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The incidence of thyroid tumors has been increasing yearly over the past decade, making it the fourth highest tumor in women. This places various biological burdens on those affected. Currently, thyroid tumors are primarily diagnosed using percutaneous fine needle aspiration and ultrasound. However, these methods are complex, expensive, and less accurate, and they may fail to detect some thyroid nodules. As an alternative, researchers are focusing on blood‐based biomarkers in addition to the traditional diagnostic methods, assisted predominantly by nanomaterials. Early identification of thyroid cancer is crucial as it is highly treatable. Various sensing systems have been developed using nanomaterial‐mediated approaches to enhance the detection system. Nanomaterials are effectively applied in biosensors for surface functionalization and are conjugated with biomolecules to improve the interaction with the target analyte. This review discusses nanomaterial‐assisted thyroid tumor detection, with a special focus on nanomaterial‐based biosensors. [ABSTRACT FROM AUTHOR]

Acute asthma exacerbation refers to the progressive deterioration of asthma symptoms that is always triggered by virus infection represented by respiratory syncytial virus (RSV). After RSV infection, exaggerated Th2‐mediated pulmonary inflammation is the critical pathological response of asthmatic patients with acute exacerbation. Significantly, airway epithelial cells, being the primary targets of RSV infection, play a crucial role in controlling the pulmonary inflammatory response by releasing airway epithelial cell‐derived exosomes (AEC‐Exos), which potentially influence the development of asthma. However, the specific role of AEC‐Exos in acute asthma exacerbation after RSV infection remains obscure. The purpose of this study was to determine the distinct function of AEC‐Exos in exacerbating acute asthma following RSV infection. Blockade of exosomes by GW reduce the enhanced pulmonary inflammation significantly. Specifically, the enhanced Th2 inflammation was induced by AEC‐Exos thorough transportation of hsa‐miR‐155‐5p–Sirtuin 1 (SIRT1) pathway during acute asthma exacerbation. Targeted inhibition of hsa‐miR‐155‐5p blocks the exaggerated Th2 inflammation effectively in mice with acute asthma exacerbation. In summary, our study showed that during acute asthma exacerbation after RSV infection, AEC‐Exos promote the enhanced Th2 inflammation through transportation of increased hsa‐miR‐155‐5p, which was mediated partly through SIRT1‐mediated pathway. hsa‐miR‐155‐5p is a potential biomarker for early prediction of acute asthma exacerbation. [ABSTRACT FROM AUTHOR]

The biological world serves as a vast reservoir of inspiration for human innovation, particularly in the realm of robotics designed to navigate intricate granular environments. Among these creatures adept at burrowing, the mole stands out due to its exceptional body structure and unparalleled efficiency, surpassing most engineering burrowing systems. Consequently, the mole serves as an ideal model for designing highly efficient burrowing robots. This study introduces a mole‐inspired robot burrowing with forelimbs, specifically designed for planetary soil exploration. By closely examining the distinctive body morphology of moles, a forelimb burrowing mechanism is devised through biomimetic mapping, and its kinematics is thoroughly analyzed. A robot prototype is developed and an experimental setup is constructed to evaluate its burrowing performance. A series of tests are conducted to assess the capabilities of the robot, including forelimb burrowing, robot crawling, and robot burrowing. The results demonstrate that the proposed mole‐inspired burrowing robot is capable of crawling and burrowing to a certain depth using its forelimbs. Although it exhibits some upward displacement, this issue can be mitigated by modifying the head configuration and adjusting the forelimb posture to effectively overcome the vertical stress and lift force exerted by granular soils due to intensity gradient. [ABSTRACT FROM AUTHOR]

As a universal second messenger, cytosolic calcium (Ca2+) functions in multifaceted intracellular processes, including growth, development and responses to biotic/abiotic stresses in plant. The plant‐specific Ca2+ sensors, calmodulin and calmodulin‐like (CML) proteins, function as members of the second‐messenger system to transfer Ca2+ signal into downstream responses. However, the functions of CMLs in the responses of cotton (Gossypium spp.) after Verticillium dahliae infection, which causes the serious vascular disease Verticillium wilt, remain elusive. Here, we discovered that the expression level of GbCML45 was promoted after V. dahliae infection in roots of cotton, suggesting its potential role in Verticillium wilt resistance. We found that knockdown of GbCML45 in cotton plants decreased resistance while overexpression of GbCML45 in Arabidopsis thaliana plants enhanced resistance to V. dahliae infection. Furthermore, there was physiological interaction between GbCML45 and its close homologue GbCML50 by using yeast two‐hybrid and bimolecular fluorescence assays, and both proteins enhanced cotton resistance to V. dahliae infection in a Ca2+‐dependent way in a knockdown study. Detailed investigations indicated that several defence‐related pathways, including salicylic acid, ethylene, reactive oxygen species and nitric oxide signalling pathways, as well as accumulations of lignin and callose, are responsible for GbCML45‐ and GbCML50‐modulated V. dahliae resistance in cotton. These results collectively indicated that GbCML45 and GbCML50 act as positive regulators to improve cotton Verticillium wilt resistance, providing potential targets for exploitation of improved Verticillium wilt‐tolerant cotton cultivars by genetic engineering and molecular breeding. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A visible‐light‐enabled, photocatalyst‐free hydroacylation reaction of azodicarboxylic acid derivatives was described. This radical conjugate addition (RCA) protocol relied on the dual role of 4‐acyl‐1,4‐dihydropyridine (acyl‐DHP) reagents that besides being as radical reservoirs, they also enabled the conversion of radical adducts to anion intermediates via reduction. Under "catalyst‐oxidant‐additive free" conditions, a wide range of structurally different acyl hydrazide products were readily obtained in 56%—99% yields. The utility of this transformation was further demonstrated by the scale‐up synthesis and downstream derivatization. [ABSTRACT FROM AUTHOR]

