Construction of a Bifunctional Redox-Site Conjugated Covalent-Organic Framework for Photoinduced Precision Trapping of Uranyl Ions.

The performance of covalent-organic frameworks (COFs) for the photocatalytic extraction of uranium is greatly limited by the number of adsorption sites. Herein, inspired by electronegative redox reactions, we designed a nitrogen-oxygen rich pyrazine connected COF (TQY-COF) with multiple redox sites as a platform for extracting uranium via combining superaffinity and enhanced photoinduction. The preorganized bisnitrogen-bisoxygen donor configuration on TQY-COF is entirely matched with the typical geometric coordination of hexavalent uranyl ions, which demonstrates high affinity (tetra-coordination). In addition, the presence of the carbonyl group and pyrazine ring effectively stores and controls electron flow, which efficaciously facilitates the separation of e-/h+ and enhances photocatalytic performance. The experimental results show that TQY-COF removes up to 99.8% of uranyl ions from actual uranium mine wastewater under the light conditions without a sacrificial agent, and the separation coefficient reaches 1.73 × 106 mL g-1 in the presence of multiple metal ions, which realizes the precise separation in the complex environment. Importantly, DFT calculations further elucidate the coordination mechanism of uranium and demonstrate the necessity of the presence of N/O atoms in the photocatalytic adsorption of uranium.

Trends in rheumatoid arthritis associated cardiovascular mortality in the United States from 1999 to 2020.

INTRODUCTION: Rheumatoid Arthritis (RA) is a risk enhancing factor for cardiovascular diseases (CVD). However, data regarding the magnitude and trends of RA associated CVD-related mortality in the United States (U.S) remains scarce. METHODS: A retrospective analysis was conducted using the Centers for Disease Control and Prevention Wide-Ranging Online Data for Epidemiologic Research (CDC WONDER) dataset. We extracted age-adjusted mortality rates (AAMR) per 100,000 persons and calculated the annual percentage change (APC) through Joinpoint regression. The outcomes were stratified to discern temporal, sex-based, racial, and geographic patterns in RA-associated CVD mortality. RESULTS: Between 1999 and 2020, 128,058 deaths related to CVD in RA patients aged 25 and above were recorded. The AAMR decreased from 3.50 in 1999 to 2.79 in 2020. However, sex disparities persisted, with females consistently experiencing a higher AAMR (3.35) compared to males (1.74). Non-Hispanic (NH) American Indian/Alaska Native had the highest AAMR (4.44) followed by NH White (2.83), NH Black or African American (2.47) and Hispanic or Latino (2.13), while NH Asian/Pacific Islander had the lowest AAMR (1.28). Geographically, the Midwestern region had the highest AAMR (3.12), while the Northeast had the lowest (2.19) with micropolitan (3.47) and nonmetropolitan (3.37) areas exhibiting higher AAMRs compared to large metropolitans (2.28). Notably, states with the highest AAMRs included North Dakota, South Dakota, Vermont, Minnesota and Wyoming. CONCLUSION: Recent trends reveal an upward incline in RA-associated CVD-related mortality with profound disparities related to sex, race, geography and regions. Redressing these disparities necessitates the implementation of targeted population level interventions.

Clinical application of metagenomic next-generation sequencing in non-immunocompromised patients with severe pneumonia supported by veno-venous extracorporeal membrane oxygenation.

