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(S)-Methoprene has been widely applied as a powerful biochemical pesticide to control disease vectors and other pestiferous arthropods of economic importance. As a juvenile hormone analogue, many products based on (S)-methoprene are developed and commercialized in the USA, Europe, and elsewhere. However, the agricultural use of (S)-methoprene and its analogues remains underexplored. Here, based on an intermediate derivatization strategy and structural modification, a series of enantiopure (S)-methoprene derivatives were designed for their expected bioactivity against two crop-threatening pests. Six compounds showed more than 2-fold stronger inhibition of emergence against Plutella xylostellathan (S)-methoprene, among which one that was designated as B2showed even superior activity to the conventional chemical pesticide and biopesticide with IE50of 0.02 mg/L. Nine compounds exhibited over 2-fold higher bioactivity against Aphis craccivoragrowth than (S)-methoprene. The physicochemical property evaluation and toxicological test showed that the potent (S)-methoprene derivatives were low toxic to the nontarget organism and the environment. Molecular docking studies further demonstrated that the high bioactivity of B2may be partially attributed to its great affinity for binding to juvenile hormone receptors of P. xylostella. The current study suggests that B2is a biochemical pesticide candidate with potency to be developed as a new agrochemical for lepidopteran control.

The past two decades has witnessed a remarkable increase in the number of microbial genomes retrieved from marine systems1,2. However, it has remained challenging to translate this marine genomic diversity into biotechnological and biomedical applications3,4. Here we recovered 43,191 bacterial and archaeal genomes from publicly available marine metagenomes, encompassing a wide range of diversity with 138 distinct phyla, redefining the upper limit of marine bacterial genome size and revealing complex trade-offs between the occurrence of CRISPR–Cas systems and antibiotic resistance genes. In silico bioprospecting of these marine genomes led to the discovery of a novel CRISPR–Cas9 system, ten antimicrobial peptides, and three enzymes that degrade polyethylene terephthalate. In vitro experiments confirmed their effectiveness and efficacy. This work provides evidence that global-scale sequencing initiatives advance our understanding of how microbial diversity has evolved in the oceans and is maintained, and demonstrates how such initiatives can be sustainably exploited to advance biotechnology and biomedicine.

To promote the generalization ability of breast tumor segmentation models, as well as to improve the segmentation performance for breast tumors with smaller size, low-contrast and irregular shape, we propose a progressive dual priori network (PDPNet) to segment breast tumors from dynamic enhanced magnetic resonance images (DCE-MRI) acquired at different centers. The PDPNet first cropped tumor regions with a coarse-segmentation based localization module, then the breast tumor mask was progressively refined by using the weak semantic priori and cross-scale correlation prior knowledge. To validate the effectiveness of PDPNet, we compared it with several state-of-the-art methods on multi-center datasets. The results showed that, comparing against the suboptimal method, the DSC and HD95 of PDPNet were improved at least by 5.13% and 7.58% respectively on multi-center test sets. In addition, through ablations, we demonstrated that the proposed localization module can decrease the influence of normal tissues and therefore improve the generalization ability of the model. The weak semantic priors allow focusing on tumor regions to avoid missing small tumors and low-contrast tumors. The cross-scale correlation priors are beneficial for promoting the shape-aware ability for irregular tumors. Thus integrating them in a unified framework improved the multi-center breast tumor segmentation performance.

Photoredox catalytic processes offer the potential for precise chemical reactions using light and materials. The central determinant is identified as interfacial charge transfer, which simultaneously engenders distinctive behavior in the overall reaction. An in-depth elucidation of the main mechanism and highlighting of the complexity of interfacial charge transfer can occur through both diffusive and direct transfer models, revealing its potential for sophisticated design in complex transformations. The fundamental photophysics uncover these comprehensive applications and offer a clue for future development. This research contributes to the growing body of knowledge on interfacial charge transfer in photoredox catalysis and sets the stage for further exploration of this fascinating area of research.

Ferroelectricity, especially the Si-compatible type recently observed in hafnia-based materials, is technologically useful for modern memory and logic applications, but it is challenging to differentiate intrinsic ferroelectric polarization from the polar phase and oxygen vacancy. Here, we report electrically controllable ferroelectricity in a Hf0.5Zr0.5O2-based heterostructure with Sr-doped LaMnO3, a mixed ionic–electronic conductor, as an electrode. Electrically reversible extraction and insertion of an oxygen vacancy into Hf0.5Zr0.5O2are macroscopically characterized and atomically imaged in situ. Utilizing this reversible process, we achieved multilevel polarization states modulated by the electric field. Our study demonstrates the usefulness of the mixed conductor to repair, create, manipulate, and utilize advanced ferroelectric functionality. Furthermore, the programmed ferroelectric heterostructures with Si-compatible doped hafnia are desirable for the development of future ferroelectric electronics.

