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In this work, the tribological properties of a novel iron‐based self‐lubricating composite as the tribopairs of a plunger pump were systematically studied on an end‐face tribometer, and the tribological mechanism was also revealed. The results show that the wear mechanism of the composite can be ascribed to adhesive wear when the sliding speed is lower than 1.5 m/s. As the sliding speed increases from 1.5 to 2.0 m/s, the wear type transforms to oxidative wear due to the increase of tribo‐oxidation. In addition, the failure criteria of the tribopair composite materials are summarised. When the average coefficient of friction is greater than 0.04, or the wear rate is greater than 9.66 μm3/(N m), the tribopair fails. This offers a valuable reference for industrial application of the tribopairs made from the iron‐based self‐lubricating composite. [ABSTRACT FROM AUTHOR]

Chemical and isotopic processes occur in every segment of the hydrological cycle. Hydrogeochemistry—the subdiscipline that studies these processes—has seen a transformation from "witch's brew" to credible science since 2000. Going forward, hydrogeochemical research and applications are critical to meeting urgent societal needs of climate change mitigation and clean energy, such as (1) removing CO2 from the atmosphere and storing gigatons of CO2 in soils and aquifers to achieve net‐zero emissions, (2) securing critical minerals in support of the transition from fossil fuels to renewable energies, and (3) protecting water resources by adapting to a warming climate. In the last two decades, we have seen extensive activity and progress in four research areas of hydrogeochemistry related to water‐rock interactions: arsenic contamination of groundwater; the use of isotopic and chemical tracers to quantify groundwater recharge and submarine groundwater discharge; the kinetics of chemical reactions and the mineral‐water interface's control of contaminant fate and transport; and the transformation of geochemical modeling from an expert‐only exercise to a widely accessible tool. In the future, embracing technological advances in machine learning, cyberinfrastructure, and isotope analytical tools will allow breakthrough research and expand the role of hydrogeochemistry in meeting society's needs for climate change mitigation and the transition from fossil fuels to renewable energies. [ABSTRACT FROM AUTHOR]

Seed dispersal by frugivorous birds facilitates plant invasions, but it is poorly known how invasive plants integrate into native communities in fragmented landscapes. We surveyed plant–frugivore interactions, including an invasive plant (Phytolacca americana), on 22 artificial land‐bridge islands (fragmented forests) in the Thousand Island Lake, China. Focusing on frugivory interactions that may lead to seed dispersal, we built ecological networks of studied islands both at the local island (community) and at landscape (metacommunity) levels. On islands with P. americana, we found that P. americana impacted local avian frugivory networks more on islands with species‐poor plant communities and on isolated islands. Moreover, as P. americana interacted mainly with local core birds (generalists), this indicates reduced seed dispersal of native plants on invaded islands. At the landscape level, P. americana had established strong interactions with generalist birds that largely maintain seed‐dispersal functions across islands, as revealed by their topologically central roles both in the regional plant–bird trophic network and in the spatial metanetwork. This indicates that generalist frugivorous birds may have facilitated the dispersal of P. americana across islands, making P. americana well integrated into the plant–frugivore mutualistic metacommunity. Taken together, our study demonstrates that the impact of plant invasion is context‐dependent and that generalist native frugivores with high dispersal potential may accelerate plant invasion in fragmented landscapes. These findings highlight the importance of taking the functional roles of animal mutualists and habitat fragmentation into account when managing plant invasions and their impact on native communities. [ABSTRACT FROM AUTHOR]

SUMMARY: Plant embryogenic calli (ECs) can undergo somatic embryogenesis to regenerate plants. This process is mediated by regulatory factors, such as transcription factors and specifically expressed genes, but the precise molecular mechanisms underlying somatic embryogenesis at the single‐cell level remain unclear. In this study, we performed high‐resolution single‐cell RNA sequencing analysis to determine the cellular changes in the EC of the woody plant species Dimocarpus longan (longan) and clarify the continuous cell differentiation trajectories at the transcriptome level. The highly heterogeneous cells in the EC were divided into 12 putative clusters (e.g., proliferating, meristematic, vascular, and epidermal cell clusters). We determined cluster‐enriched expression marker genes and found that overexpression of the epidermal cell marker gene GDSL ESTERASE/LIPASE‐1 inhibited the hydrolysis of triacylglycerol. In addition, the stability of autophagy was critical for the somatic embryogenesis of longan. The pseudo‐timeline analysis elucidated the continuous cell differentiation trajectories from early embryonic cell division to vascular and epidermal cell differentiation during the somatic embryogenesis of longan. Moreover, key transcriptional regulators associated with cell fates were revealed. We found that ETHYLENE RESPONSIVE FACTOR 6 was characterized as a heat‐sensitive factor that negatively regulates longan somatic embryogenesis under high‐temperature stress conditions. The results of this study provide new spatiotemporal insights into cell division and differentiation during longan somatic embryogenesis at single‐cell resolution. Significance Statement: Plant embryogenic calli can undergo somatic embryogenesis to regenerate plants. The single‐cell RNA‐seq results described herein provide new spatiotemporal insights into cell division and differentiation in the Dimocarpus longan (longan) embryogenic callus. The generated gene expression map will enable us to investigate how embryonic cells differentiate into vascular and epidermal cells. The results may provide the foundation for future molecular and cellular investigations into the mechanisms mediating longan somatic embryogenesis and zygotic embryogenesis. [ABSTRACT FROM AUTHOR]

The difunctionalization of unsaturated bonds plays a vital role in the enrichment of molecular complexity. While various catalytic methods for alkene and alkyne difunctionalization have been developed in recent years, hetero‐functionalization the introduction of two different atoms has been less explored. This is mainly due to the challenges associated with achieving high chemo‐, regio‐, and stereoselectivity, especially when adding two similar atoms from the same group across unsaturated bonds. In this study, we describe a nickel‐catalyzed, three‐component reductive protocol for group 14 element hetero‐difunctionalization of 1,3‐enynes using electrochemistry. This new method is mild, selective, and general, allowing for the silyl‐, germanyl‐, and stannyl‐alkylation of enynes. Various chlorosilanes as well as chlorogermans, and chlorostannanes can be successfully used in combination with aryl/alkyl‐substituted 1,3‐enynes and primary, secondary, and tertiary alkyl bromides in the electroreductive coupling. [ABSTRACT FROM AUTHOR]