Objectives: This study aims to explore the pathogen-detected effect of mNGS technology and its clinical application in non-immunocompromised patients with severe pneumonia supported by vv-ECMO. Methods: A retrospective analysis was conducted on a cohort of 50 non-immunocompromised patients who received vv-ECMO support for severe pneumonia between January 2016 and December 2022. These patients were divided into two groups based on their discharge outcomes: the deterioration group (Group D), which included 31 cases, and the improvement group (Group I), consisting of 19 cases. Baseline characteristics and clinical data were collected and analyzed. Results: Among the 50 patients enrolled, Group D exhibited a higher prevalence of male patients (80.6% vs. 52.6%, p < 0.05), more smokers (54.8% vs. 21.1%, p < 0.05), and were older than those in Group I (55.16 ± 16.34 years vs. 42.32 ± 19.65 years, p < 0.05). Out of the 64 samples subjected to mNGS detection, 55 (85.9%) yielded positive results, with a positivity rate of 83.7% (36/43) in Group D and 90.5% (19/21) in Group I. By contrast, the positive rate through traditional culture stood at 64.9% (74/114). Among the 54 samples that underwent both culture and mNGS testing, 23 (42.6%) displayed consistent pathogen identification, 13 (24.1%) exhibited partial consistency, and 18 (33.3%) showed complete inconsistency. Among the last cases with complete inconsistency, 14 (77.8%) were culture-negative, while two (11.1%) were mNGS-negative, and the remaining two (11.1%) presented mismatches. Remarkably, mNGS surpassed traditional culture in pathogen identification (65 strains vs. 23 strains). Within these 65 strains, 56 were found in Group D, 26 in Group I, and 17 were overlapping strains. Interestingly, a diverse array of G+ bacteria, fungi, viruses, and special pathogens were exclusive to Group D. Furthermore, Acinetobacter baumannii, Pseudomonas aeruginosa, and Klebsiella pneumoniae were more prevalent in Group D compared to Group I. Importantly, mNGS prompted antibiotic treatment adjustments in 26 patients (52.0%). Conclusions: Compared with the conventional culture, mNGS demonstrated a higher positive rate, and emerges as a promising method for identifying mixed pathogens in non-immunodeficient patients with severe pneumonia supported by vv-ECMO. However, it is crucial to combine the interpretation of mNGS data with clinical information and traditional culture results for a comprehensive assessment.

Synthesis of propenone-linked covalent organic frameworks via Claisen-Schmidt reaction for photocatalytic removal of uranium.

The type of reactions and the availability of monomers for the synthesis of sp2-c linked covalent organic frameworks (COFs) are considerably limited by the irreversibility of the C=C bond. Herein, inspired by the Claisen-Schmidt condensation reaction, two propenone-linked (C=C-C=O) COFs (named Py-DAB and PyN-DAB) are developed based on the base-catalyzed nucleophilic addition reaction of ketone-activated α-H with aromatic aldehydes. The introduction of propenone structure endows COFs with high crystallinity, excellent physicochemical stability, and intriguing optoelectronic properties. Benefitting from the rational design on the COFs skeleton, Py-DAB and PyN-DAB are applied to the extraction of radionuclide uranium. In particular, PyN-DAB shows excellent removal rates (>98%) in four uranium mine wastewater samples. We highlight that such a general strategy can provide a valuable avenue toward various functional porous crystalline materials.

The relationship of social isolation and sleep in older adults: evidence from cross-sectional and longitudinal studies.

OBJECTIVES: This study aimed to explore the relationship between social isolation and sleep in later life and the role of loneliness in this relationship. METHODS: In Study 1, we conducted a cross-sectional analysis of the correlation between social isolation and sleep in community-dwelling older adults (N = 108). This relationship was assessed using subjective and objective measures. Moreover, we examined the mediating role of loneliness cross-sectionally (Study 1) and longitudinally (Study 2). Longitudinal study was based on three waves of data from the National Scale Life, Health, and Aging Project (N = 1, 554). RESULTS: The results showed that social isolation was robustly associated with sleep in the general population of older adults. Specifically, subjective social isolation was associated with subjective sleep, and objective social isolation was associated with objective sleep. The results of the longitudinal study showed that loneliness mediated the reciprocal link between social isolation and sleep across time after controlling for autoregressive effects and basic demographics. CONCLUSIONS: These findings address the gap in the literature on the link between social isolation and sleep in older adults, extending the understanding of improvement in older adults' social networks, sleep quality, and psychological well-being.

Recent Advances in Organocatalyzed Asymmetric Sulfa-Michael Addition Triggered Cascade Reactions.

The sulfa-Michael addition reaction is a crucial subset of the Michael addition reaction, and aroused the interest of numerous synthetic biologists and chemists. In particular, sulfa-Michael addition triggered cascade reaction has developed quickly in recent years because it offers an efficient method to construct C-S bonds and other bonds in one approach, which is widely applicable for building chiral pharmaceuticals, their intermediates, and natural compounds. This review emphasizes the recent advancements in sulfa-Michael addition-triggered cascade reactions for the stereoselective synthesis of sulfur-containing compounds, including sulfa-Michael/aldol, sulfa-Michael/Henry, sulfa-Michael/Michael, sulfa-Michael/Mannich and some sulfa-Michael triggered multi-step processes. Moreover, some reaction mechanisms and derivatization experiments are introduced appropriately.