Ego-pose estimation and 3D object tracking are two critical problems that autonomous driving systems must solve. The solutions to these problems are usually based on their respective assumptions, i.e., the static world assumption for simultaneous localization and mapping (SLAM) and the accurate ego-pose assumption in object tracking. However, these assumptions may not hold in dynamic road scenarios, where SLAM and object tracking are closely correlated. Therefore, we propose DL-SLOT, a tightly-coupled dynamic LiDAR SLAM and 3D object tracking method that addresses both problems simultaneously. This method integrates the state estimations of both the autonomous vehicle and the stationary and dynamic objects in the environment in a unified optimization framework. First, we use object detection to identify all points belonging to potentially dynamic objects. Subsequently, LiDAR odometry is performed using the filtered point cloud. Simultaneously, we propose a sliding window-based 3D multi-object tracking method considering the historical trajectories of the tracked objects. The states of the ego-vehicle, stationary objects, and dynamic objects are jointly estimated by the sliding window-based collaborative graph optimization to achieve SLOT. True stationary objects are restored from the potentially dynamic object set to join the optimization. Finally, a global pose graph is implemented to eliminate the accumulated error. Experiments on the KITTI datasets demonstrate that our method achieves better accuracy than SLAM and 3D object tracking baseline methods. This confirms that solving SLAM and object tracking simultaneously is mutually beneficial, and dramatically improves the robustness and accuracy of SLAM and object tracking in dynamic road scenarios.

In view of the fact that a driver's smoking behavior seriously affects the driving safety, a feature pyramid network (FPN)-based smoking behavior identification method has been studied in order to reduce the occurrence of the driver smoking. Most of the existing research has been focused on detection and recognition based on movements while smoking or smog characteristics. Therefore, the probability of misjudgment in such methods is high, thus to address this issue, the present work proposes a method based on FPN to detect the driver's smoking behavior. FPN has been combined with the dilated convolution technique in order to detect a small target object in the driver's image and recognize their smoking behavior. By using the driver behavior images collected from the vehicle platform, a simulation experiment was carried out by employing the behavior identification method proposed in this work. The experimental results show that the accuracy of the proposed method is 94.75%, the recall rate is 96%, the precision rate is 95.05% and the area under the receiver operating characteristic curve is 95.5%.

Control of charge separation and recombination is critical for dye-sensitized solar cells and photoelectrochemical cells, and for p-type cells, the latter process limits their photovoltaic performance. We speculated that the lateral electron hopping between dyes on a p-type semiconductor surface can effectively separate electrons and holes in space and retard recombination. Thus, device designs where lateral electron hopping is promoted can lead to enhanced cell performance. Herein, we present an indirect proof by involving a second dye to monitor the effect of electron hopping after hole injection into the semiconductor. In mesoporous NiO films sensitized with peryleneimide (PMI) or naphthalene diimide (NDI) dyes, dye excitation led to ultrafast hole injection into NiO from either excited PMI* (τ < 200 fs) or NDI* (τ = 1.2 ps). In cosensitized films, surface electron transfer from PMI–to NDI was rapid (τ = 24 ps). Interestingly, the subsequent charge recombination (ps−μs) with NiO holes was much slower when NDI–was generated by electron transfer from PMI–than when NDI was excited directly. We therefore indicate that the charge recombination is slowed down after the charge hopping from the original PMI sites to the NDI sites. The experimental results supported our hypothesis and revealed important information on the charge carrier kinetics for the dye-sensitized NiO photoelectrode system.

Plants can recruit beneficial microbes to help improve their fitness under abiotic or biotic stress. Our previous studies found that Panax notoginsengcould enrich beneficial Burkholderiasp. B36 in the rhizosphere soil under autotoxic ginsenoside stress. Here, we clarified that ginsenoside stress activated the phenylpropanoid biosynthesis and α-linolenic acid metabolism pathways of roots to increase the secretion of cinnamic acid, 2-dodecenoic acid, and 12-oxo-phytodienoic acid. These metabolites could promote the growth of B36. Importantly, cinnamic acid could simultaneously promote the chemotaxis and growth of B36, enhance the colonization of B36 in the rhizosphere, and eventually increase the survival rate of P. notoginseng. Overall, the plants could promote the growth and colonization of beneficial bacteria through key metabolites in root exudates under autotoxin stress. This finding will facilitate the practical application of beneficial bacteria in agricultural production and lead to successful and reproducible biocontrol efficacy by the exogenous addition of key metabolites.

The neutral oxygen reduction reaction (ORR) has attracted tremendous attention for its broad prospects in next-generation power storage systems. However, the extremely sluggish cathodic reaction process and the limited cognition of the reaction mechanism greatly hinder its practical application. Here, we demonstrate a dynamic reconstruction behavior induced by sulfur of the iron-nitrogen (Fe-Nx) species in neutral solution. Our developed FeS1N3-OH configuration effectively optimizes the reaction kinetics by regulating the adsorption energy of oxygen intermediates for central catalytic sites. Consequently, this structure exhibits over 363% enhancement in ORR mass activity compared to the pristine FeN4sites under neutral electrolyte. Moreover, a neutral zinc-air battery assembled with this electrocatalyst reached an ultrahigh peak power density (81.2 mW cm−2), robust stability (more than 100 h) as well as superior tolerance to extreme environments (operating between −20 °C and 60 °C), representing a critical breakthrough for neutral ORR exploration and application.