Probing biomolecular interactions at cellular interfaces is crucial for understanding and interfering with life processes. Although affinity binders with site specificity for membrane proteins are unparalleled molecular tools, a high demand remains for novel multi‐functional ligands. In this study, a synthetic peptide (APQQ) with tight and specific binding to the untargeted extracellular loop of CD81 evolved from a genetically encoded peptide pool. With tailored affinity, APQQ flexibly accesses, site‐specifically binds, and forms a complex with CD81, enabling in‐situ tracking of the dynamics and activity of this protein in living cells, which has rarely been explored because of the lack of ligands. Furthermore, APQQ triggers the relocalization of CD81 from diffuse to densely clustered at cell junctions and modulates the interplay of membrane proteins at cellular interfaces. Motivated by these, efficient suppression of cancer cell migration, and inhibition of breast cancer metastasis were achieved in vivo. [ABSTRACT FROM AUTHOR]

SUMMARY: Ginger is cultivated in tropical and subtropical regions and is one of the most crucial spices worldwide owing to its special taste and scent. Here, we present a high‐quality genome assembly for 'Small Laiwu Ginger', a famous cultivated ginger in northern China. The ginger genome was phased into two haplotypes, haplotype A (1.55Gb), and haplotype B (1.44Gb). Analysis of Ty1/Copia and Ty3/Gypsy LTR retrotransposon families revealed that both have undergone multiple retrotransposon bursts about 0–1 million years ago. In addition to a recent whole‐genome duplication event, there has been a lineage‐specific expansion of genes involved in stilbenoid, diarylheptanoid, and gingerol biosynthesis, thereby enhancing 6‐gingerol biosynthesis. Furthermore, we focused on the biosynthesis of 6‐gingerol, the most important gingerol, and screened key transcription factors ZoMYB106 and ZobHLH148 that regulate 6‐gingerol synthesis by transcriptomic and metabolomic analysis in the ginger rhizome at four growth stages. The results of yeast one‐hybrid, electrophoretic mobility shift, and dual‐luciferase reporter gene assays showed that both ZoMYB106 and ZobHLH148 bind to the promoters of the key rate‐limiting enzyme genes ZoCCOMT1 and ZoCCOMT2 in the 6‐gingerol synthesis pathway and promote their transcriptional activities. The reference genome, transcriptome, and metabolome data pave the way for further research on the molecular mechanism underlying the biosynthesis of 6‐gingerol. Furthermore, it provides precious new resources for the study on the biology and molecular breeding of ginger. Significance Statement: We present a high‐quality genome assembly for 'Small Laiwu Ginger' with two haplotypes, haplotype A (1.55Gb) and haplotype B (1.44Gb). We find that ZoMYB106 and ZobHLH148 bind to the promoters of the key rate‐limiting enzyme genes ZoCCOMT1 and ZoCCOMT2 in the 6‐gingerol synthesis pathway and promote their transcriptional activities. [ABSTRACT FROM AUTHOR]

Diamond, with ultrahigh hardness, high wear resistance, high thermal conductivity, and so forth, has attracted worldwide attention. However, researchers found emergent reactions at the interfaces between diamond and ferrous materials, which significantly affects the performance of diamond‐based devices. Herein, combing experiments and theoretical calculations, taking diamond–iron (Fe) interface as a prototype, the counter‐diffusion mechanism of Fe/carbon atoms has been established. Surprisingly, it is identified that Fe and diamond first form a coherent interface, and then Fe atoms diffuse into diamond and prefer the carbon vacancies sites. Meanwhile, the relaxed carbon atoms diffuse into the Fe lattice, forming Fe3C. Moreover, graphite is observed at the Fe3C surface when Fe3C is over‐saturated by carbon atoms. The present findings are expected to offer new insights into the atomic mechanism for diamond‐ferrous material's interfacial reactions, benefiting diamond‐based device applications. [ABSTRACT FROM AUTHOR]

Mitochondrial base editing with DddA‐derived cytosine base editor (DdCBE) is limited in the accessible target sequences and modest activity. Here, the optimized DdCBE tools is presented with improved editing activity and expanded C‐to‐T targeting scope by fusing DddA11 variant with different cytosine deaminases with single‐strand DNA activity. Compared to previous DdCBE based on DddA11 variant alone, fusion of the activation‐induced cytidine deaminase (AID) from Xenopus laevis not only permits cytosine editing of 5′‐GC‐3′ sequence, but also elevates editing efficiency at 5′‐TC‐3′, 5′‐CC‐3′, and 5′‐GC‐3′ targets by up to 25‐, 10‐, and 6‐fold, respectively. Furthermore, the A‐to‐G editing efficiency is significantly improved by fusing the evolved DddA6 variant with TALE‐linked deoxyadenosine deaminase (TALED). Notably, the authors introduce the reported high‐fidelity mutations in DddA and add nuclear export signal (NES) sequences in DdCBE and TALED to reduce off‐target editing in the nuclear and mitochondrial genome while improving on‐target editing efficiency in mitochondrial DNA (mtDNA). Finally, these engineered mitochondrial base editors are shown to be efficient in installing mtDNA mutations in human cells or mouse embryos for disease modeling. Collectively, the study shows broad implications for the basic study and therapeutic applications of optimized DdCBE and TALED. [ABSTRACT FROM AUTHOR]

Nitrogen‐doped graphene (C2N), a novel graphene‐based materials, has been proposed as a potential alternative to graphene oxide (GO) in biomedical applications. However, due to the challenges in synthesizing C2N, reports in the biomedical field are currently rare. Here, we have modified the reported procedure and successfully synthesized C2N nanoparticles at 120°C, which we refer to as C2N‐120. The toxicity and biocompatibility of GO and C2N‐120 were evaluated using a mouse model injected with GO/C2N‐120 via the tail vein, as well as cell models treated with GO/C2N‐120. In vivo studies revealed that GO/C2N‐120 showed similar distribution patterns after tail vein injection. The liver, spleen, and lung are the major nanoparticle uptake organs of GO and C2N‐120. However, GO deposition in the major nanoparticle uptake organs was more significant than that of C2N‐120. In addition, GO deposition caused structural abnormalities, increased apoptotic cells, and enhanced macrophage infiltration whereas C2N‐120 exhibited fewer adverse effects. In vitro experiments were conducted using different cell lines treated with GO/C2N‐120. Unlike GO which induced mitochondrial damage, oxidative stress, inflammatory response, autophagic flux blockage and cell apoptosis, C2N‐120 showed lower cytotoxicity in cell models. Our data demonstrated that C2N‐120 exhibits higher biocompatibility than GO, both in vivo and in vitro, suggesting its potential for biomedical application in the future. [ABSTRACT FROM AUTHOR]