Mechanically robust conjugated microporous polymer membranes prepared using polyvinylpyrrolidone (PVP) electrospun nanofibers as a template for efficient PM capture.

Air pollution has become a challenging environmental problem worldwide due to rapid industrial development and excessive emissions of vehicle exhaust. Herein, we report a preparation of conjugated microporous polymer membranes (CMPM) with a hierarchical porous structure by electrospun polyvinylpyrrolidone (PVP) nanofibers as a template for effective removal of PM from airborne and vehicle exhaust. CMP membranes have hierarchical holes, where the macropores are from electrospun nanofiber membranes and the mesopores are from polymer synthesis. Taking advantage of its inherent physicochemical and thermal stability and hierarchical hole characteristics, the CMPM-based filter can work continuously for up to 36 h and still maintains a high removal efficiency (>99.56%), and also has a high filtration efficiency in the treatment of vehicle exhausts, with 95.18% for PM0.3, 98% for PM0.5 and >99% for PM2.5-10.0. The superior mechanical properties of CMPM allow the filter to be cleaned and reused. After three cycles, the filtration effectiveness of CMPM is still 94.83% for respirable particulate matter. Under high humidity (RH ≥ 95%) conditions, the CMPM-based filter showed higher than 95.37% filtration of PM0.3-10, and the oil adsorption rate could be maintained at 284% at high speed, proving the great potential of CMPM to clean air in complex situations.

Flexible three-dimensional covalent organic frameworks for ultra-fast and selective extraction of uranium via hydrophilic engineering.

It has been considered challenging to develop ideal adsorbents for efficient and lower adsorption time uranium extraction, especially 3D covalent organic frameworks with interpenetrating topologies and tunable porous structures. Here, a "soft" three-dimensional (3D) covalent organic framework (TAM-DHBD) with a fivefold interpenetrating structure is prepared as a novel porous platform for the efficient extraction of radioactive uranium. The resultant TAM-DHBD appears exceptional crystallinity, prominent porosity and excellent chemical stability. Based on the strong mutual coordination between phenolic-hydroxyl/imine-N on the main chain and uranium, TAM-DHBD can effectively avert the competition of other ions, showing high selectivity for uranium extraction. Impressively, the 3D ultra-hydrophilic transport channels and multi-directional uniform pore structure of TAM-DHBD lay the foundation for the ultra-high-speed diffusion of uranium (the adsorption equilibrium can be reached within 60 min under a high-concentration environment). Furthermore, the utilization of lightweight structure not only increases the adsorption site density, but renders the adsorption process flexible, achieving a breakthrough adsorption capacity of 1263.8 mg g-1. This work not only highlights new opportunities for designing microporous 3D COFs, but paves the way for the practical application of 3D COFs for uranium adsorption.

Appropriate oxygen vacancies and Mo-N bond synergistically modulate charge transfer dynamics of MoO3-x/S-CN for superior photocatalytic disinfection: Unveiling synergistic effects and disinfection mechanism.

Highly efficient charge transfer is a critical factor to modulate the photocatalytic activity. However, the conscious modulation of charge transfer efficiency is still a great challenge. Herein, a novel interfacial Mo-N bond and appropriate oxygen vacancies (OVs) modulated S-scheme MoO3-x/S-CN heterojunction was rationally fabricated for efficient photocatalytic disinfection. The results of characterizations and density functional theory (DFT) calculations suggested that the enhanced charge transfer dynamics is ascribed to the optimizing oxygen vacancies density and forming interfacial Mo-N bond. It can improve charge transfer efficiency from 36.4% (MoO3-x) to 52.5% (MoO3-x/S-CN) and produce more reactive oxygen species (ROS), achieving entirely inactivate of 7.60-log E. coli and S. aureus within 50 min and 75 min. Besides, MoO3-x/S-CN can well resist the disturbance from the coexisting substances, and can be applied in a wide pH range, and even authentic water bodies. Monitoring of bacterial antioxidant systems and membrane integrity revealed that bacterial inactivation begins with the oxidation of cell membrane and dies from leakage of intracellular substances and destruction of cell structure. This work provides an inspiration on consciously modulating S-scheme charge transfer efficiency by optimizing oxygen vacancies density and atomic-level interface control for promoting the photocatalytic antibacterial activity.