The spin of electrons plays a vital role in chemical reactions and processes, and the excited state generated by the absorption of photons shows abundant spin-related phenomena. However, the importance of electron spin in photochemistry studies has been rarely mentioned or summarized. In this review, we briefly introduce the concept of spin photochemistry based on the spin multiplicity of the excited state, which leads to the observation of various spin-related photophysical properties and photochemical reactivities. Then, we focus on the recent advances in terms of light-induced magnetic properties, excited-state magneto-optical effects and spin-dependent photochemical reactions. The review aims to provide a comprehensive overview to utilize the spin multiplicity of the excited state in manipulating the above photophysical and photochemical processes. Finally, we discuss the existing challenges in the emerging field of spin photochemistry and future opportunities such as smart magnetic materials, optical information technology and spin-enhanced photocatalysis.This review provides an overview on the concept of spin photochemistry, and summarizes some recent advances on spin-related excited state phenomena in terms of magnetism, luminescence and reactivity.

Objective:Regular retrospective analysis is necessary for potential improvement in clinical practice for the treatment of hard-to-heal wounds. Comorbidities and outcomes have demonstrated spatial and temporal diversity, emphasising the importance of updates in epidemiology. The complexity of healing hard-to-heal wounds has long been known, and so we sought evidence-based improvement on the current principles of treatment.Method:Demographic and clinical information of patients from the WoundCareLog database was collected. Patients who met the inclusion criteria and completed follow-up after treatment were included. Comorbidities were diagnosed and classified into eight categories based on ICD-10. We compared the demographic and aetiological characteristics between patients with and without comorbidities by t-test and Chi-squared test. The impact of comorbidities on wound healing were evaluated with a multivariate Cox model.Results:A total of 2163 patients met the inclusion criteria and were enrolled, of whom 37.0% were aged 61–80 years, 36.0% were aged 41–60 years and 60.8% were male. The lower extremities and buttocks were the most commonly affected areas with hard-to-heal wounds. Non-traumatic wounds accounted for 66.6% of cases, and infection, pressure and diabetes were the most common causes. Paralysis and diabetes were the most important factors which led to a prolonged healing process and inferior clinical outcomes.Conclusion:Comorbidities of hard-to-heal wounds were treated as separate contributors and their weighted effect on outcome was calculated through correlation analysis. Paralysis and diabetes were the most unfavourable comorbidities affecting the treatment of non-traumatic hard-to-heal wounds. Our study highlighted the priority of comorbidity treatment through data-driven approaches. It provides potential value in developing better public health strategies and preventive medicine.

Magnetic van der Waals (vdW) materials possess versatile spin configurations stabilized in reduced dimensions. One magnetic order is the interlayer antiferromagnetism in A-type vdW antiferromagnet, which may be effectively modified by the magnetic field, stacking order, and thickness scaling. However, atomically revealing the interlayer spin orientation in the vdW antiferromagnet is highly challenging, because most of the material candidates exhibit an insulating ground state or instability in ambient conditions. Here, we report the layer-dependent interlayer antiferromagnetic spin reorientation in air-stable semiconductor CrSBr using magnetotransport characterization and first-principles calculations. We reveal an odd–even layer effect of interlayer spin reorientation, which originates from the competitions among interlayer exchange, magnetic anisotropy energy, and extra Zeeman energy of uncompensated magnetization. Furthermore, we quantitatively constructed the layer-dependent magnetic phase diagram with the help of a linear-chain model. Our work uncovers the layer-dependent interlayer antiferromagnetic spin reorientation engineered by magnetic field in the air-stable semiconductor.

Sarcopenia was thought to be associated with adverse outcomes and will cause lots of health expenditure. But the relationship between sarcopenia and catastrophic health expenditure (CHE) had been little explored. Here, we examined the distribution of sarcopenia in relation to medical and payment burdens. We used data from three waves of China Health and Retirement Longitudinal Study including 14 130 participants from 9077 households aged over 50 years old. Sarcopenia was operationalized according to the Asian Working Group for Sarcopenia 2019. Medical expenditure was obtained by self‐reported data, and CHE was identified by WHO definitions. We used the negative binomial regression model and logistic mixed‐effects models to examine the associations between sarcopenia and medical and CHE. A total of 14 130 participants [52.2% female, aged 60.8 (SD 9.3)] from 9077 households were included in this study. The prevalence of sarcopenia was 19.8%, 11.9% for moderate sarcopenia, and 7.9% for severe sarcopenia, respectively. We identified 1416 household CHE events in all three waves. Severe sarcopenia was associated with an increase in the number of inpatient visits [incidence rate ratio 1.31, 95% confidence interval (CI): 1.03–1.66, P= 0.03] and the risk of CHE (odds ratio: 1.04, 95% CI: 1.01–1.07, P< 0.01). We saw similar effects in health service use of sarcopenia in different socio‐economic groups. Moderate sarcopenia increased the risk of CHE in the lowest socio‐economic group (odds ratio 1.03, 95% CI: 1.01–1.06, P= 0.03) and had no statistical significance in other groups. The association between severe sarcopenia and CHE did not attenuate after the adjustment of disease factors. Severe sarcopenia may increase the risk of CHE. Timely and effective intervention on moderate sarcopenia from severe sarcopenia will contribute to reduce the health burden.