The difunctionalization of unsaturated bonds plays a vital role in the enrichment of molecular complexity. While various catalytic methods for alkene and alkyne difunctionalization have been developed in recent years, hetero‐functionalization the introduction of two different atoms has been less explored. This is mainly due to the challenges associated with achieving high chemo‐, regio‐, and stereoselectivity, especially when adding two similar atoms from the same group across unsaturated bonds. In this study, we describe a nickel‐catalyzed, three‐component reductive protocol for group 14 element hetero‐difunctionalization of 1,3‐enynes using electrochemistry. This new method is mild, selective, and general, allowing for the silyl‐, germanyl‐, and stannyl‐alkylation of enynes. Various chlorosilanes as well as chlorogermans, and chlorostannanes can be successfully used in combination with aryl/alkyl‐substituted 1,3‐enynes and primary, secondary, and tertiary alkyl bromides in the electroreductive coupling. [ABSTRACT FROM AUTHOR]

Bidirectional modulation of synaptic weight lays the basis for learning and memory in the brain, and the development of brain‐inspired photonic synaptic devices is hindered by deficient light‐stimulated inhibition. In this report, a type of organic thin film neuromorphic devices with a planar two‐terminal architecture, featuring as the inhibitory regulation of synaptic weight over two orders of magnitude upon selective UV illumination is developed. The in situ monitoring on the floating electrode potential and the corresponding simulation results demonstrate the effect of cumulative hole trapping in the polymer electret layer, which modulates the device conductance in a nonvolatile manner. Remarkably, UV‐induced long‐term depression is accompanied by enhanced short‐term potentiation in the device that may preserve a stable level of total synaptic activities. The UV‐stimulated inhibition and the adaptive short‐term plasticity, as well as the ON and OFF responses to light in the organic photonic synaptic device, suggest its potential applications in photonic neuromorphic computing. [ABSTRACT FROM AUTHOR]

(Deuterium‐labeled) CF2H‐ and CFH2‐moieties are of high interest in drug discovery. The high demand for the incorporation of these fluoroalkyl moieties into molecular structures has witnessed significant synthetic progress, particularly in the (deutero)hydrodefluorination of CF3‐containing compounds. However, the controllable replacement of fluorine atoms while maintaining high chemoselectivity remains challenging. Herein, we describe the development of a selective (deutero)hydrodefluorination reaction via electrolysis. The reaction exhibits a remarkable chemoselectivity control, which is enabled by the addition of different organoboron sources. The procedure is operationally simple and scalable, and provides access in one step to high‐value building blocks for application in medicinal chemistry. Furthermore, density functional theory (DFT) calculations have been carried out to investigate the reaction mechanism and to rationalize the chemoselectivity observed. [ABSTRACT FROM AUTHOR]

(Deuterium‐labeled) CF2H‐ and CFH2‐moieties are of high interest in drug discovery. The high demand for the incorporation of these fluoroalkyl moieties into molecular structures has witnessed significant synthetic progress, particularly in the (deutero)hydrodefluorination of CF3‐containing compounds. However, the controllable replacement of fluorine atoms while maintaining high chemoselectivity remains challenging. Herein, we describe the development of a selective (deutero)hydrodefluorination reaction via electrolysis. The reaction exhibits a remarkable chemoselectivity control, which is enabled by the addition of different organoboron sources. The procedure is operationally simple and scalable, and provides access in one step to high‐value building blocks for application in medicinal chemistry. Furthermore, density functional theory (DFT) calculations have been carried out to investigate the reaction mechanism and to rationalize the chemoselectivity observed. [ABSTRACT FROM AUTHOR]

Here, the fabrication of an addressable 8 × 8 photodetector array is reported by combining In2Se3 nanofilm with periodic inverse micropyramid‐Si (PIMP‐Si), which is obtained through colloidal lithography and anisotropic wet etching. Due to the unique configuration and the outstanding light trapping effect, the as‐fabricated heterojunction device presents an excellent self‐powered photoresponse over the broadband wavelength range from 265 to 1300 nm, with a peak sensitivity at ≈810 nm. The responsivity, specific detectivity, and rise/fall time are estimated to be 0.58 A W−1, 1.76 × 1012 Jones, and 5.1/18 µs, respectively, which are competitive in comparison with other devices with similar geometries. Meanwhile, the photodetector array displays a satisfactory pixel‐to‐pixel uniformity, which allows the device to record the full‐color image of "HFUT" with satisfying resolution, revealing the potential application of the PIMP‐Si/In2Se3 heterojunction photodetector array for real‐time red‐green‐blue‐infrared image sensing and video capturing. [ABSTRACT FROM AUTHOR]

Herein, we report a reductive cross‐coupling reaction of α‐oxy halides, simply generated from aldehydes, with a series of C(sp2)‐ and C(sp)‐electrophiles. A wide range of aryl and heteroatom aryl halides, vinyl bromides, alkynyl bromides, and acyl chlorides react with unhindered and hindered aldehyde‐derived α‐oxy halides by providing protected alcohols as well as α‐hydroxy ketones. Noteworthy, the reductive couplings are achieved not only through thermal catalysis with the use of metal reductants but also by photocatalysis, electrochemistry, and mechanochemistry. The unrestricted interchange of the four strategies indicates their underlying mechanistic similarities. The generation of NiI intermediate is proposed to be the key point for ketyl radical formation via a single‐electron transfer (SET) event, which was rationalized by an array of control experiments and density functional theory (DFT) calculations. [ABSTRACT FROM AUTHOR]

Herein, we report a reductive cross‐coupling reaction of α‐oxy halides, simply generated from aldehydes, with a series of C(sp2)‐ and C(sp)‐electrophiles. A wide range of aryl and heteroatom aryl halides, vinyl bromides, alkynyl bromides, and acyl chlorides react with unhindered and hindered aldehyde‐derived α‐oxy halides by providing protected alcohols as well as α‐hydroxy ketones. Noteworthy, the reductive couplings are achieved not only through thermal catalysis with the use of metal reductants but also by photocatalysis, electrochemistry, and mechanochemistry. The unrestricted interchange of the four strategies indicates their underlying mechanistic similarities. The generation of NiI intermediate is proposed to be the key point for ketyl radical formation via a single‐electron transfer (SET) event, which was rationalized by an array of control experiments and density functional theory (DFT) calculations. [ABSTRACT FROM AUTHOR]

It remains challenging to manipulate the nature of photoluminescence as either fluorescence or phosphorescence for a correlated cluster series. In this work, two correlated nanoclusters, Au5Ag11(SR)8(DPPOE)2 and Pt1Ag16(SR)8(DPPOE)2 with comparable structure features, were synthesized and structurally determined. These two alloy nanoclusters displayed distinct photoluminescent nature—the Au5Ag11 nanocluster is fluorescent, whereas the Pt1Ag16 nanocluster is phosphorescent. The decay processes of the excited electrons in these two nanoclusters have been explicitly mapped out by both experimental and theoretical approaches, disclosing the mechanisms of their fluorescence and phosphorescence. Specifically, the metallic compositions of the nanocluster kernels mattered in determining their photoluminescent nature. The results herein provide an intriguing nanomodel that enables us to grasp the origin of photoluminescence at the atomic level, which further paves the way for fabricating novel nanoclusters or cluster‐based nanomaterials with customized photophysical properties. [ABSTRACT FROM AUTHOR]