Objective: This study aims to construct an artificial intelligence (AI) model capable of effectively discriminating between abdominal Henoch‐Schönlein purpura (AHSP) and acute appendicitis (AA) in pediatric patients. Methods: A total of 6965 participants, comprising 2201 individuals with AHSP and 4764 patients with AA, were enrolled in the study. Additionally, 53 laboratory indicators were taken into consideration. Five distinct artificial intelligence (AI) models were developed employing machine learning algorithms, namely XGBoost, AdaBoost, Gaussian Naïve Bayes (GNB), MLPClassifier (MLP), and support vector machine (SVM). The performance of these prediction models was assessed through receiver operating characteristic (ROC) curve analysis, calibration curve assessment, and decision curve analysis (DCA). Results: We identified 32 discriminative indicators (p <.05) between AHSP and AA. Five indicators, namely the lymphocyte ratio (LYMPH ratio), eosinophil ratio (EO ratio), eosinophil count (EO count), neutrophil ratio (NEUT ratio), and C‐reactive protein (CRP), exhibited strong performance in distinguishing AHSP from AA (AUC ≥ 0.80). Among the various prediction models, the XGBoost model displayed superior performance evidenced by the highest AUC (XGBoost = 0.895, other models < 0.89), accuracy (XGBoost = 0.824, other models < 0.81), and Kappa value (XGBoost = 0.621, other models < 0.60) in the validation set. After optimization, the XGBoost model demonstrated remarkable diagnostic performance for AHSP and AA (AUC > 0.95). Both the calibration curve and decision curve analysis suggested the promising clinical utility and net benefits of the XGBoost model. Conclusion: The AI‐based machine learning model exhibits high prediction accuracy and can differentiate AHSP and AA from a data‐driven perspective. [ABSTRACT FROM AUTHOR]

A growing body of evidence from neuroimaging studies suggests that inflammatory bowel disease (IBD) is associated with functional and structural alterations in the central nervous system and that it has a potential link to emotional symptoms, such as anxiety and depression. However, the neurochemical underpinnings of depression symptoms in IBD remain unclear. We hypothesized that changes in cortical gamma‐aminobutyric acid (GABA+) and glutamine (Glx) concentrations are related to cortical thickness and resting‐state functional connectivity in IBD as compared to healthy controls. To test this, we measured whole‐brain cortical thickness and functional connectivity within the medial prefrontal cortex (mPFC), as well as the concentrations of neurotransmitters in the same brain region. We used the edited magnetic resonance spectroscopy (MRS) with the MEGA‐PRESS sequence at a 3 T scanner to quantitate the neurotransmitter levels in the mPFC. Subjects with IBD (N = 37) and healthy control subjects (N = 32) were enrolled in the study. Compared with healthy controls, there were significantly decreased GABA+ and Glx concentrations in the mPFC of patients with IBD. The cortical thickness of patients with IBD was thin in two clusters that included the right medial orbitofrontal cortex and the right posterior cingulate cortex. A seed‐based functional connectivity analysis indicated that there was higher connectivity of the mPFC with the left precuneus cortex (PC) and the posterior cingulate cortex, and conversely, lower connectivity in the left frontal pole was observed. The functional connectivity between the mPFC and the left PC was negatively correlated with the IBD questionnaire score (r = −0.388, p = 0.018). GABA+ concentrations had a negative correlation with the Hamilton Depression Scale (HAMD) score (r = −0.497, p = 0.002). Glx concentration was negatively correlated with the HAMD score (r = −0.496, p = 0.002) and positively correlated with the Short‐Form McGill Pain Questionnaire score (r = 0.330, p = 0.046, uncorrected). There was a significant positive correlation between the ratio of Glx to GABA+ and the HAMD score (r = 0.428, p = 0.008). Mediation analysis revealed that GABA+ significantly mediated the main effect of the relationship between the structural and functional alterations and the severity of depression in patients with IBD. Our study provides initial evidence of neurochemistry that can be used to identify potential mechanisms underlying the modulatory effects of GABA+ on the development of depression in patients with IBD. [ABSTRACT FROM AUTHOR]

In the context that coal remains the main energy source of China now, the safety of coal mine production is still worth our attention. For the factors influencing the roof accident of coal mine roadway have great complexity and uncertainty, a new risk prediction method of coal mine roof accidents integrating T‐S fuzzy fault tree and Bayesian network (BN) is proposed. The constructed method determines the BN and the conditional probability tables according to the established T‐S fuzzy fault tree. The fault state and fuzzy fault rate of root nodes are described according to the fuzzy number. And the forward inference of Bayesian is used to calculate the probability of the accidents on the roadway roof based on the fault probability of the root nodes and actual fault probability during construction respectively, to realize the risk prediction of roof accidents. Finally, practical data are used to verify the new fusion risk evaluation method by taking two mines as cases. The results show that the influencing factors calculated by the new fusion risk prediction method are completely consistent with the actual situation, confirming the effectiveness and reliability of this method, which providing new ideas for the research about the risk prediction of coal mine roof accidents. [ABSTRACT FROM AUTHOR]

This study presents an intelligent soft robotic system capable of perceiving, describing, and sorting objects based on their physical properties. This work introduces a bimodal self‐powered flexible sensor (BSFS) based on the triboelectric nanogenerator and giant magnetoelastic effect. The BSFS features a simplified structure comprising a magnetoelastic conductive film and a packaged liquid metal coil. The BSFS can precisely detect and distinguish touchless and tactile models, with a response time of 10 ms. By seamlessly integrating the BSFSs into the soft fingers, this study realizes an anthropomorphic soft robotic hand with remarkable multimodal perception capabilities. The touchless signals provide valuable insights into object shape and material composition, while the tactile signals offer precise information regarding surface roughness. Utilizing a convolutional neural network (CNN), this study integrates all sensing information, resulting in an intelligent soft robotic system that accurately describes objects based on their physical properties, including materials, surface roughness, and shapes, with an accuracy rate of up to 97%. This study may lay a robotic foundation for the hardware of the general artificial intelligence with capacities to interpret and interact with the physical world, which also serves as an interface between artificial intelligence and soft robots. [ABSTRACT FROM AUTHOR]