An ionic vinylene-linked three-dimensional covalent organic framework for selective and efficient trapping of ReO4- or 99TcO4.

The synthesis of ionic olefin linked three-dimensional covalent organic frameworks (3D COFs) is greatly challenging given the hardness of the formation of stable carbon-carbon double bonds (-C = C-). Herein, we report a general strategy for designing porous positively charged sp2 carbon-linked 3D COFs through the Aldol condensation promoted by quaternization. The obtained 3D COFs, namely TFPM-PZI and TAPM-PZI, showed impressive chemical stability. Furthermore, the positively charged frameworks with regular porosity endow 3D ionic COFs with selective capture radioactive ReO4-/TcO4- and great removal efficiency in simulated Hanford waste. This research not only broadens the category of 3D COFs but also promotes the application of COFs as efficient functional materials.

The Effect of Nighttime Snacking on Cognitive Function in Older Adults: Evidence from Observational and Experimental Studies.

Evidence shows that supplementary snacking could provide older adults with nutrients that cannot be obtained through three meals a day. However, whether and how supplementary snacking, especially nighttime snacking, affects older adults' cognitive function remain unclear. The present study examined the effect of nighttime snacking on cognitive function for older adults. In study 1, we investigated the association between nighttime snacking and cognitive function based on data from 2618 community-dwelling older adults from the China health and nutrition survey (CHNS). In study 2, we conducted an experiment (n = 50) to explore how nighttime acute energy intake influences older adults' performance on cognitive tasks (immediate recall, short-term delayed recall, and long-term delayed recall). Both the observational and experimental studies suggested that nighttime snacking facilitated older adults' cognitive abilities, such as memory and mathematical ability, as indicated by subjective measures (study 1) and objective measures (studies 1 and 2). Moreover, this beneficial effect was moderated by cognitive load. These findings bridge the gap in the literature on the relationships between older adults' nighttime snacking and cognitive function, providing insight into how to improve older adults' dietary behaviors and cognitive function.

Enantioselective Michael/Hemiketalization Cascade Reactions between Hydroxymaleimides and 2-Hydroxynitrostyrenes for the Construction of Chiral Chroman-Fused Pyrrolidinediones.

In this paper, the organocatalytic asymmetric Michael addition/hemiketalization cascade reactions between hydroxymaleimides and 2-hydroxynitrostyrenes were developed, which provided a new protocol for building a chiral ring-fused chroman skeleton. This squaramide-catalyzed cascade reaction provided chiral chroman-fused pyrrolidinediones with three contiguous stereocenters in good to high yields (up to 88%), with excellent diastereoselectivities (up to >20:1 dr) and enantioselectivities (up to 96% ee) at −16 °C. Moreover, a scale-up synthesis was also carried out, and a possible reaction mechanism was proposed.

Enantioselective synthesis of isoxazole-containing spirooxindole tetrahydroquinolines via squaramide-catalysed cascade reactions.

A class of o-sulfonylaminostyryl isoxazole synthons were designed and demonstrated to be useful building blocks in asymmetric cascade aza-Michael/Michael reaction with 3-olefinic oxindoles. This squaramide-catalysed cascade reaction afforded structurally complex isoxazole-containing spirooxindole tetrahydroquinolines bearing three contiguous stereocenters in good to excellent yields (up to 99%) with high diastereoselectivities (up to >20 : 1 dr) and enantioselectivities (up to 88% ee). Moreover, the gram-scale synthesis and synthetic transformations were also demonstrated.

Insights into the role of reactive oxygen species in photocatalytic H2O2 generation and OTC removal over a novel BN/Zn3In2S6 heterojunction.