It remains challenging to manipulate the nature of photoluminescence as either fluorescence or phosphorescence for a correlated cluster series. In this work, two correlated nanoclusters, Au5Ag11(SR)8(DPPOE)2 and Pt1Ag16(SR)8(DPPOE)2 with comparable structure features, were synthesized and structurally determined. These two alloy nanoclusters displayed distinct photoluminescent nature—the Au5Ag11 nanocluster is fluorescent, whereas the Pt1Ag16 nanocluster is phosphorescent. The decay processes of the excited electrons in these two nanoclusters have been explicitly mapped out by both experimental and theoretical approaches, disclosing the mechanisms of their fluorescence and phosphorescence. Specifically, the metallic compositions of the nanocluster kernels mattered in determining their photoluminescent nature. The results herein provide an intriguing nanomodel that enables us to grasp the origin of photoluminescence at the atomic level, which further paves the way for fabricating novel nanoclusters or cluster‐based nanomaterials with customized photophysical properties. [ABSTRACT FROM AUTHOR]

Summary: Biological nitrogen fixation performed by diazotrophs forms a cornerstone of Earth's terrestrial ecosystem productivity. However, the composition, diversity and distribution of soil diazotrophs are poorly understood across different soil ecosystems. Furthermore, the biological potential of the key diazotroph species in relation to key environmental parameters is unknown. To address this, we used meta‐analysis approach to merge together 39 independent diazotroph amplicon sequencing (nifH gene) datasets consisting of 1988 independent soil samples. We then employed multiple statistical analyses and machine‐learning approaches to compare diazotroph community differences and indicator species between terrestrial ecosystems on a global scale. The distribution, composition and structure of diazotroph communities varied across seven different terrestrial ecosystems, with community composition exhibiting an especially clear effect. The Cyanobacteria were the most abundant taxa in crust ecosystems (accounting for ~45% of diazotrophs), while other terrestrial ecosystems were dominated by Proteobacteria, including Alpha‐, Beta‐ and Gamma‐Proteobacteria (accounting for ~70% of diazotrophs). Farmland ecosystems harboured the highest and crust ecosystems the lowest alpha and phylogenetic diversities. Azospirillum zeae, Skermanella aerolata and four Bradyrhizobium species were identified as key indicator species of potential diazotroph activity. Overall, diazotroph abundances and distribution were affected by multiple environmental parameters, including soil pH, nitrogen, organic carbon, C:N ratio and annual mean precipitation and temperature. Together, our findings suggest that based on the relative abundance and diversity of nifH marker gene, diazotrophs have adapted to a range of environmental niches globally. [ABSTRACT FROM AUTHOR]

The separation performance of a membrane is not only related to the membrane, but also to the operating conditions. The operation conditions of superhydrophobic zeolitic imidazolate framework‐90 (S‐ZIF‐90)/polydimethylsiloxane hybrid membranes for pervaporation were optimized using response surface methodology. The separation performances of hybrid membranes were evaluated by regulating the rotation rate, operation temperature, and feed concentration. The regression equations between the operation variables and the separation performance of the hybrid membranes were established and applied to predict and optimize the separation performance of these membranes. The main effects, quadratic effects, and interactions of the three variables on the permeation flux and the separation factor of hybrid membranes were analyzed. [ABSTRACT FROM AUTHOR]

The formation of C‐heteroatom bonds represents an important type of bond‐forming reaction in organic synthesis and often provides a fast and efficient access to privileged structures found in pharmaceuticals, agrochemical and materials. In contrast to conventional Pd‐ or Cu‐catalyzed C‐heteroatom cross‐couplings under high‐temperature conditions, recent advances in homo‐ and heterogeneous Ni‐catalyzed C‐heteroatom formations under mild conditions are particularly attractive from the standpoint of sustainability and practicability. The generation of NiIII and excited NiII intermediates facilitate the reductive elimination step to achieve mild cross‐couplings. This review provides an overview of the state‐of‐the‐art approaches for mild C‐heteroatom bond formations and highlights the developments in photoredox and nickel dual catalysis involving SET and energy transfer processes; photoexcited nickel catalysis; electro and nickel dual catalysis; heterogeneous photoredox and nickel dual catalysis involving graphitic carbon nitride (mpg‐CN), metal organic frameworks (MOFs) or semiconductor quantum dots (QDs); as well as more conventional zinc and nickel dual catalyzed reactions. [ABSTRACT FROM AUTHOR]

The formation of C‐heteroatom bonds represents an important type of bond‐forming reaction in organic synthesis and often provides a fast and efficient access to privileged structures found in pharmaceuticals, agrochemical and materials. In contrast to conventional Pd‐ or Cu‐catalyzed C‐heteroatom cross‐couplings under high‐temperature conditions, recent advances in homo‐ and heterogeneous Ni‐catalyzed C‐heteroatom formations under mild conditions are particularly attractive from the standpoint of sustainability and practicability. The generation of NiIII and excited NiII intermediates facilitate the reductive elimination step to achieve mild cross‐couplings. This review provides an overview of the state‐of‐the‐art approaches for mild C‐heteroatom bond formations and highlights the developments in photoredox and nickel dual catalysis involving SET and energy transfer processes; photoexcited nickel catalysis; electro and nickel dual catalysis; heterogeneous photoredox and nickel dual catalysis involving graphitic carbon nitride (mpg‐CN), metal organic frameworks (MOFs) or semiconductor quantum dots (QDs); as well as more conventional zinc and nickel dual catalyzed reactions. [ABSTRACT FROM AUTHOR]

Although Co-IP has been widely used to examine I in vivo i protein-protein interactions, especially for strong and stable protein interactions, it needs to be performed with great experimental caution for weak or transient interactions, such as those that occur between a kinase and its substrates. Under normal conditions, TOR kinase phosphorylates ABA receptors (PYR1/PYL/RCARs) to abolish their ABA binding ability, thereby preventing stress signaling activation and promoting plant growth. In the presence of abscisic acid or environmental stress, activated SnRK2s transiently phosphorylate Raptor1B, a regulatory component of the TOR complex, to inhibit plant growth. As phosphorylation of hundreds of proteins has been shown to be dependent on SnRK2s (Umezawa et al., 2013; Wang et al., 2013, 2018, 2020), it is not surprising there are other kinases/signal components that can mediate stress adaptation processes downstream of SnRK2s. [Extracted from the article]