Selenium (Se), is an essential trace element in the diet of fish and aquatic animals needed for growth, thyroid hormone metabolism, antioxidant activity, and immunity. Thus, this study has evaluated the dietary selenium yeast (Se-yeast) impact on the growth performance, antioxidant capacity, and gut bacterial community of zebrafish, Danio rerio. The fish with an average weight of 0.247 g ± 0.005 were distributed in 12 glass aquariums. 30 fish per aquarium in three replicates per group were exposed to different dietary Se-yeast concentrations: 0.3 mg/kg (control), 0 mg/kg, 3 mg/kg, and 30 mg/kg for three weeks. The result indicated a higher body weight gain and specific growth rate in the 3 mg/kg group in all groups. Se significantly accumulated in the liver, muscle, gill, and gut. The antioxidant genes superoxide dismutase 1 (SOD1),catalase (CAT), and glutathione peroxidase 1 (GPx1), and the gut marker genes: solute carrier family 15 member 1b (slc15a1b),fatty acid binding protein 2 (fabp2),cytochrome P450 family 8 subfamily B member 1 (cyp8b1),and cytochrome P450 family 3 subfamily A, polypeptide 65 (cyp3a65) were significantly expressed in the gut tissue. The 16 s rRNA sequencing showed a significant difference at phyla Proteobacteria, Fusobacteria, Firmicutes,and Actinobacteriaand Cetobacterium, Aeromonas, mycobacterium,and Lactobacillusat the genus level. It was concluded that dietary Se 3 mg/kg can promote growth performance and antioxidant status, furthermore, dietary Se yeast has a significant impact on the gut microbiota of D. rerio.

α-Amino acids are essential for life as building blocks of proteins and components of diverse natural molecules. In both industry and academia, the incorporation of unnatural amino acids is often desirable for modulating chemical, physical and pharmaceutical properties. Here we report a protocol for the economical and practical synthesis of optically active α-amino acids based on an unprecedented stereocontrolled 1,3-nitrogen shift. Our method employs abundant and easily accessible carboxylic acids as starting materials, which are first connected to a nitrogenation reagent, followed by a highly regio- and enantioselective ruthenium- or iron-catalysed C(sp3)–H amination. This straightforward method displays a very broad scope, providing rapid access to optically active α-amino acids with aryl, allyl, propargyl and alkyl side chains, and also permits stereocontrolled late-stage amination of carboxylic-acid-containing drugs and natural products.

Nonalcoholic steatohepatitis (NASH), as a severe form of nonalcoholic fatty liver disease (NAFLD), is characterized by liver steatosis, inflammation, hepatocellular injury and different degrees of fibrosis. The pathogenesis of NASH is complex and multifactorial, obesity and type 2 diabetes mellitus (T2DM) have been implicated as major risk factors. Glucagon-like peptide-1 receptor (GLP-1R) is one of the most successful drug targets of T2DM and obesity, and its peptidic ligands have been proposed as potential therapeutic agents for NASH. In this article we provide an overview of the pathophysiology and management of NASH, with a special focus on the pharmacological effects and possible mechanisms of GLP-1 mimetics in treating NAFLD/NASH, including dual and triple agonists at GLP-1R, glucose-dependent insulinotropic polypeptide receptor or glucagon receptor.

MnBi2Te4(MBT) is the first intrinsic magnetic topological insulator with the interaction of spin-momentum locked surface electrons and intrinsic magnetism, and it exhibits novel magnetic and topological phenomena. Recent studies suggested that the interaction of electrons and magnetism can be affected by the Mn-doped Bi2Te3phase at the surface due to inevitable structural defects. Here, we report an observation of nonreciprocal transport, that is, current-direction-dependent resistance, in a bilayer composed of antiferromagnetic MBT and nonmagnetic Pt. The emergence of the nonreciprocal response below the Néel temperature confirms a correlation between nonreciprocity and intrinsic magnetism in the surface state of MBT. The angular dependence of the nonreciprocal transport indicates that nonreciprocal response originates from the asymmetry scattering of electrons at the surface of MBT mediated by magnon. Our work provides an insight into nonreciprocity arising from the correlation between magnetism and Dirac surface electrons in intrinsic magnetic topological insulators.

Micro/nano topographic structures have shown great utility in many biomedical areas including cell therapies, tissue engineering, and implantable devices. Computer-assisted informatics methods hold great promise for the design of topographic structures with targeted properties for a specific medical application. To benefit from these methods, researchers and engineers require a highly reusable “one structural parameter – one set of cell responses” database. However, existing confounding factors in topographic cell culture devices seriously impede the acquisition of this kind of data. Through carefully dissecting the confounding factors and their possible reasons for emergence, we developed corresponding guideline requirements for topographic cell culture device development to remove or control the influence of such factors. Based on these requirements, we then suggested potential strategies to meet them. In this work, we also experimentally demonstrated a topographic cell culture device with controlled confounding factors based on these guideline requirements and corresponding strategies. A “guideline for the development of topographic cell culture devices” was summarized to instruct researchers to develop topographic cell culture devices with the confounding factors removed or well controlled. This guideline aims to promote the establishment of a highly reusable “one structural parameter – one set of cell responses” database that could facilitate the application of informatics methods, such as artificial intelligence, in the rational design of future biotopographic structures with high efficacy.

