarker and/or a therapeutic target in EOC.

Fossil Ginkgoales cuticle fine details data from East Inner Mongolia, Northeast China.

The data presented in this article are related to the research paper entitled "Cuticle ultrastructure of Baiera furcata from Northeast China and its implication in Taxonomy and Palaeoenvironment" (Guignard et al. 2019 [1]. The data correspond to a study of the ultrastructural fine cuticle details of fossil Baiera furcata (Ginkgoales) from the Lower Cretaceous Huolinhe Formation in Holingola of East Inner Mongolia, Northeast China. Two sets of data are provided here: 1/ thickness measurements of the layers of four types of cuticles, i.e. ordinary epidermal cells and stomatal apparatus, 2/ ten EDS element analysis of ordinary epidermal cell cuticle layers; the latter data also contain cuticle layers values of Sphenobaiera huangii from the Lower Jurassic Xiangxi Formation in Zigui of Hubei Province, Central China used for comparison in the research article; EDS cell remnant values of Baiera furcata are also included. Some of these data have been used efficiently for taxonomy and palaeoenvironment topics. As they are the first data for genera Baiera and Sphenobaiera of the Ginkgoales, they can serve in the future for considerations of taxonomical comparisons, palaeoreconstructions, palaeoenvironment and evolution.