A new cross‐coupling of trifluoromethyl arenes has been realized via multiphoton photoredox catalysis. Trifluoromethyl arenes were demonstrated to undergo selective mono‐defluorinative alkylation under mild reaction conditions providing access to a series of valuable α,α‐difluorobenzylic compounds. The reaction shows broad substrate scope and general functional group tolerance. In addition to the electron‐deficient trifluoromethyl arenes that are easily reduced to the corresponding radical anion, more challenging electron‐rich substrates were also successfully applied. Steady‐State Stern‐Volmer quenching studies indicated that the trifluoromethyl arenes were reduced by the multiphoton excited Ir‐based photocatalyst. [ABSTRACT FROM AUTHOR]

Vegetation carbon stock (Cveg) in global forests, which is important for C cycle‐climate feedbacks, commonly increases with forest age. Due to the allometric growth of plants, the nonlinear increase in Cveg with woody fraction (fw) is expected across space. However, it remains unclear whether such a nonlinear relationship between Cveg and fw can be constrained by observations and further used to benchmark Earth system models (ESMs). Here, based on the in situ measurements at 1,145 forest sites, we found that the nonlinear relationship between Cveg and fw followed an exponential equation (i.e., Cveg=bea·fw). Then, we showed that such an exponential dependence of Cveg on fw also exists in ESMs of CMIP5 and CMIP6 (all P < 0.01), even though age‐dependent processes have not been incorporated in most models. However, the exponential Cveg‐fw relationship varied greatly among the models, and the coefficient b was systematically lower in the ESMs (0.08 ± 0.11; mean ± SD) than the observations (0.28). Based on a compiled forest age data set, we further found that the observed nonlinear increase of Cveg with forest age across the Northern Hemisphere (>30°N) was not captured by ESMs. These findings reveal a high disagreement on the spatially nonlinear relationship between vegetation carbon stock and woody fraction in current ESMs. The exponential relationship based on observations provides one useful benchmark for ESMs when they implement the age‐dependent processes in the future. Plain Language Summary: Forest age plays an important role in vegetation carbon stock (Cveg) predictions. This study detects a nonlinear increase of Cveg with woody fraction (fw) in aging forests across 1,145 in situ observations. The nonlinear Cveg‐fw relationship was then used to benchmark the age impacts on Cveg predictions in Earth system models (ESMs). Combined with a global forest age data set, we show that current ESMs divergently represent the relationship between Cveg and forest age. Our study suggests that the Cveg‐fw relationship could be one useful benchmark for evaluating ESMs. Key Points: Observations constrain an exponential relationship in Cveg and fwThe exponential relationship in Cveg and fw could be one useful benchmark for ESMsESMs show divergent relationships between Cveg and forest age [ABSTRACT FROM AUTHOR]

In eukaryotic cells, gene expression is greatly influenced by the dynamic chromatin environment. Epigenetic mechanisms, including covalent modifications to DNA and histone tails and the accessibility of chromatin, create various chromatin states for stress‐responsive gene expression that is important for adaptation to harsh environmental conditions. Recent studies have revealed that many epigenetic factors participate in abiotic stress responses, and various chromatin modifications are changed when plants are exposed to stressful environments. In this review, we summarize recent progress on the cross‐talk between abiotic stress response pathways and epigenetic regulatory pathways in plants. Our review focuses on epigenetic regulation of plant responses to extreme temperatures, drought, salinity, the stress hormone abscisic acid, nutrient limitations and ultraviolet stress, and on epigenetic mechanisms of stress memory. [ABSTRACT FROM AUTHOR]

Background: It has been documented that Helicobacter hepaticus (H hepaticus) infection is linked to chronic hepatitis and liver cancer. However, our understanding of the molecular mechanisms underlying progression of the H hepaticus‐induced hepatic inflammation to cellular hepatocarcinoma is still limited. Materials and methods: In our study, male BALB/c mice were infected by H hepaticus for 8, 12, 16, 20, and 24 weeks. Histopathology, H hepaticus colonization dynamics, select signaling pathways, and expression of key inflammatory cytokines in the liver were examined. Results: We found that H hepaticus was detectible in feces of mice at 7 days postinfection (DPI) by PCR, but it was not detected in the livers by PCR until 8 weeks postinfection (WPI). In addition, abundance of colonic and hepatic H hepaticus was progressively increased over the infection duration. H hepaticus‐induced hepatic inflammation and fibrosis were aggravated over the infection duration, and necrosis or cirrhosis developed in the infected liver at 24 WPI H hepaticus infection increased levels of alanine aminotransferase and aspartate aminotransferase. Moreover, mRNA levels of Il‐6 and Tnf‐α were significantly elevated in the livers of H hepaticus‐infected mice compared to uninfected control from 8 WPI to 24 WPI. Furthermore, Stat3, nuclear factor‐κB (p65), and MAPK (Erk1/2 and p38) were activated by H hepaticus infection. Conclusions: These data demonstrated that male BALB/c mice can be used as a new mouse model of H hepaticus‐induced liver diseases and that the H hepaticus‐induced liver injury is triggered by NF‐κB, Jak‐Stat, and MAPK signaling pathways. [ABSTRACT FROM AUTHOR]

Alkynes are an important class of organic molecules due to their utility as versatile building blocks in synthesis. Although efforts have been devoted to the difunctionalization of alkynes, general and practical strategies for the direct hydroalkylation and alkylarylation of terminal alkynes under mild reaction conditions are less explored. Herein, we report a photoredox/nickel dual‐catalyzed anti‐Markovnikov‐type hydroalkylation of terminal alkynes as well as a one‐pot arylalkylation of alkynes with alkyl carboxylic acids and aryl bromides via a three‐component cross‐coupling. The results indicate that the transformations proceed via a new mechanism involving a single‐electron transfer with subsequent energy‐transfer activation pathways. Moreover, steady‐state and time‐resolved fluorescence‐spectroscopy measurements, density functional theory (DFT) calculations, and wavefunction analysis have been performed to give an insight into the catalytic cycle. [ABSTRACT FROM AUTHOR]

Alkynes are an important class of organic molecules due to their utility as versatile building blocks in synthesis. Although efforts have been devoted to the difunctionalization of alkynes, general and practical strategies for the direct hydroalkylation and alkylarylation of terminal alkynes under mild reaction conditions are less explored. Herein, we report a photoredox/nickel dual‐catalyzed anti‐Markovnikov‐type hydroalkylation of terminal alkynes as well as a one‐pot arylalkylation of alkynes with alkyl carboxylic acids and aryl bromides via a three‐component cross‐coupling. The results indicate that the transformations proceed via a new mechanism involving a single‐electron transfer with subsequent energy‐transfer activation pathways. Moreover, steady‐state and time‐resolved fluorescence‐spectroscopy measurements, density functional theory (DFT) calculations, and wavefunction analysis have been performed to give an insight into the catalytic cycle. [ABSTRACT FROM AUTHOR]