[Display omitted] Fact extraction, which aims to extract (entity, attribute, value)-tuples from massive text corpora, is crucial in the area of text data mining. Recent approaches have focused on extracting facts by mining textual patterns with semantic types, where the quality of a pattern is evaluated based on content-based criteria, such as frequency. However, these approaches overlook the dimension of pattern reliability , which reflects how likely the extracted facts are correct. As a result, a pattern of good content-quality (e.g., high frequency) may still extract incorrect facts. In this study, we consider both pattern reliability and fact trustworthiness in addressing the pattern-based fact extraction problem. To learn the complex relationship between pattern reliability and fact trustworthiness, we propose a novel deep learning model using a hybrid of the CNN and LSTM architecture. For fact embedding, we adopt CNN to extract a fix-sized representation of each component, i.e., entity, attribute, and value, of the fact. For pattern embedding, we represent the pattern as a semantic composition of its extracted fact representations. To de-emphasis the noisy facts, we consider the fact trustworthiness and frequency during the process of pattern embedding, where the features of the tuple trustworthiness information are extracted by a long short-term memory (LSTM) model. To learn the pattern-fact relational dependency, we train the model with both pattern and tuple labels. Extensive experiments involving three real-world datasets demonstrated that the proposed model significantly improves the quality of the patterns and the extracted facts in the pattern-based information extraction. [ABSTRACT FROM AUTHOR]

Crohn's disease activates the inflammatory reactions to induce intestinal disorders. Enteral nutrition (EN) could exert general immunomodulatory effects. Cecal ligation and perforation (CLP) surgery was utilized to establish Crohn's disease mice models. Survival analysis, hematoxylin-eosin staining, flow cytometry, ELISA, Western blot and liquid chromatography-tandem MS were applied. Baicalein was added to inhibit lipoxygenases. The survival rate was restored and inflammatory injury, exudate neutrophils in peritoneal lavage and serum levels of IL-6 and TNF-α were ameliorated by EN treatment as compared with CLP treatment. EN also increased ILC-3 content, 5/15-LOX level and RvD1-RvD5 in peritoneal lavage. Baicalein reversed all the detected effects of EN except ILC-3 content. EN could activate special pro-resolving mediators (SPMs) through ILCs to mitigate injuries of Crohn's disease.

A design method and corresponding fabrication procedures are proposed for a dual frusto-conical reflector of a downlight luminaire. The profile of the dual frusto-conical reflector consists of two flat-slant reflective surfaces with slightly different slopes. The optimum dual frusto-conical reflector can be obtained with the proposed design method. The finished product of the dual frusto-conical reflector is fabricated by a 3D printer and followed by surface polishing and reflection paint spraying. The measurement results show that luminaires exhibited 70% optimum illuminance confined within an illumination area of 1.8m^2, and the optimum illumination intensity is at 252 lux. The optimum efficiency of the proposed luminaire can reach 158 lm/W for normal-white light-emitting diode (LED) and 119 lm/W for warm-white LED, respectively.

This study reports the catalytic deracemization of ketones bearing stereocenters in the α-position in a single reaction via deprotonation, followed by enantioselective protonation. The principle of microscopic reversibility, which has previously rendered this strategy elusive, is overcome by a photoredox deprotonation through single electron transfer and subsequent hydrogen atom transfer (HAT). Specifically, the irradiation of racemic pyridylketones in the presence of a single photocatalyst and a tertiary amine provides nonracemic carbonyl compounds with up to 97% enantiomeric excess. The photocatalyst harvests the visible light, induces the redox process, and is responsible for the asymmetric induction, while the amine serves as a single electron donor, HAT reagent, and proton source. This conceptually simple light-driven strategy of coupling a photoredox deprotonation with a stereocontrolled protonation, in conjunction with an enrichment process, serves as a blueprint for other deracemizations of ubiquitous carbonyl compounds.

FeTe1–xSex, a promising layered material used to realize Majorana zero modes, has attracted enormous attention in recent years. Pulsed laser deposition (PLD) and molecular-beam epitaxy (MBE) are the routine growth methods used to prepare FeTe1–xSexthin films. However, both methods require high-vacuum conditions and polished crystalline substrates, which hinder the exploration of the topological superconductivity and related nanodevices of this material. Here we demonstrate the growth of the ultrathin FeTe1–xSexsuperconductor by a facile, atmospheric pressure chemical vapor deposition (CVD) method. The composition and thickness of the two-dimensional (2D) FeTe1–xSexnanosheets are well controlled by tuning the experimental conditions. The as-prepared FeTe0.8Se0.2nanosheet exhibits an onset superconducting transition temperature of 12.4 K, proving its high quality. Our work offers an effective strategy for preparing the ultrathin FeTe1–xSexsuperconductor, which could become a promising platform for further study of the unconventional superconductivity in the FeTe1–xSexsystem.

The typical Haber technical process for industrial NH3production involves plenty of energy-consumption and large quantities of greenhouse gas emission. In contrast, electrochemical N2reduction proffers environment-friendly and energy-efficient avenues to synthesize NH3at mild conditions but demands efficient electrocatalysts for the N2reduction reaction (NRR). Herein we report for the first time that commercial indium-tin oxide glass (ITO/G) can be used as a catalyst electrode toward artificial N2fixation, as it demonstrates excellent selectivity at mild conditions. Such ITO/G delivers excellent NRR performance with a NH3yield of 1.06 × 10−10mol s−1cm−2and a faradaic efficiency of 6.17% at –0.40 V versus the reversible hydrogen electrode (RHE) in 0.5 M LiClO4. Furthermore, the ITO/G also possesses good electrochemical stability and durability. Finally, the possible reaction mechanism for the NRR on the ITO catalysts was explored using first-principles calculations.