Developing photocatalysts with superior performance to generate hydrogen peroxide (H2O2) and degrade oxytetracycline (OTC) is an effective strategy for the treatment of energy crisis and water purification. Herein, BN nanosheets were anchored onto the Zn3In2S6 microspheres for the research. Experimental and density functional theory (DFT) results demonstrate that due to different work functions and unique 2D/2D contact, the electron is spatially separated in BN/Zn3In2S6 nanocomposite, which increases the electron transfer efficiency from 43.7% (Zn3In2S6) to 55.6% (BN/ZIS-4). As a result, BN/ZIS-4 with optimal ratio of BN and Zn3In2S6 exhibits the highest OTC degradation efficiency (84.5%) and H2O2 generation rate (115.5 µmol L-1) under visible light illumination, which is 2.2 and 2.9 times than that of pristine Zn3In2S6. H2O2 generation is dominated by two pathways: two-step single-electron process (O2 → ∙O2- → H2O2) and another way (O2 → ∙O2- → 1O2 → H2O2). In the process of degrading OTC, ∙O2-, 1O2 and ∙OH are regarded as the main active species. This work offers a new insight for designing efficient, stable and reusable photocatalysts to solve current environmental conundrums.

3D Ionic Olefin-Linked Conjugated Microporous Polymers for Selective Detection and Removal of TcO4-/ReO4- from Wastewater.

Technetium (99Tc) is a highly toxic radioactive nuclear wastewater contaminant. Real-time detection of 99Tc is very difficult due to its difficult-to-complex nature. Herein, a novel three-dimensional ionic olefin-linked conjugated microporous polymer (TFPM-EP-Br) is constructed using tetrakis(4-aldehyde phenyl)methane (TFPM) as the central monomer. The unique cationic cavity and highly hydrophobic framework enable TFPM-EP-Br to act as a fluorescent sensor for TcO4-. The fluorophores of TFPM-EP-Br can be quenched due to electron transfer from TFPM-EP-Br to TcO4- and the formation of strongly nonfluorescent complexes. Meanwhile, the regular pore channels are beneficial for the fast mass transfer of TcO4-, resulting in an ultrafast response time (less than 2 s) with an ultralow detection limit (33.3 nM). In addition, the ultrahigh specific surface area enables TFPM-EP-Br to combine the ability to synergistically detect and remove radioactive 99Tc. From this perspective, the novel conjugated microporous polymer has made a breakthrough in the detection and extraction of radioactive contaminants.

[Microplastics in the stomach and intestine of pelagic squid: A case study of Dosidicus gigas in open sea of Peru]. / å¤§æ´‹æ€§å¤´è¶³ç±»èƒƒå’Œè‚ é“ä¸­çš„å¾®å¡‘æ–™­­ä»¥ç§˜é²å¤–海茎柔鱼为例.

Microplastic (MP) ingestion by marine animals has been well documented, but less being known about pelagic squid. Jumbo squid Dosidicus gigas supports the world's largest cephalopod fishery and plays an important ecological role in the Eastern Pacific Ocean. In this study, D. gigas taken from the open sea of the Peruvian Exclusive Economic Zone were selected as research objects. We estimated the abundance and characteristics of MPs in the stomach and intestine of D. gigas and investigated the differences between tissues and sexes. Similar abundance and characteristics of MPs were observed in the same tissue of females and males. However, the stomach had a higher abundance of MPs with larger size than the intestine, while the MP abundance by stomach wet weight was lower than that of the intestine. The MPs were predominantly fiber-shaped, with blue or black color. The most frequent polymers were high-density cellophane and polyacrylic acid. These polymers could sink into deeper sea layers and were available for D. gigas living there during the daytime. Our findings revealed the distribution pattern of MPs in the waters of the Peruvian fishing ground. This study could improve our understanding of the MP contamination level in pelagic squid, and have implications for evaluating the ecological effects of MP on cephalopods.

A squaramide-catalysed asymmetric cascade Michael addition/acyl transfer reaction between unsaturated benzothiophenones and α-nitroketones.

An efficient and practical organocatalytic asymmetric strategy was developed using unsaturated benzothiophenones and α-nitroketones catalysed by bifunctional squaramide via Michael addition and acyl transfer steps. A broad range of chiral acyloxybenzothiophene derivatives were obtained in good yields (up to 97%) with excellent enantioselectivities (up to 98% ee). What's more, employing different chiral squaramide catalysts and unsaturated benzothiophenones can deliver the acyloxy unit at the 2-position or 3-position of benzothiophene.

Integrating the Z-scheme heterojunction and hot electrons injection into a plasmonic-based Zn2In2S5/W18O49 composite induced improved molecular oxygen activation for photocatalytic degradation and antibacterial performance.