Chemical transformations based on cascade reactions have the potential to simplify the preparation of diverse and architecturally complex molecules dramatically. Herein, we disclose an unprecedented and efficient method for the cross‐coupling of radical precursors, dienes, and electrophilic coupling partners via a photoredox‐ and nickel‐enabled cascade cross‐coupling process. The cascade reaction furnishes a diverse array of saturated carbo‐ and heterocyclic scaffolds, thus providing access to a quick gain in C−C bond saturation. [ABSTRACT FROM AUTHOR]

Chemical transformations based on cascade reactions have the potential to simplify the preparation of diverse and architecturally complex molecules dramatically. Herein, we disclose an unprecedented and efficient method for the cross‐coupling of radical precursors, dienes, and electrophilic coupling partners via a photoredox‐ and nickel‐enabled cascade cross‐coupling process. The cascade reaction furnishes a diverse array of saturated carbo‐ and heterocyclic scaffolds, thus providing access to a quick gain in C−C bond saturation. [ABSTRACT FROM AUTHOR]

Internal consistency implies, at a minimum, that the thermodynamic relationships, reference and standard states, and activity coefficient models are consistently applied to all data within a given TDF. A TDF provides equilibrium constants for reactions involving solids, aqueous species, gases, adsorbed surface species, and ion-exchange species. A TDF may also provide parameters for modeling kinetics of mineral dissolution and precipitation, activity coefficients of aqueous species, and fugacity coefficients of gaseous species. [Extracted from the article]

The carbon‐carbon (C—C) σ‐bonds construct the fundamental frameworks of organic molecules. The direct functionalization of C—C bonds represents one of the most efficient and step‐economical transformations in synthetic chemistry. The past few decades have witnessed the fast development of transition‐metal mediated C—C bond activation. In contrast, the radical‐promoted C—C bond cleavage has received relatively less attention. As the occurrence of ring strain significantly facilitates the fission of cyclic C—C bonds via radical approaches, the strain relief‐driven C—C bond activation mostly relies on the three‐ and four‐membered rings. The C—C activation of non‐strained molecules such as medium‐ or large‐sized rings and linear alkanes remains challenging. In this review, we will focus on the recent advances in radical‐mediated C—C bond activation of non‐strained molecules. Herein, the alkoxy‐ and iminyl‐radical triggered scission of non‐strained C—C bonds and C—C cleavage via the strategy of remote functional group migration is summarized. The recent advances in radical‐mediated C—C bond activation of non‐strained molecules are summarized in this review. These transformations are mainly accomplished during the past three years, thus representing an emerging topic in organic chemistry. The alkoxy‐ and iminyl‐radical triggered cleavage of non‐strained C—C bonds and the C—C activation via the strategy of remote functional group migration are discussed in details. [ABSTRACT FROM AUTHOR]

Summary: Aquaculture has been challenged to explore alternative proteins to develop efficient feed formulations that foster a sustainable future growth. Largemouth bass (LMB) are economically important cultured fish with a high demand for protein. One of the traditional ingredients used to develop protein diets is fish meal (FM). With the aquaculture industry expanding, the FM price climbs with broadening the imbalance between the supply and requirement. Hence, there is a requisite to explore novel alternative proteins sources. In this review, we summarised recent knowledge about the alternative sources of proteins with potential to partially or fully substitute FM in LMB feed and the shortcomings of present alternative proteins. We also highlight the challenges faced for LMB feed in the substitution of FM with alternative proteins, which need more in‐depth investigations in the future. [ABSTRACT FROM AUTHOR]

Fluorine incorporation by concomitant fluoroalkyl radical addition to alkene or alkyne and functional group migration (FGM) represents an ingenious and robust strategy for the synthesis of structurally diverse fluorinated compounds. This account gives an overview of related studies in our group, in which three main reaction modes are discussed: 1) radical fluoroalkylative difunctionalization of unactivated alkenes via intramolecular FGM; 2) alkene difunctionalization by docking‐migration process using fluoroalkyl‐containing bifunctional reagents; 3) incorporation of fluoroalkyl group into C(sp3)−H bond via consecutive hydrogen atom transfer (HAT) and FGM. Relying on these methods, a variety of trifluoromethylation and di‐/mono‐fluoroalkylation reactions along with the migration of cyano, heteroaryl, oximino, formyl, alkynyl, and alkenyl groups have been accomplished under mild conditions. [ABSTRACT FROM AUTHOR]

Abstract: Cycloalkanols prove to be privileged precursors for the synthesis of distally substituted alkyl ketones and polycyclic aromatic hydrocarbons (PAHs) by virtue of cleavage of their cyclic C−C bonds. Direct functionalization of cyclobutanols to build up other chemical bonds (e. g., C−F, C−Cl, C−Br, C−N, C−S, C−Se, C−C, etc.) has been achieved by using the ring‐opening strategy. Mechanistically, the C−C cleavage of cyclobutanols can be involved in two pathways: (a) transition‐metal catalyzed β‐carbon elimination; (b) radical‐mediated ‘radical clock’‐type ring opening. The recent advances of our group for the ring‐opening functionalization of tertiary cycloalkanols are described in this account. [ABSTRACT FROM AUTHOR]

Abstract: Cooperative swarms of robots equipped with cameras are robust against failures and can explore Global Navigation Satellite System‐denied environments efficiently. Applying Visual Simultaneous Localization and Mapping (VSLAM) techniques, vehicles can estimate their trajectories and simultaneously reconstruct the map of the environment using visual cues. Due to constraints on payload size, weight, and costs, many Visual Simultaneous Localization and Mapping applications must be based on a single camera. The associated monocular estimation of the trajectory and map is ambiguous by a scale factor. This work shows that by exploiting sparse range measurements between a pair of dynamic rovers in planar motion, the correct scale factors of both cameras and the relative position, as well as the relative attitude between the rovers, can be estimated. Neither images nor feature vectors are required to be transmitted over the communication channel for the proposed method, which is a significant advantage in practice. Copyright © 2018 Institute of Navigation. [ABSTRACT FROM AUTHOR]