Subduction processes play a pivotal role in facilitating material exchange between the crust and mantle, contributing to the growth of continents. However, the onset and evolution of subduction remain hotly debated. Here, we developed a high‐dimensional machine learning (ML) model to use multiple compositional data (e.g., Nb/La, Nb, Ti, Nb/U, Pb/Nd, and Nb/Th) to distinguish arc‐type from non‐arc basalts worldwide, then applied this well‐trained ML model to identify and delineate the secular occurrence of Archean arc‐type basalts. Our findings indicate that basaltic arc magmatism can be traced back to only a few early Archean cratons. A noticeable increase in the prevalence of arc‐type basalts during the Mesoarchean and Neoarchean suggests the synchronous formation of Archean subduction across different cratons. This observation hints at transitioning from the predominantly stagnant geodynamic regime to the early, more mobile tectonic regime. Deep beneath the Earth's surface, subduction moves material from the crust to the mantle, generating magma and igneous activity. This process is crucial for building the continental crust. Despite its importance, how the subduction process evolved over billions of years remains debated. To better understand when and where subduction began, we trained a machine learning model to distinguish between arc (subduction‐related) and non‐arc (not subduction‐related) basalts to recognize the chemical “fingerprints” of subduction in these rocks. By applying the same model to ancient basalts, we could trace basaltic arc‐like magmatism back to several Archean eon cratons, known as cratons, early in Earth's history (during the Archean Eon). The number of arc‐type basalts increased during the Mesoarchean and late Archean, suggesting that subduction expanded to different regions for about 700 million years. The transition suggests a significant shift in how the Earth's crust moved and changed, from a primarily steady state to a more mobile tectonics as observed today. Our study sheds new light on the ancient history of our planet and helps us understand how the Earth's crust has evolved over billions of years. Machine learning can accurately distinguish between arc and non‐arc basalts worldwideSubduction‐related basaltic magmatism may have produced on several cratons during the early ArcheanSubduction‐related processes may have started in cratons worldwide during the late Archean Machine learning can accurately distinguish between arc and non‐arc basalts worldwide Subduction‐related basaltic magmatism may have produced on several cratons during the early Archean Subduction‐related processes may have started in cratons worldwide during the late Archean

Strong light–matter coupling generates hybrid states that inherit properties of both light and matter, effectively allowing the modification of the molecular potential energy landscape. This phenomenon opens up a plethora of options for manipulating the properties of molecules, with a broad range of applications in photochemistry and photophysics. In this article, we use strong light–matter coupling to transform an endothermic triplet–triplet annihilation process into an exothermic one. The resulting gradual on–off photon upconversion experiment demonstrates a direct conversion between molecular states and hybrid light–matter states. Our study provides a direct evidence that energy can relax from nonresonant low energy molecular states directly into hybrid light–matter states and lays the groundwork for tunable photon upconversion systems that modify molecular properties in situ by optical cavities rather than with chemical modifications.

Ultrathin freestanding membranes with a pronounced metal–insulator transition (MIT) have huge potential for future flexible electronic applications as well as provide a unique aspect for the study of lattice–electron interplay. However, the reduction of the thickness to an ultrathin region (a few nm) is typically detrimental to the MIT in epitaxial films, and even catastrophic for their freestanding form. Here, we report an enhanced MIT in VO2-based freestanding membranes, with a lateral size up to millimeters and the VO2thickness down to 5 nm. The VO2membranes were detached by dissolving a Sr3Al2O6sacrificial layer between the VO2thin film and the c-Al2O3(0001) substrate, allowing the transfer onto arbitrary surfaces. Furthermore, the MIT in the VO2membrane was greatly enhanced by inserting an intermediate Al2O3buffer layer. In comparison with the best available ultrathin VO2membranes, the enhancement of MIT is over 400% at a 5 nm VO2thickness and more than 1 order of magnitude for VO2above 10 nm. Our study widens the spectrum of functionality in ultrathin and large-scale membranes and enables the potential integration of MIT into flexible electronics and photonics.

Accurate and sensitive detection of single-base mutations in RNAs is of great value in basic studies of life science and medical diagnostics. However, the current available RNA detection methods are challenged by heterogeneous clinical samples in which trace RNA mutants usually existed in a large pool of normal wild sequences. Thus, there is still great need for developing the highly sensitive and highly specific methods in detecting single-base mutations of RNAs in heterogeneous clinical samples. In the present study, a new chimeric DNA probe-aided ligase chain reaction-based electrochemical method (cmDNA-eLCR) was developed for RNA mutation detection through the BSA-based carrier platform and the horseradish peroxidase-hydrogen peroxide-tetramethylbenzidine (HRP-H2O2-TMB) system. The denaturing polyacrylamide gel electrophoresis and a fluorophore-labeled probe was ingeniously designed to demonstrate the advantage of cmDNA in ligation to normal DNA templated by RNA with the catalysis of T4 RNA ligase 2 as well as its higher selectivity than DNA ligase system. Finally, the proposed cmDNA-eLCR, compared with the traditional eLCR, showed excellent performance in discriminating single base-mismatched sequences, where the signal response for mismatched targets at a high concentration could overlap completely with that for the blank control. Besides, this cmDNA-eLCR assay had a wide linear range crossing six orders of magnitude from 1.0 × 10–15to1.0 × 10–10M with a limit of detection as low as 0.6 fM. Furthermore, this assay was applied to detect RNA in real sample with a satisfactory result, thereby demonstrating its great potential in diagnosis of RNA-related diseases.