The semiconductor-based photocatalysts with local surface plasmon resonance (LSPR) effect can extend light response to near-infrared region (NIR), as well as promote charge-carriers transfer, which provide a novel insight into designing light-driven photocatalyst with excellent photocatalytic performance. Here, we designed cost-effective wide-spectrum Zn2In2S5/W18O49 composite with enhanced photocatalytic performance based on a dual-channel charge transfer pathway. Benefiting from the synergistic effect of Z-scheme heterostructure and unique LSPR effect, the interfacial charge-carriers transfer rate and light-absorbing ability of Zn2In2S5/W18O49 were enhanced significantly under visible and NIR (vis-NIR) light irradiation. More reactive oxygen species (ROS) were formed by efficient molecular oxygen activation, which were the critical factors for both Escherichia coli (E. coli) photoinactivation and tetracycline (TC) photodegradation. The enhancement of molecular oxygen activation (MOA) ability was verified via quantitative analyses, which evaluated the amount of ROS through degrading nitrotetrazolium blue chloride (NBT) and p-phthalic acid (TA). By combining theoretical calculations with diverse experimental results, we proposed a credible photocatalytic reaction mechanism for antibiotic degradation and bacteria inactivation. This study develops a new insight into constructing promising photocatalysts with efficient photocatalytic activity in practical wastewater treatment.

Metal-organic framework-derived CuCo/carbon as an efficient magnetic heterogeneous catalyst for persulfate activation and ciprofloxacin degradation.

Herein, the authors synthesis an efficient and easily recycled CuCo/C catalyst through one-step carbonization of Cu@Co-MOF-71 (Abbreviated as Cu@Co-MOF in this work) precursor. The prepared CuCo/C has a high degradation efficiency of 90% for ciprofloxacin (CIP) by activating PMS in a wide value of pH 3-9 within 30 min. After pyrolysis, the carbon matrix as a dispersant can promote the highly uniform distribution of active metals. Additionally, the CIP removal efficiency was 85% after four cycles and the catalyst was easily separated from the solution by using magnets, showing the good stability and reusability. To further study the superiority of CuCo/C activated PMS in degrading CIP, the factors such as pH, the dosage of PMS and catalyst, temperature, inorganic ions and pollutant (CIP) concentration were investigated. Furthermore, the Liquid chromatography-mass spectrometry (LC-MS) was utilized to analyze the intermediate products and possible degradation pathways of CIP. Typically, the quenching experiments and electron paramagnetic resonance (EPR) technology were investigated to confirm the main reaction species including SO4▪-, OH▪ and O2▪- radicals as well as nonradical (1O2). This work put forward a simple method for synthesis of metal-organic framework (MOF) derived catalysts and its application in treatment of organic pollutants.

Global Graph Attention Embedding Network for Relation Prediction in Knowledge Graphs.

The incompleteness of knowledge graphs triggers considerable research interest in relation prediction. As the key to predicting relations among entities, many efforts have been devoted to learning the embeddings of entities and relations by incorporating a variety of neighbors' information which includes not only the information from direct outgoing and incoming neighbors but also the ones from the indirect neighbors on the multihop paths. However, previous models usually consider entity paths of limited length or ignore sequential information of the paths. Either simplification will make the model lack a global understanding of knowledge graphs and may result in the loss of important and indispensable information. In this article, we propose a novel global graph attention embedding network (GGAE) for relation prediction by combining global information from both direct neighbors and multihop neighbors. Concretely, given a knowledge graph, we first introduce the path construction algorithms to obtain meaningful paths, then design path modeling methods to capture the potential long-distance sequential information in the multihop paths, final propose an entity graph attention and a relation graph attention mechanisms to obtain entity embeddings and relation embeddings. Moreover, an entity graph attention mechanism is proposed to calculate the entity embeddings by aggregating direct incoming and outgoing neighbors from: 1) an original knowledge graph with the original entity and relation embeddings and 2) a new knowledge graph constructed by the paths whose embeddings are updated by path modeling methods. for each relation, we construct a new graph with related entities and present a relation graph attention to learn the features. Therefore, our model can encapsulate the information from different distance neighbors, and enable the embeddings of entities and relations to better capture all-sided semantic information. The experimental results on benchmark datasets verify the superiority of our model over the state-of-the-art ones.