Objectives: Belief inflexibility has been suggested to maintain delusions. Different measures of assessing belief inflexibility have been developed, and it remains unclear whether patients with delusions display belief inflexibility similarly across measures. As delusions consist of multiple dimensions, the aim of this meta‐analytic review was to examine how belief inflexibility is related to different aspects of delusions (conviction, distress, and preoccupation) and to compare these associations between interview‐based and task‐based measures of belief inflexibility. Methods: We conducted a systematic database search (PsycINFO, PsycARTICLES, PubMed, and MEDLINE) and identified relevant articles using the following search items: belief*, delusion*, or overvalued idea*; psychosis or schizo*; flexib*, inflexib*, change, revision, or update. Meta‐analyses were conducted for each dimension of delusions and were reported according to the PRISMA guidelines. Results: A total of 16 studies, with a total sample of 1,065, were included in the analysis. Belief inflexibility was associated with global severity of delusions (Hedges' g = 0.452, p < .001). Specifically, all dimensions of delusions were significantly associated with belief inflexibility (conviction: Hedges' g = 0.678, p < .001; preoccupation: Hedges' g = 0.274, p = .002; distress: Hedges' g = 0.200, p = .025). There was no significant heterogeneity across studies for each dimension. Preliminary subgroup analysis did not find any significant between‐measure differences in the relationship between belief inflexibility and overall severity of delusions. Conclusions: Belief inflexibility, across measures, was robustly associated with delusions, with a particularly strong association for delusional conviction. Our results carried implications for process‐based interventions for delusions. Practitioner points: Positive clinical implications Belief inflexibility is consistently associated with the maintenance of delusions. Assessing belief inflexibility in routine clinical practice will inform psychological interventions for patients with persistent delusions. Interview‐ and task‐based measures of belief inflexibility may be used complementarily to facilitate our understanding of this reasoning bias. Aetiological factors may be more closely associated with some aspects of delusions than the others. In line with a multidimensional view of delusions, interventions targeting different dimensions of delusions may have different therapeutic emphases.Limitations The current review focused on three core dimensions of delusions only (conviction, preoccupation, distress). Other ways of dissecting delusions are possible. Comparisons between the two measures of belief inflexibility may benefit from further research. [ABSTRACT FROM AUTHOR]

Abstract: An efficient photoredox/nickel catalyzed sulfonylation reaction of aryl, heteroaryl, and vinyl halides has been achieved for the first time. This newly developed sulfonylation protocol provides a versatile method for the synthesis of diverse aromatic sulfones at room temperature and shows excellent functional group tolerance. The electrophilic coupling partners are not limited to aryl, heteroaryl, and vinyl bromides and iodides, but also includes less reactive aryl chlorides as suitable substrates for this transformation. [ABSTRACT FROM AUTHOR]

Abstract: An efficient photoredox/nickel catalyzed sulfonylation reaction of aryl, heteroaryl, and vinyl halides has been achieved for the first time. This newly developed sulfonylation protocol provides a versatile method for the synthesis of diverse aromatic sulfones at room temperature and shows excellent functional group tolerance. The electrophilic coupling partners are not limited to aryl, heteroaryl, and vinyl bromides and iodides, but also includes less reactive aryl chlorides as suitable substrates for this transformation. [ABSTRACT FROM AUTHOR]

The solar‐driven evolution of hydrogen from water using particulate photocatalysts is considered one of the most economical and promising protocols for achieving a stable supply of renewable energy. However, the efficiency of photocatalytic water splitting is far from satisfactory due to the sluggish electron‐hole pair separation kinetics. Herein, isolated Mo atoms in a high oxidation state have been incorporated into the lattice of Cd0.5Zn0.5S (CZS@Mo) nanorods, which exhibit photocatalytic hydrogen evolution rate of 11.32 mmol g−1 h−1 (226.4 μmol h−1; catalyst dosage 20 mg). Experimental and theoretical simulation results imply that the highly oxidized Mo species lead to mobile‐charge imbalances in CZS and induce the directional photogenerated electrons transfer, resulting in effectively inhibited electron‐hole recombination and greatly enhanced photocatalytic efficiency. [ABSTRACT FROM AUTHOR]

The solar‐driven evolution of hydrogen from water using particulate photocatalysts is considered one of the most economical and promising protocols for achieving a stable supply of renewable energy. However, the efficiency of photocatalytic water splitting is far from satisfactory due to the sluggish electron‐hole pair separation kinetics. Herein, isolated Mo atoms in a high oxidation state have been incorporated into the lattice of Cd0.5Zn0.5S (CZS@Mo) nanorods, which exhibit photocatalytic hydrogen evolution rate of 11.32 mmol g−1 h−1 (226.4 μmol h−1; catalyst dosage 20 mg). Experimental and theoretical simulation results imply that the highly oxidized Mo species lead to mobile‐charge imbalances in CZS and induce the directional photogenerated electrons transfer, resulting in effectively inhibited electron‐hole recombination and greatly enhanced photocatalytic efficiency. [ABSTRACT FROM AUTHOR]

Immunotherapy is being increasingly recognized as a key therapeutic modality to treat cancer and represents one of the most exciting treatments for the disease. Fighting cancer with immunotherapy has revolutionized treatment for some patients and therapies targeting the immune checkpoint molecules such as CTLA-4 and PD-1 have achieved durable responses in melanoma, renal cancer, Hodgkin's diseases and lung cancer. However, the success rate of these treatments has been low and a large number of cancers, including colorectal cancer remain largely refractory to CTLA-4 and PD-1 blockade. This has provided impetus to identify other co-inhibitory receptors that could be exploited to enhance response rates of current immunotherapeutic agents and achieve responses to the cancers that are refectory to immunotherapy. Tim-3 is a co-inhibitory receptor that is expressed on IFN-g-producing T cells, FoxP3+ Treg cells and innate immune cells (macrophages and dendritic cells) where it has been shown to suppress their responses upon interaction with their ligand(s). Tim-3 has gained prominence as a potential candidate for cancer immunotherapy, where it has been shown that in vivo blockade of Tim-3 with other check-point inhibitors enhances anti-tumor immunity and suppresses tumor growth in several preclinical tumor models. This review discusses the recent findings on Tim-3, the role it plays in regulating immune responses in different cell types and the rationale for targeting Tim-3 for effective cancer immunotherapy. [ABSTRACT FROM AUTHOR]

Fire is a common disturbance in many biomes, with both beneficial and detrimental effects on soil biology, which largely depend on fire intensity. However, little is known about the impact of fire on soil nematode communities in terrestrial ecosystem. In the present study, we investigated the effects of short‐term prescribed fire on soil nematode communities and soil properties in an old‐field grassland in Northern China. The results showed that burning significantly increased soil nematode abundance by 77% and genus richness by 49% compared to the control. Burning also decreased taxon dominance by 45% (Simpson's D) and increased nematode diversity by 31% (Shannon‐Weaver H'). However, burning increased plant parasites (particularly genera Cephalenchus and Pratylenchus) and shifted community to more bacterial‐feeding genera (i.e., decreased Channel Index). Generally, burning increased soil bio‐available nitrogen (NH4+–N and NO3−–N) content, which would be the main drivers causing nematode community to flourish via a "bottom‐up" effect. These results suggest that prescribed fire increases nematode diversity and alters community composition toward more plant parasites and bacterial feeders. Our findings highlight the importance of prescribed fire management in shaping short‐term nematode community structure and function, but the long‐term effects and impacts of these changes on soil nutrient and carbon cycling remain unknown. [ABSTRACT FROM AUTHOR]