The marine bacterial pathogen Vibrio parahaemolyticusis a major cause of food-borne gastroenteritis. Recent findings have demonstrated that protein phosphorylation is fundamental to the regulation of many physiological processes in pathogenic bacteria, including bacterial virulence. However, the underlying mechanisms remain to be completely clarified. Using bioinformatics analysis, we found that VP0057 may be a potential Ser/Thr protein kinase with phosphorylation activity. Thus, we constructed the vp0057-deletion mutant (Δvp0057) from the wild-type V. parahaemolyticusserotype O3:K6 and employed a mass spectrometry-based proteomic strategy to characterize proteome-wide changes in response to vp0057deletion, owing to the potential roles of VP0057 in V. parahaemolyticus. One hundred ninety-seven differentially expressed proteins were identified in the Δvp0057strain compared with the wild-type strain, among which 135 proteins were upregulated and 62 proteins were downregulated. Detailed annotation of these differentially expressed proteins was conducted. Notably, iron-related and T6SS1-related proteins were upregulated in the Δvp0057strain, corroborating the results by quantitative PCR. Further experiments proved that vp0057deletion promotes Fe2+and Fe3+uptake and provides a growth competition advantage, which is controlled by iron-related and T6SS1-related proteins, respectively. Although the regulatory roles and mechanisms of VP0057 remain to be revealed in V. parahaemolyticus, our systemic analysis of the protein profile of Δvp0057provides a promising starting point for the intensive exploration of VP0057.

The ultrathin layer-by-layer graphene coatings on stainless steel (SS) were fabricated through Marangoni self-assembly of graphene nanosheets. The anti-corrosion performance of the coatings were studied and the optimized 3-layer graphene coating achieve a corrosion potential increase of 0.15 V and a corrosion current density decrease of 1.23 × 10−7A/cm2comparing to SS.

Rapid detection of tea polyphenol is necessary in food and beverages. In this work, we used cassava fibers as a substrate on which iron nanoparticles were immobilized. The proposed composite was used for surface modification of glassy carbon electrodes to prepare an electrochemical sensor for the detection of tea polyphenols. The SEM characterization results show that the iron nanoparticles on the surface of the cassava fibers were distributed uniformly. We investigated the electrochemical behavior of tea polyphenols on the surface of modified electrodes. The result indicated that the iron nanoparticles could facilitate the electron transfer rate and subsequently enhance the sensing performance. Meanwhile, we have optimized the detection parameters. The proposed sensor can linearly increase the peak current of tea polyphenol oxidation in the range of 3.5–31.5 µM with a equation of I (µA) = 0.01285c + 0.89734 (r = 0.9958). The detection limit can be calculated to be 0.1 µM. In addition, we have validated the proposed sensors in real samples. The results demonstrate that this sensor can be potentially used for the detection of tea polyphenols in beverages.

ABSTRACTThe gut microbiota system plays a vital role in liver diseases. This study aimed to address the diversity of gut microbiota and its correlations with clinical parameters in healthy individuals, chronic liver disease (CLD), and hepatocellular carcinoma (HCC) patients. Fecal specimens of nine healthy individuals, 11 CLD, and 21 HCC were collected. The diversity of gut microbiota was examined by PCR and Illumina MiSeq sequencing and analyzed using 16S rRNA gene sequencing database. The correlations between gut microbiota and the clinical parameters of participants were also addressed. Compared to healthy individuals, Firmicutesat a phylum level decreased in CLD and HCC patients and Proteobacteriaincreased (p < 0.05). The composition of Blautiaon a genus level in CLD and HCC patients significantly decreased compared to healthy controls (p < 0.05). Firmicutescomposition was negatively associated with age and number of males (p < 0.05) and was positively associated with monocytes, high-density lipoprotein cholesterol (HDL-C), and estimated glomerular filtration rate (eGFR) levels (p < 0.05). At a genus level, Blautiacomposition was negatively associated with cirrhosis, age, and number of males (p < 0.01), while it was positively associated with red blood cells (RBCs), triglycerides, HDL-C, and lymphocyte levels (p < 0.05). Conclusively, there was a significant compositional difference in gut microbiota in CLD and HCC patients compared with healthy subjects. Firmicutesand Blautiain gut microbiota system lessened in CLD and HCC patients. Clinical biochemical parameters have an impact on the diversity of gut microbiota in liver diseases.

Inflammatory bowel disease (IBD) is an immune-mediated chronic inflammatory disease. Although the etiology is uncertain, there is marked disbalance of mucosal immune responses in part shaped by genetic susceptibility and intestinal microbial dysbiosis. Suppressing inflammatory activity adequately and maintaining this suppression are the main goals of current therapies. However, corticosteroids are only suitable for therapy of active disease, and the effects of immunosuppressive agents are mainly limited to maintenance of remission. Biologics have become widely available and provide therapeutic benefits to IBD patients. However, only a part of patients benefits from them. Thus, there is an urgent need for the development of new substances in the therapy of IBD. Exosomes are nanosized lipid vesicles identified recently. They are secreted from all living cells and then distributed in various human body fluids. The components, such as microRNAs and functional proteins, secreted by exosomes in different cells have been reported to be involved in the pathogenesis of IBD. Therefore, exosomes have the potential to become appealing particles in treating IBD as a cell-free therapeutic approach as well as biomarkers for diagnosis and monitoring disease status. Further studies are needed to investigate the practicality, safety and desirable effects of exosomes in clinical applications in IBD.