The influence of Cu doping on phase transition, thermal strain, and thermal expansion property of polycrystalline Ni50Mn23−xCuxGa27(x = 1, 3, 5, 6 and 7) alloys is investigated. The results show that with increasing Cu concentration, martensitic transformation gradually gets close to Curie transition. A magnetostructural transition (MST) is observed in samples with x = 6 and 7. Such MST can enhance magnitude of transformation strain. Besides, Ni50Mn23−xCuxGa27 alloys possess an isotropic, recoverable, and thermally stable thermal strain. Excitedly, Cu doping can effectively tune the phase transition, thermal strain, and thermal expansion properties of Ni50Mn23−xCuxGa27 alloys. Adjustable coefficients of thermal expansion from positive to negative are obtained by Cu‐doped Ni50Mn23−xCuxGa27 alloys. The average linear expansion coefficient (α) between −140.44 and −207.70 ppm K−1 is observed in samples with x = 6 and 7 for a narrow temperature span of 11–14 K. When the temperature span is about 72 K (x = 6) and 73 K (x = 7), which is the largest temperature span observed in Ni–Mn–Ga‐based alloys recently, the α values decrease to about −36 ppm K−1. These findings are beneficial for manipulating the thermal expansion property of Ni–Mn–Ga–Cu alloys and their multifunctional applications. [ABSTRACT FROM AUTHOR]

Poly(dimethyl siloxane) (PDMS) elastomers play a significant role in smart materials, actuators, and flexible electronics. However, current PDMS lacks adhesion abilities and intelligent responsive properties, which limit its further application. In this study, the polydimethylsiloxane‐ureidopyrimidinone impact hardening polymer (PDMS‐UI) composites are manufactured by a dual cross‐linking compositing tactic. PDMS, a chemically stable cross‐linked network, acts as a framework owing to its excellent mechanical strength, whereas UI, a reversible dynamic physically cross‐linked network with quadruple hydrogen bonding, endows the PDMS‐UI with excellent self‐healing ability (efficiency > 90%) and energy absorption (75.23%). Impressively, owing to multivalent hydrogen bonds, the PDMS‐UI exhibits superior adhesion performance: the adhesion strength on various substrates exceed 150 kPa and that on the Ferrum substrate reaches 570 kPa. These outstanding properties make the PDMS‐UI a potential candidate for application in both well‐developed fields, such as, wearable protective materials, artificial skin and soft robotics. [ABSTRACT FROM AUTHOR]

In this study, the blank hydrogels and the niosomal hydrogels loading coenzyme Q10 (CoQ10) were prepared by carbomer (CBM) and scleroglucan (SCL), and their physicochemical properties were characterized in terms of rheological and texture measurement, FTIR, SEM, DSC, and DLS. First, the blank hydrogels CBM‐SCL‐Gel were prepared. With the increase of SCL concentration, the viscosity and modulus increased, displaying better shear thinning behavior of pseudoplastic fluid. A dense network structure was formed in CBM‐SCL‐Gel, especially for CBM/SCL at 5/4 and 5/5, due to hydrogen bonding between CBM and SCL. The swelling behaviors of the composite gels conformed to pseudo‐second‐order kinetics, and CBM/SCL at 5/1 exhibited the highest swelling capability. The addition of SCL made the water absorption mechanism tend to a non‐Fickian diffusion mode. Then, the niosomal hydrogel was prepared by the optimized gel formulation with the CoQ10‐loaded niosome. It was found that the gel properties were insignificantly affected by the CoQ10 niosomes. The particle sizes of the niosomes in the gel were a little larger than that in aqueous suspension. After storage for 30 days, the CoQ10 retention rate in the niosomal gel remained at 92% (4°C, N‐Gel), representing high stability of CoQ10. [ABSTRACT FROM AUTHOR]

This article deals with the false data injection attack (FDIA) detection problem for multi‐area power systems. Considering the large‐scale characteristic of the multi‐area power systems, a novel decentralized detection scheme is proposed to detect FDIAs. First, an unknown input sliding mode observer (UI‐SMO) is designed to decouple the interconnected terms, meanwhile, a robust term in the UI‐SMO can attenuate the effect of the load variation, by which the obtained residual is only sensitive to local FDIAs. The strict reachability of the sliding surface in the estimate error space is ensured by the robust term with an auxiliary variable, and the stability of the sliding mode dynamics is achieved. Then, a detection logic is delicately designed based on a two‐phase residual threshold. Due to the strong attenuating ability to load variation, the proposed detection scheme shows better detectability than some existing works with only decoupling interconnections. Finally, the theoretical results are backed up by a three‐area power system simulation with comparison between proposed UI‐SMO‐based and traditional UIO‐based detection scheme. [ABSTRACT FROM AUTHOR]

The coronavirus disease 2019 (COVID‐19) pandemic posed great impacts on public health. To fight against the pandemic, robust immune responses induced by vaccination are indispensable. Previously, we developed a subunit vaccine adjuvanted by aluminum hydroxide, ZF2001, based on the dimeric tandem‐repeat RBD immunogen, which has been approved for clinical use. This dimeric RBD design was also explored as an mRNA vaccine. Both showed potent immunogenicity. In this study, a DNA vaccine candidate encoding RBD‐dimer was designed. The humoral and cellular immune responses induced by homologous and heterologous prime‐boost approaches with DNA‐RBD‐dimer and ZF2001 were assessed in mice. Protection efficacy was studied by the SARS‐CoV‐2 challenge. We found that the DNA‐RBD‐dimer vaccine was robustly immunogenic. Priming with DNA‐RBD‐dimer followed by ZF2001 boosting induced higher levels of neutralizing antibodies than homologous vaccination with either DNA‐RBD‐dimer or ZF2001, elicited polyfunctional cellular immunity with a TH1‐biased polarization, and efficiently protected mice against SARS‐CoV‐2 infection in the lung. This study demonstrated the robust and protective immune responses induced by the DNA‐RBD‐dimer candidate and provided a heterologous prime‐boost approach with DNA‐RBD‐dimer and ZF2001. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A new electrochemical strategy for the atom transfer radical addition (ATRA) of polychloroalkanes across olefins has been realized by the synergism of paired electrolysis and halogen bonding activation. Notably, readily accessible 4,4‐di‐tert‐butyl bipyridine (dtbpy), acting as a halogen bonding acceptor, shifted the reduction potential of C—Cl bonds positively by 110 mV. The decreased operating potential leads to a wide substrate scope and excellent functional group compatibility. A diverse array of terminal and internal alkenes such as (hetero)aryl olefins, unactive aliphatic olefins, and natural products and drugs‐derived olefins were well compatible. [ABSTRACT FROM AUTHOR]