Single‐step conversion of methane to methanol in the gaseous phase is required for high value added application of methane and environmental protection, but it is challenging. Here, direct oxidation of methane to methanol under gaseous condition on iridium promoted Cu/CeO2 catalyst, prepared using a sol‐gel method, is investigated. The addition of iridium can effectively upgrade the redox properties and oxygen storage capacity due to intense metal interaction, stimulating a prominent catalytic performance for methane conversion to methanol on Cu−Ir@CeO2 catalyst. Approximately 26.2 μmol/gcat methanol yield and 68 % methanol selectivity are achieved on the trimetallic 5Cu0.5Ir@CeO2 catalyst at 550 °C in 2 h. Consequences of the analysis of XRD, SEM, HRTEM, Raman, FI‐IR and XPS demonstrate that highly‐dispersed Ir and Cu species are uniformly distributed on CeO2 surface, and partial Cu or Ir atoms replace Ce4+ in CeO2 lattice due to the metal interaction in the colloidal structure, which can impact the catalyst's electronic properties. H2 temperature‐programmed reduction (H2‐TPR) and CH4 temperature‐programmed desorption (CH4‐TPD) results disclose that the unique ternary surface exhibits excellent redox properties and strong adsorption capacity for methane, which can activate the first C−H bond of methane to methyl species, and then react with OH− to form methanol. The good stability in cyclic operation is an additional attribute, rendering this type of catalyst a "front‐runner" in future catalyst development for direct methane‐to‐methanol. This composite catalyst design provides hope for developing ternary metal‐oxide catalysts for functionalization of methane. [ABSTRACT FROM AUTHOR]

Herein, we report a reductive cross‐coupling reaction of α‐oxy halides, simply generated from aldehydes, with a series of C(sp2)‐ and C(sp)‐electrophiles. A wide range of aryl and heteroatom aryl halides, vinyl bromides, alkynyl bromides, and acyl chlorides react with unhindered and hindered aldehyde‐derived α‐oxy halides by providing protected alcohols as well as α‐hydroxy ketones. Noteworthy, the reductive couplings are achieved not only through thermal catalysis with the use of metal reductants but also by photocatalysis, electrochemistry, and mechanochemistry. The unrestricted interchange of the four strategies indicates their underlying mechanistic similarities. The generation of NiI intermediate is proposed to be the key point for ketyl radical formation via a single‐electron transfer (SET) event, which was rationalized by an array of control experiments and density functional theory (DFT) calculations. [ABSTRACT FROM AUTHOR]

Arylboronic acids and their derivatives have been widely exploited as important synthetic precursors in organic synthesis, materials science, and pharmaceutical development. In addition to numerous applications in transition metal-mediated cross-coupling reactions, transition metal-free transformations involving arylboronic acids and derivatives have recently received a surge of attention for converting the CB bond to CC, CN, CO, and many other CX bonds. Consequently, a wide range of useful compounds, e.g., phenols, anilines, nitroarenes, and haloarenes, has been readily synthesized. Amongst these efforts, many versatile reagents have been developed and a lot of practical approaches demonstrated. The research in this promising field is summarized in the current review and organized on the basis of the type of bonds being formed. [ABSTRACT FROM AUTHOR]

Summary: Previous intensive research has described the molecular impacts of high‐pressure processing (HPP) on fish meat chemical composition, such as myofibril structural proteins, enzymes, myoglobin and lipids. This work aims to collect articles on sensory evaluation of pressure‐treated aquatic products to determine the practical effects of HPP on aquatic products, especially sensory properties, by comparing the differences between instrumental tests and sensory evaluation, between trained sensory assessors and consumers to guide and improve the processing of aquatic products. The findings indicate that laboratory devices such as spectrophotometers, texture analysers and electronic noses, and trained sensory assessors can detect pressure‐induced changes in appearance, texture, off‐odour, and flavour, such as discoloration, whitening, increased hardness and initiation of lipids oxidation. However, consumers did not perceive the pressure‐induced changes in odour and colour. Besides, consumers' attitudes towards pressure‐treated aquatic products are ambiguous in the range of 300 to 600 MPa, and professional testing and assessment fail to replace hedonic tests. In complex matrices of aquatic products, particular attention is needed to be paid to changes in sensory qualities dominated by microorganisms, endogenous enzymes and bioactive compounds after HPP treatment and throughout commercial storage. [ABSTRACT FROM AUTHOR]

Extracellular vesicles (EVs) derived from differentiating induced stem cells maintain their original stemness and differentiating trends and possess strong immunoregulatory capability. Biomaterials equipped with EVs are very promising in regenerative medicine. However, surface EV‐decoration on osteoimplants remains a challenge, due to the complexity of traditional molecular conjugations and the fragility of EVs. Here, mussel‐like molecular adhesion is combined with bioorthogonal click conjugation to introduce EVs on titanium (Ti) implants. The biomimetic adhesion and clickable molecular linkage allow mild and stable tethering of pre‐osteogenic mesenchymal stem cell (MSC)‐derived EVs on Ti implants. EV‐decorated implants exhibit significantly enhanced osseointegration on the bone‐implant surface under diabetic conditions, promoting increased expression of osteogenic genes. Modified surfaces impelled phenotypic alterations in macrophage polarization via multi‐pathway regulation, decreasing proinflammatory M1 macrophage formation, which can lead to the promotion of surface osteogenesis. On Ti rods implanted in a diabetic rat model, EV coating inhibited M1macrophages around the prosthesis, resulting in satisfactory long‐term osseointegration. This study offers a new perspective to represent a simple and effective means for surface EV decoration, providing an osteoimmunomodulatory effect to enhance the diabetic osseointegration of implants. [ABSTRACT FROM AUTHOR]

Background Case Presentation Conclusions Mobile bearing fracture is a rare long‐term complication of unicompartmental knee arthroplasty (UKA), and relevant reports are sparse. Hence, its treatment options need further exploration.This study presents the case of fracture of a polyethylene insert that occurred 12 years after mobile bearing medial UKA in a 75‐year‐old overweight woman who then underwent surgical intervention at our institution. However, we encountered significant challenges in removing the fragments from the broken bearing, resulting in retention of the remaining one‐third of the fragment. We solved this problem by replacing the fractured insert with thicker mobile bearing. During the 1‐month postoperative follow‐up, the patient achieved good range of motion and excellent satisfaction, with no reported complications and a Knee Society Score of 90. Additionally, we reviewed the literature on the treatment for mobile bearing fractures after UKA.Bearing fracture is a rare cause of failure of mobile bearing UKA. This case highlights the challenges of UKA fracture bearing retrieval and underscores that mobile bearing replacement can be an effective intervention. The case we report shows that when removal of a residual meniscal bearing in a posterior dislocation is difficult to achieve, compromise may be an appropriate option because it does not cause additional complaints to the patient. This case emphasizes the importance of the surgeon having a thorough preoperative understanding of the location and potential pitfalls of fracture fragments in such situations. [ABSTRACT FROM AUTHOR]