Transition-metal-catalyzed C–N bond-forming reactions have emerged as fundamental and powerful tools to construct arylamines, a common structure found in drug agents, natural products, and fine chemicals. Reported herein is an alternative access to heteroarylamine via radical–radical cross-coupling pathway, powered by visible light catalysis without any aid of external oxidant and reductant. Only by visible light irradiation of a photocatalyst, such as a metal-free photocatalyst, does the cascade single-electron transfer event for amines and heteroaryl nitriles occur, demonstrated by steady-state and transient spectroscopic studies, resulting in an amine radical cation and aryl radical anion in situ for C–N bond formation. The metal-free and redox economic nature, high efficiency, and site-selectivity of C–N cross-coupling of a range of available amines, hydroxylamines, and hydrazines with heteroaryl nitriles make this protocol promising in both academic and industrial settings.

The ability to direct the flow of excitons enable molecular systems to perform highly advanced functions. Intramolecular energy transfer in donor–bridge–acceptor systems can occur by different mechanisms, and the ability to control the excited state energy pathways depends on the capacity to favor one process over another. Here, we show an anticorrelation between the rates of Förster and Dexter types of energy transfer in two isomeric donor–bridge–acceptor systems. Both dyads display intramolecular Förster triplet-to-singlet and Dexter triplet-to-triplet energy transfers. However, as the bridge–acceptor connection point changes, the rate of one energy transfer process increases at the same time as the other one decreases, allowing us to control the energy flow direction. This work shows how rational design can be used to tune excited state energy pathways in molecular dyads, which is of importance for advanced functions such as multiplicity conversion in future molecular materials.

Pt nanodendrites were electrodeposited at activated carbon as a catalyst for electrochemical hydrogen production. The fabricated Pt nanodendrites exposed numerous highly active atoms at (111) facet, which contribute to a low Tafel slope of 22.2 mV/dec and improvement of hydrogen production efficiency.

Background and Purpose: Hemorrhagic transformation (HT) has an adverse effect on the prognosis of patients with acute ischemic stroke, and it is currently known associated with coagulation system. But the conclusion is not consistent and remains to be identified. The aim of this study was to investigate the association between coagulation function and spontaneous hemorrhagic transformation. Methods: Patients within 7 days from the onset of ischemic stroke who did not receive reperfusion therapy (thrombolysis or endovascular treatment) were included between January 2016 and October 2017. Coagulation function indicators, including prothrombin time (PT), activated partial thromboplastin time (APTT), international normalized ratio (INR), thrombin time (TT) and fibrinogen (FIB), were tested within 24 h after admission. HT was defined as hemorrhage presented on follow-up magnetic resonance imaging (MRI) or computed tomography (CT) but not on baseline CT. We performed binary logistic regression to examine the association between coagulation function and HT. The coagulation indicators were entered into logistic regression analysis as continuous variables (per 1-unit/L increase) and four-categorized variables (with data collapsed into quartiles), respectively. Results: A total of 1141 patients were included (mean age, 64 ± 15 years; 63.7% males). 102 patients experienced HT (8.9%), of whom 14 patients experienced symptomatic HT (sHT, 1.2%). After adjustment for confounders, TT in the highest quartile is inversely associated with risk of HT (as continuous variable, odds ratio [OR] 0.85; 95% confidence level [CI] 0.73-0.99, P = 0.042; as four-categorized variable, OR 0.36, 95% CI 0.18 - 0.7, P = 0.003). Whether as continuous variables or four-categorized variables, PT, INR, APTT and FIB had no association with HT. Conclusion: Not the whole process of coagulation function is associated with spontaneous HT. Prolonged TT, which may indicate an extension of the last step of the coagulation process, is independently and inversely associated with spontaneous HT in patients with acute ischemic stroke.

Cultivation of medicinal crops, which synthesize hundreds of substances for curative functions, was focused on the synthesis of secondary metabolites rather than biomass accumulation. Nutrition is an important restrict factor for plant growth and secondary metabolites, but little attention has been given to the plasticity of nutrient uptake and secondary metabolites synthesis response to soil nitrogen (N) change.

Sensitized triplet–triplet annihilation (sTTA) is the most promising mechanism for pooling the energy of two visible photons, but its applications in solution were so far limited to organic solvents, with a current maximum of the excited-singlet state energy of 3.6 eV. By combining tailor-made iridium complexes with naphthalenes, we demonstrate blue-light driven upconversion in water with unprecedented singlet-state energies approaching 4 eV. The annihilators have outstanding excited-state reactivities enabling challenging photoreductions driven by sTTA. Specifically, we found that an aryl-bromide bond activation can be achieved with blue photons, and we obtained full conversion for the very energy-demanding decomposition of a persistent ammonium compound as typical water pollutant, not only with a cw laser but also with an LED light source. These results provide the first proof-of-concept for the usage of low-power light sources for challenging reactions employing blue-to-UV upconversion in water and pave the way for the further development of sustainable light-harvesting applications.