Multicomponent Synthesis of 5-Cyano-pyrazolo[1,5-a]pyrimidines Enabled by Aerobic Manganese Catalysis Keywords: Manganese catalysis; Strecker reaction; Multicomponent reaction; Cyanation EN Manganese catalysis Strecker reaction Multicomponent reaction Cyanation 871 876 6 03/27/23 20230321 NES 230321 An aerobic Mn(III)-catalyzed one-pot three-component synthesis of 5-cyano-pyrazolo[1,5- I a i ]pyrimidines has been described. These results revealed that the tandem reaction starts with the Strecker reaction and Mn(OAc) SB 3 sb - 2H SB 2 sb O is essential in the following oxidative cyclization process. All of these control experiments strongly support that this tandem reaction involves the Strecker reaction and the sequential Mn-catalyzed cyclization to afford the desired product B 4 aa b . [Extracted from the article]

Aims/Introduction: To investigate the impact of visceral adipose tissue (VAT) on atherosclerosis in type 2 diabetes patients with normal bodyweight (OB[−]) in the Chinese population, and to further assess the sex–age differences between them. Materials and Methods: A total of 8,839 type 2 diabetes patients from two of the National Metabolic Management Centers in China were included in this study. Participants were classified into four groups by visceral fat area (VFA; cm2) and body mass index (BMI; kg/m2): VFA < 100 and BMI < 23.9 (VA[−]OB[−]), VFA < 100 and BMI ≥ 23.9 (VA[−]OB[+]), VFA ≥ 100 and BMI < 23.9 (VA[+]OB[−]), VFA ≥ 100 and BMI ≥ 23.9 (VA[+]OB[+]). Atherosclerosis was defined by brachial‐ankle pulse wave velocity (baPWV; cm/s), and we analyzed the association between VFA, BMI and the tertiles of baPWV values. Results: The VA(+)OB(−) prevalence was 3.7% among these participants. Patients with VA(+)OB(−) had the highest baPWV value (P < 0.001) and the highest proportion of the tertile 3 of baPWV (P < 0.001) among four groups, and were significantly associated with baPWV (standardized β = 0.026, P = 0.008). VFA was significantly related to tertile 2 to tertile 3 of baPWV in (OB[−]) type 2 diabetes patients, when compared with tertile 1 of baPWV, respectively. In sex–age stratified analysis, the association of VFA and the tertiles of baPWV showed sex differences. For the 55 years age stratification analysis, there was no age difference in the relationship between VFA and baPWV in (OB[−]) patients. Conclusion: Increased VAT was an independent risk factor for atherosclerosis in female type 2 diabetes patients with normal weight. [ABSTRACT FROM AUTHOR]

Herein, regulation of the growth mode through manipulating the V–III ratio during metal‐organic chemical vapor deposition (MOCVD) growth of AlN films on c‐plane sapphire substrates and optimization of the crystalline quality and surface morphology of AlN films are demonstrated. Based on detailed analyses of the evolution process of surface morphology, dislocation annihilation, and stress state of the AlN film during MOCVD growth, it is found that 2D rather than 3D growth mode introduces tensile stress as well as promotes edge‐type threading dislocation (ETD) propagation and crack generation, while 3D growth mode produces rough surface. These results would help to further understand the AlN growth mechanism and provide important guidance on the preparation of AlN‐related epitaxial structure. [ABSTRACT FROM AUTHOR]

GaN decomposition at high‐temperature annealing after ion implantation is a huge hurdle to the further maturation of GaN technology. To solve this issue, this work studies the impact of different protective layer structures on high‐temperature annealing of GaN under 1200–1250 °C, including single‐layer structures and double‐layer structures. Single‐layer structures are the SiN layer grown by low‐pressure chemical vapor deposition (LPCVD) and the SiON layer by plasma‐enhanced chemical vapor deposition (PECVD). Double‐layer structures include oxides (Al2O3, SiO2, HfO2) deposited by atomic layer deposition (ALD) on top of low‐stress SiN by LPCVD or SiON grown by PECVD and epitaxial AlN by metal–organic chemical vapor deposition (MOCVD) with sputtered AlN. It is found that either SiO2 with the low‐stress SiN or AlN double capping layers was capable of completely preventing GaN decomposition in the temperature range of 1200–1250 °C. Finally, the protective layer with 20 nm Al2O3 and 300 nm low‐stress LP‐SiN is utilized in the annealing of Si‐implanted GaN high electron mobility transistor (HEMT) structure for activation. The excellent electrical performance are characterized. This work can provide valuable information on the ion implantation and high‐temperature annealing of GaN, which is critical for the further development of gold‐free ohmic contact with GaN devices. [ABSTRACT FROM AUTHOR]