Objective Methods Results Conclusion Total hip arthroplasty (THA) combined with proximal femoral reconstruction is a novel osteotomy technique developed to address severe hip deformities. There is a paucity of robust clinical and radiological evidence regarding the outcomes of this novel osteotomy technique. This study aimed to evaluate the clinical and radiological outcomes of THA combined with proximal femoral reconstruction during the early follow‐up.This is a retrospective case series of 63 hips who underwent THA combined with proximal femoral reconstruction at a single institution between January 2020 and July 2023. The mean age of patients was 39.6 ± 12.6 years. The mean follow‐up was 25.6 ± 3.8 months. Surgical characteristics and perioperative variables were evaluated to assess the efficacy of this technique. Harris hip score (HHS) was utilized to evaluate hip function. Leg length discrepancy (LLD) was evaluated in X‐ray. The incidence of major adverse events including deep vein thrombosis (DVT), osteolysis, nonunion of the osteotomy, intraoperative femoral fracture, and infection was also evaluated. Paired‐samples t‐test was used to compare preoperative and postoperative HHS and LLD.The mean operative time was 125.1 min. The mean size of the acetabular components used was 45.2 mm, and the stem size was 7.5. The primary friction interface was ceramic‐on‐ceramic, accounting for 92.1% of cases. The average length of hospital stay was 8.5 days. The mean cost of treatment was 46,296.0 Yuan. There was a significant improvement in postoperative HHS (p < 0.001) and LLD (p < 0.001) compared to preoperative values. The incidence of deep venous thrombosis was 4.8%; osteolysis rates for the cup and stem were 4.8% and 6.4%, respectively. The non‐union and dislocation rates were 1.6% and 3.2%, respectively. There was no incidence of postoperative infection.The novel osteotomy surgical procedure yields reliable and impressive clinical and radiological outcomes, with minimal complications. We advocate for its use in complex primary THA cases involving severe proximal femoral deformities. [ABSTRACT FROM AUTHOR]

ABSTRACT Deep sowing is a traditional method for drought resistance in maize production, and mesocotyl elongation is strongly associated with the ability of maize to germinate from deep soil. However, little is known about the functional genes and mechanisms regulating maize mesocotyl elongation. In the present study, we identified a plant‐specific SIMILAR TO RCD‐ONE (SRO) protein family member, ZmSRO1e, involved in maize mesocotyl elongation. The expression of ZmSRO1e is strongly inhibited upon transfer from dark to white light. The loss‐of‐function zmsro1e mutant exhibited a dramatically shorter mesocotyl than the wild‐type in both constant light and darkness, while overexpression of ZmSRO1e significantly promoted mesocotyl elongation, indicating that ZmSRO1e positively regulates mesocotyl elongation. We showed that ZmSRO1e physically interacted with ZmbZIP61, an ortholog of Arabidopsis ELONGATED HYPOCOTYL 5 (HY5) and showed a function similar to that of HY5 in regulating photomorphogenesis. We found that ZmSRO1e repressed the transcriptional activity of ZmbZIP61 toward target genes involved in the regulation of cell expansion, such as ZmEXPB4 and ZmEXPB6, by interfering with the binding of ZmbZIP61 to the promoters of target genes. Our results provide a new understanding of the mechanism by which SRO regulates photomorphogenesis and highlight its potential application in deep sowing‐resistant breeding. [ABSTRACT FROM AUTHOR]

Objective: The specific role of fibroblast‐like synoviocytes (FLSs) in the pathogenesis of rheumatoid arthritis (RA) is still not fully elucidated. This study aimed to explore the molecular mechanisms of epigenetic pathways, including three epigenetic factors, microRNA (miRNA)‐22 (MIR22), ten‐eleven translocation methylcytosine dioxygenase 3 (TET3), and MT‐RNR2 like 2 (MTRNR2L2), in RA‐FLSs. Methods: The expression of MIR22, TET3, and MTRNR2L2 in the synovium of patients with RA and arthritic mice were determined by fluorescence in situ hybridization, quantitative polymerase chain reaction (qPCR), immunohistochemistry, and Western blot. Mir22−/− and Tet3+/− mice were used to establish a collagen antibody–induced arthritis (CAIA) model. Mir22 angomir and Tet3 small interfering RNA (siRNA) were used to illustrate the therapeutic effects on arthritis using a collagen‐induced (CIA) model. Bioinformatics, luciferase reporter assay, 5‐hydroxymethylcytosine (5hmC) dot blotting, chromatin immunoprecipitation–qPCR, and hydroxymethylated DNA immunoprecipitation were conducted to show the direct repression of MIR22 on the TET3 and transcriptional activation of TET3 on MTRNR2L2. Results: The Mir22−/− CAIA model and RA‐FLS–related in vitro experiments demonstrated the inhibitory effect of MIR22 on inflammation. MIR22 can directly inhibit the translation of TET3 in RA‐FLSs by binding to its 3′ untranslated region in TET3. The Tet3+/− mice–established CAIA model showed less severe symptoms of arthritis in vivo. In vitro experiments further confirmed the proinflammatory effect of TET3 in RA. In addition, the CIA model was used to validate the therapeutic effects of Mir22 angomir and Tet3 siRNA. Finally, TET3 exerts its proinflammatory effect by promoting 5hmC production in the promoter of its target MTRNR2L2 in RA‐FLSs. Conclusion: The key role of the MIR22‐TET3‐MTRNR2L2 pathway in RA‐FLSs provided an experimental basis for further studies into the pathogenesis and related targets of RA from the perspective of FLSs. [ABSTRACT FROM AUTHOR]

Recurrent bacterial infections, impenetrable microbial biofilms, and irremediable antibiotic resistance are the most perilous threats in orthopedic implant‐associated infections (IAIs). Recently, chemodynamic therapy (CDT) has been considered a promising therapy, while the clinical practices for existing CDT agents are limited by the low therapeutic efficiency in physiological circumstances. Herein, it is demonstrated that silica‐copper nanosheets (Si@Cu NSs) exhibit a combined therapeutic photothermal‐chemodynamic strategy for IAIs treatment with superior capacity and biocompatibility. This unique design endows the nanostructure with enhanced copper‐based Fenton‐like properties via p‐d orbital hybridization by incorporating copper nanoclusters (Cu NCs) on silicene nanosheets (Si NSs) matrix, integrating inherent photothermal performance of Si NSs with specific catalytic anti‐infection of Cu NCs against planktonic bacteria and biofilms both in vitro and in vivo. This study not only reveals the promising bio‐application prospects of 2D nanocatalytic biomaterials but also demonstrates the feasibility of constructing novel CDT agents by orbital hybridization for the catalytic treatment of IAIs. [ABSTRACT FROM AUTHOR]