Objectives: To investigate relationships between hypersensitive C‐reactive protein (hs‐CRP), tumor necrosis factor ‐α (TNF‐α), interleukin‐17A (IL‐17A), and interferon ‐γ (IFN‐γ), with left ventricular geometry (LVG) and function in patients with primary hypertension (PHT). Methods: A total of 396 PHT patients were assigned into four groups: Normal Geometry (NG), Concentric Remodeling (CR), Eccentric Hypertrophy (EH), and Concentric Hypertrophy (CH). The correlation between hs‐CRP, TNF‐α, IL‐17A, IFN‐γ, and clinical, biochemical parameters were analyzed by Pearson correlation analysis and Logistic regression. Receiver Operating Characteristic (ROC) curve was used to analyze the clinical values of hs‐CRP, TNF‐α, IL‐17A, and IFN‐γ for abnormal LVG prediction. Results: NG, CR, EH, and CH group all presented increasingly higher levels of Hs‐CRP, TNF‐α, IL‐17A, and IFN‐γ, and the increase was the most prominent in the CH group. Pearson correlation analysis showed that hs‐CRP, IL‐17A, and IFN‐γ were all positively correlated with LASct. Hs‐CRP, TNF‐α, and IL‐17A were all negatively correlated with GLS, LASr, and LAScd. However, IFN‐γ was only negatively correlated with GLS and LAScd. Logistic regression analysis showed that hs‐CRP and IL‐17A were independently correlated with CR; hs‐CRP, TNF‐α, IFN‐γ, and IL‐17A were independently correlated with EH and CH. ROC curve analysis showed that the area under the curve (AUC) of hs‐CRP was 0.816. When the optimal diagnostic threshold of hs‐CRP was 3.04 mg/L, the sensitivity and specificity of the abnormal LVG were 72.1% and 81.5%, respectively. Conclusion: In PHT patients, hs‐CRP, TNF‐α, IL‐17A, and IFN‐γ were correlated with abnormal LVG and left ventricular function, suggesting that inflammatory cytokines may be involved in the process of PHT‐induced abnormal left ventricular structure and function. In addition, hs‐CRP can be used as a health screening index for patients at high risk of abnormal LVG. [ABSTRACT FROM AUTHOR]

Rich functionalities have been identified for domain walls (DWs, naturally occurring interfaces in ferroics), e.g., enhanced conductance and photovoltaic effect, which specify the interest in their internal structure. The dimension/width and type are of particular interest, which is the carrier of their functionality. Recent attention has been focused on head‐to‐head or tail‐to‐tail charged DWs with greatly enhanced conductivity compared to the inner domains, which are found to be an order of magnitude thicker (tens of unit cells) than normal neutral DWs. In this study, ultrathin non‐Ising charged DWs are found, where polarization switched their direction within 2–3 unit cells in self‐assembled BiFeO3 nanocrystals. An analytical model and finite element method simulation are used to interpret the origin of this phenomenon, i.e., electrostatic constraints linked to DW configurations in a ferroelectric. This study indicates that as an intrinsic property, the width of the ferroic DWs varies with different electrostatic constraints and must be taken into consideration during its applications. [ABSTRACT FROM AUTHOR]

In this review, we highlighted the main achievements in the field of electrocatalytic generation of acyl radicals and their applications. These electrochemical strategies were introduced with an emphasis on the substrate scope, reaction limitation and underlying mechanism. The related reactions were categorized according to the pathways of acyl radical generation, including outer‐sphere electron transfer (ET), inner‐sphere ET, and hydrogen atom transfer (HAT) processes. [ABSTRACT FROM AUTHOR]

Background: DNA damage in airway epithelia under exogenous disruptors can trigger various pulmonary diseases. Integrin beta 4 (ITGB4) is a structural adhesion molecule, which is indicated to regulate the process of DNA damage in airway epithelia for its unique long cytoplasmic domain subunit. Methods: The expression level of ITGB4 and the degree of DNA damage were observed in the house dust mite (HDM)‐stressed model and ozone‐challenged model, respectively. Besides, ITGB4 conditional knockout mice and ITGB4‐deficient airway epithelial cells were constructed to observe the influence of ITGB4 deficiency on DNA damage. Furthermore, the influence of ITGB4 deficiency on HDAC1 expression in airway epithelia was determined under stress stimulation. Finally, corresponding intervention strategies were carried out to verify the involvement of the ITGB4‐mediated HDAC1 pathway in DNA damage of airway epithelial cells. Results: HDM stress and ozone challenge reduced the expression of ITGB4, which is accompanied by the increased expression of 8‐oxoG and γ‐H2AX both in vivo and in vitro. Moreover, ITGB4 deficiency in airway epithelia aggravates the degree of DNA damage under HDM stimulation and ozone stress, respectively. Furthermore, ITGB4 deficiency downregulated the expression of HDAC1 during DNA damage, and restoring HDAC1 can reverse the enhanced DNA damage in airway epithelial cells after exogenous stress. Conclusions: This study confirmed the involvement of ITGB4 in the regulation of DNA damage through mediating HDAC1 in airway epithelial cells under exogenous stress. These results supply some useful insights into the mechanism of DNA damage in airway epithelial cells, which would provide possible targets for early prediction and intervention of pulmonary diseases. [ABSTRACT FROM AUTHOR]

Biodiversity across multiple trophic levels is required to maintain multiple ecosystem functions. Yet it remains unclear how multitrophic diversity and species interactions regulate ecosystem multifunctionality. Here, combining data from 9 different trophic groups (including trees, shrubs, herbs, leaf mites, small mammals, bacteria, pathogenic fungi, saprophytic fungi, and symbiotic fungi) and 13 ecosystem functions related to supporting, provisioning, and regulating services, we used a multitrophic perspective to evaluate the effects of elevation, diversity, and network complexity on scale‐dependent subalpine forest multifunctionality. Our results demonstrated that elevation and soil pH significantly modified species composition and richness across multitrophic groups and influenced multiple functions simultaneously. We present evidence that species richness across multiple trophic groups had stronger effects on multifunctionality than species richness at any single trophic level. Moreover, biotic associations, indicating the complexity of trophic networks, were positively associated with multifunctionality. The relative effects of diversity on multifunctionality increased at the scale of the larger community compared to a scale accounting for neighboring interactions. Our results highlight the paramount importance of scale‐ and context‐dependent multitrophic diversity and interactions for a better understanding of mountain ecosystem multifunctionality in a changing world. [ABSTRACT FROM AUTHOR]

Work function strongly impacts the surficial charge distribution, especially for metal‐support electrocatalysts when a built‐in electric field (BEF) is constructed. Therefore, studying the correlation between work function and BEF is crucial for understanding the intrinsic reaction mechanism. Herein, we present a Pt@CoOx electrocatalyst with a large work function difference (ΔΦ) and strong BEF, which shows outstanding hydrogen evolution activity in a neutral medium with a 4.5‐fold mass activity higher than 20 % Pt/C. Both experimental and theoretical results confirm the interfacial charge redistribution induced by the strong BEF, thus subtly optimizing hydrogen and hydroxide adsorption energy. This work not only provides fresh insights into the neutral hydrogen evolution mechanism but also proposes new design principles toward efficient electrocatalysts for hydrogen production in a neutral medium. [ABSTRACT FROM AUTHOR]

The Minisci alkylation of N‐heteroarenes with unactivated alkanes under external oxidant‐free conditions provides an economically attractive route to access alkylated N‐heteroarenes but remains underdeveloped. Herein, a new electrophotocatalytic strategy to access alkyl radicals from strong C(sp3)−H bonds was reported for the following Minisci alkylation reactions in the absence of chemical oxidants. This strategy realized the first example of cerium‐catalyzed Minisci alkylation reaction directly from abundant unactivated alkanes with excellent atom economy. It is anticipated that the general design principle would enrich catalytic strategies to explore the functionalizations of strong C(sp3)−H bonds under external oxidant‐free conditions with H2 evolution. [ABSTRACT FROM AUTHOR]

Nonmetal heteroatom incorporation into the lattice of host materials is a common way to regulate the surface electronic structure of electrocatalysts to boost their electrocatalytic performance. However, the heteroatom incorporation will inevitably trigger lattice strain and vacancy, which may lead to large changes in the structure of host materials. In this situation, the reconstruction of doped catalysts easily occurs during the catalytic process under harsh alkaline media, which hinders understanding the structure–activity correlation between catalysts and catalytic performance. Herein, taking cobalt nitride as an example, it is promulgated that a low‐temperature selenium sublimation strategy can effectively optimize the surface electronic structure in Co4N nanowire arrays with no significant change of bulk phase structure. Benefiting from surface selenium modification, the optimized SeCo4N nanowire arrays exhibit a 6.5 times enhancement of catalytic activity with structural phase stability for hydrogen evolution reaction in basic media. These findings may provide a new concept to design stable structured catalysts for energy‐related applications. [ABSTRACT FROM AUTHOR]

Morphological trait‐matching and species abundance are thought to be the main factors affecting the frequency and strength of mutualistic interactions. However, the relative importance of trait‐matching and species abundance in shaping species interactions across environmental gradients remains poorly understood, especially for plant–insect mutualisms involving generalist species.Here, we characterised variation in species and trait composition and the relative importance of trait‐matching and species abundance in shaping plant–Hymenoptera and plant–Diptera mutualisms in four meadows across an elevational gradient (2,725–3,910 m) in Yulong Snow Mountain, Southwest China. We also evaluated the effects of morphological traits of flower visitors and plant composition on their foraging specialisation (d' and normalised degree).There was a high degree of dissimilarity in the composition of Hymenoptera and Diptera visitors and their visited plants between communities. This variation was mainly driven by the spatial replacement of species. Both for plant–Hymenoptera and plant–Diptera networks, trait‐matching between nectar tube depth and proboscis length was a stronger predictor of the interactions between temporally co‐occurring plants and flower visitors than species abundance. Fourth‐corner analyses revealed statistically significant trait‐matching between nectar tube depth and proboscis length in plant–Hymenoptera networks at all sites, suggesting that Hymenoptera consistently foraged on plant species with nectar tube depths matching their proboscis lengths. By contrast, significant trait‐matching in plant–Diptera networks was only observed at the two lower elevation sites. The species‐level specialisation d' of flower visitors increased significantly as the proboscis length and the difference in nectar tube depth between the plant community and the plants visited by flower visitors increased.Our results highlight that the importance of trait‐matching in shaping pairwise interactions and niche partitioning depends on the specific features (e.g. species composition and trait availability) of the plant–pollinator system. For specialised plant–Hymenoptera systems, trait‐matching is an important determinant of species interactions, whereas for generalist plant–Diptera systems, trait‐matching is relatively unimportant. [ABSTRACT FROM AUTHOR]

A deep extraterrestrial drilling mission potentially adds a new level of complexity, and it is crucial to understand the associated challenges. To cope with China's Chang'E 5 mission to return subsurface regolith samples from the Moon, a series of laboratory tests were performed to validate the lunar robotic drilling from 2015 to 2018. The tests took place in a simulated thermal‐vacuum regolith environment, a highly relevant lunar analog site. Force and temperature sensors were integrated into a 2‐m class dry auger coring drill to assess the mechanical and thermophysical status of the sampling process. The operation of the entire testing system was automated, covering regolith penetration and data collection and storage. The science team used sensing data to characterize the subsurface geologic strata, assess the conditions of the drilling robot, and direct the sampling strategy. This experiment represents an essential first step in understanding the technology and operational requirements for lunar drilling and sampling mission. Many laboratory tests have helped guide the design and implementation of the highly successful lunar regolith‐sampling task in the Chang'E 5 mission. This paper documents the experimental system design, highlighting some critical design criteria and design tradeoffs. It also discusses the results of laboratory testing and lists some of the key technological lessons learned. [ABSTRACT FROM AUTHOR]

The crystalline structures and magnetic and thermodynamic properties of a Gd4Ga2O9 single crystal grown with the optical floating zone technique have been investigated. Gd4Ga2O9 crystallizes in a monoclinic structure with the space group P21/c at room temperature. Temperature‐dependent magnetic susceptibility measurements along the three crystallographic axes reveal a paramagnetic (PM) behavior between 2 and 300 K. A Curie–Weiss (CW) law fit was carried out and the CW temperature gθCW and magnetic frustration parameter f were calculated; these suggest antiferromagnetic (AFM) interactions between Gd3+ spins and a strong magnetic frustration. The field dependence of the magnetization at 2 K further confirms the magnetic frustration characteristics. A distinct λ‐shaped peak at 1.4 K in the heat capacity curves suggests a transition from the PM to AFM phase. The magnetic entropy is contributed solely by Gd3+ ions. [ABSTRACT FROM AUTHOR]

The atomically precise control over the size, shape and structure of nanographenes (NGs) or the introduction of heteroatom dopants into their sp2‐carbon lattice confer them valuable electronic, optical and magnetic properties. Herein, we report on the design and synthesis of a hexabenzocoronene derivative embedded with graphitic nitrogen in its honeycomb lattice, achieved via on‐surface assisted cyclodehydrogenation on the Au(111) surface. Combined scanning tunnelling microscopy/spectroscopy and non‐contact atomic force microscopy investigations unveil the chemical and electronic structures of the obtained dicationic NG. Kelvin probe force microscopy measurements reveal a considerable variation of the local contact potential difference toward lower values with respect to the gold surface, indicative of its positive net charge. Altogether, we introduce the concept of cationic nitrogen doping of NGs on surfaces, opening new avenues for the design of novel carbon nanostructures. [ABSTRACT FROM AUTHOR]

Interfacially asymmetric magnetic multilayers made of heavy metal/ferromagnet have attracted considerable attention in the spintronics community for accommodating spin‐orbit torques (SOTs) and meanwhile for hosting chiral spin textures. In these multilayers, the accompanied interfacial Dzyaloshinskii–Moriya interaction (iDMI) permits the formation of Néel‐type spin textures. While significant progresses have been made in Co, CoFeB, Co2FeAl, CoFeGd based multilayers, it would be intriguing to identify new magnetic multilayers that could enable spin‐torque controllability and meanwhile host nanoscale skyrmions. In this report, first, thin films made of permanent magnet SmCo5 with perpendicular magnetic anisotropy are synthesized, in which the deterministic SOT switching, enabled by the spin Hall effect, in Pt/SmCo5/Ta trilayer is demonstrated. Further, the stabilization of room‐temperature skyrmions with diameters ≈100 nm in [Pt/SmCo5/Ta]15, together with a skyrmionium‐like spin texture in [Pt/SmCo5/Ir]15 multilayers is shown. Based on the material specific parameters, micromagnetic simulations are also carried out. The results confirm the presence of chiral spin textures in this new material family. Through interfacial engineering, the results thus demonstrate that rare earth permanent magnets could be a new platform for studying interfacial chiral spintronics. [ABSTRACT FROM AUTHOR]

Congeneric species may coexist at fine spatial scales through niche differentiation, however, the magnitude to which the effects of functional traits and phylogenetic relatedness contribute to their distribution along elevational gradients remains understudied. To test the hypothesis that trait and elevational range overlap can affect local speciesʼ coexistence, we first compared phylogenetic relatedness and trait (including morphological traits and leaf elements) divergence among closely related species of Rhododendron L. on Yulong Mountain, China. We then assessed relationships between the overlap of multiple functional traits and the degree of elevational range overlap among species pairs in a phylogenetic context. We found that phylogeny was a good predictor for most functional traits, where closely related species showed higher trait similarity and occupied different elevational niches at our study site. Species pairs of R. subgen. Hymenanthes (Blume) K. Koch showed low elevational range overlap and some species pairs of R. subgen. Rhododendron showed obvious niche differentiation. Trait divergence is greater for species in R. subgen. Rhododendron, and it plays an important role between species pairs with low elevational range overlap. Trait convergent selection takes place between co‐occurring closely related species that have high elevational range overlap, which share more functional trait space due to environmental filtering or ecological adaptation in more extreme habitats. Our results highlight the importance of evolutionary history and trait selection for species coexistence at fine ecological scales along environmental gradients. [ABSTRACT FROM AUTHOR]

Superhydrophobic surface with anisotropic wetting and no low‐surface‐energy modification is investigated in which laser ablation, ultrasonic cleaning with degreasing solution, and electrodeposition are used sequentially. The macrogrooves are prepared by laser, and the micro–nanoscale structures on macrogrooves are prepared by electrodeposition, which is important to study the effect of hierarchical structures on anisotropic wetting. Herein, the surface morphology and surface crystal structure are discussed with respect to the laser‐ablated surface and the subsequent degreasing solution super‐cleaning/electrodeposited surfaces. At the same time, stainless steel surfaces with grooves of different periodic intervals (30–150 μm) and depths (10–40 μm) are systematically fabricated by laser only. When the periodic interval is smaller (<=50 μm), the static anisotropy is not obvious (5°–7°). However, the smaller the groove periodic interval and the greater the depth (<=30 μm), the more obvious the sliding anisotropy. Finally, dense and uniform micro–nanostructures on laser‐ablated grooves are prepared by electrodeposition. The micro–nanohierarchical structures prepared by electrodeposition not only can make the droplets have superhydrophobic properties but also enhance the water drop's anisotropic sliding ability. [ABSTRACT FROM AUTHOR]

The introduction of heteroatoms is one of the most important ways to modulate the intrinsic electronic structure of electrocatalysts to improve their catalytic activity. However, for transition metal chalcogenides with highly symmetric crystal structure (HS‐TMC), the introduction of heteroatoms, especially those with large atomic radius, often induces large lattice distortion and vacancy defects, which may lead to structural phase transition of doped materials or structural phase reconstruction during the catalytic reaction. Such unpredictable situations will make it difficult to explore the connection between the intrinsic electronic structure of doped catalysts and catalytic activity. Herein, taking thermodynamically stable cubic CoSe2 phase as an example, we demonstrate that nitrogen incorporation can effectively regulate the intrinsic electronic structure of HS‐TMC with structural phase stability and thus promote its electrocatalytic activity for the hydrogen evolution activity (HER). In contrast, the introduction of phosphorus can lead to structural phase transition from cubic CoSe2 to orthorhombic phase, and the structural phase of phosphorus‐doped CoSe2 is unstable for HER. [ABSTRACT FROM AUTHOR]

Organic electrosynthesis has gained increasing research interest as it harvests electric current as redox regents, thereby providing a sustainable alternative to conventional approaches. Compared with direct electrosynthesis, indirect electrosynthesis employs mediator(s) to lower the overpotentials for substrate activation, and enhance the reaction efficiency and functional group compatibility by shifting the heterogenous electron transfer process to be homogenous. As one of the most versatile and cost‐efficient mediators, halogen mediators are always combined with an irreversible halogenation reaction. Thus, the electrochemical reaction between halogen mediators and substrates doesn't directly controlled by the two standard potentials difference. In this account, our recent developments in the area of halogen‐mediated indirect electrosynthesis are summarized. The anodically generated halogen species from halogenide salts have the abilities to undergo electron‐transfer (ET) or hydrogen‐atom‐ transfer (HAT) processes. The reaction features, scopes, limitations, and mechanistic rationalisations are discussed in this account. We hope our studies will contribute to the future developments to broaden the scope of halogen‐mediated electrosynthesis. [ABSTRACT FROM AUTHOR]