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The transition-metal-catalyzed alkenylation strategy of propargylic alcohol derivatives provides an efficient protocol to access multifunctional products in a double-nucleophilic attack pattern. While limited relevant asymmetric examples have been reported via palladium catalysis, here we first demonstrate that a nonprecious Ni(0)-based chiral complex can efficiently promote the tandem substitution process between propargylic carbonates and N-trifluoroethyl ketimines via consecutive aza-vinylogous activations, finally accomplishing a (3 + 2) annulation reaction to afford products embedding a 4-methylene-3,4-dihydro-2H-pyrrole framework with high regio-, diastereo-, and enantiocontrol. Their assemblies with a few all-carbon-based vinylogous precursors are also successful, and enantioenriched adducts containing a 3-methylenecyclopentene scaffold are furnished effectively. The substitution patterns for both types of substrates are substantial, and an array of synthetic elaborations is conducted to deliver more versatile architectures with high application potential. In addition, density functional theory calculations and control experiments have been conducted to rationalize the catalytic pathways and regio- and enantioselectivity control.

Dynamic DNA nanodevices, particularly DNA walkers, have proven to be versatile tools for target recognition, signal conversion, and amplification in biosensing. However, their ability to detect low-abundance analytes in complex biological samples is often compromised by limited amplification depth and severe signal leakage. To address these challenges, we developed a simple yet highly efficient strategy to engineer a self-replicating bipedal DNAzyme (SEDY) walker for sensitive and selective electrochemiluminescence (ECL) bioanalysis. Unlike conventional DNA walkers that are typically constructed by catalytic DNA assembly in a single direction, the SEDY walker integrates a self-replicating feedback mechanism that greatly enhances both the selectivity and sensitivity of bioanalysis. First, the SEDY walker is assembled through a target-triggered, enzyme-free, self-replicating catalytic approach, minimizing the risk of undesired side reactions and signal leakage by simplifying reactant complexity. Furthermore, the SEDY walker features newly exposed trigger sequences that facilitate its autonomous replication, leading to a robust and exponential amplification of its products. Our experiments demonstrate that the SEDY walker can sensitively and selectively detect acetamiprid by navigating specific probes within cross-shaped DNA orbits. The ECL biosensor offers a linear detection range from 1 × 10–15M to 1 × 10–9M, with a limit of detection as low as 5.8 × 10–16M. We anticipate that the SEDY walker will be a powerful tool for detecting various analytes in biological applications.

Quinazolines are essential structural constituents of many pharmaceuticals and bioactive natural products. Quinazoline-derived azomethine imines (QAIs) have emerged recently as valuable building blocks for the synthesis of various quinazoline derivatives. This Synopsis presents recent advances in (formal) cycloaddition reactions of QAIs for the synthesis of quinazoline-fused 5- to 8-membered heterocycles as well as three-dimensional compounds.

Bacterial aromatic polyketides are compounds with multiple aromatic rings synthesized by bacterial type II polyketide synthases (PKSs), some of which have been developed into clinical drugs. Compounds containing aromatic polyketides synthesized by hybrid type I and type II PKSs are extremely rare. Here, we report the discovery of a gene cluster encoding both modular type I and type II PKSs as well as KAS III through extensive bioinformatics analysis, leading to the characterization of the hybrid polyketide, spirocycline A. The structure of spirocycline A is rare among all aromatic polyketides, featuring a unique starter unit and four spirocycles and forming a dimer. Biosynthetic studies indicate that the starter unit of this molecule is synthesized by type I PKS in collaboration with two trans-acting ketoreductase (KR) and enoylreductase (ER). It is then transferred by KAS III to the type II PKS system, which synthesizes the tricyclic aromatic polyketide backbone. The subsequent formation of the spirocycle and dimerization are carried out by four redox enzymes encoded in the gene cluster. Overall, the discovery of spirocycline A provides a new approach for identifying novel aromatic polyketides and offers potential enzymatic tools for the bioengineering of these hybrid polyketides.

We investigate the structures and properties of Ge4C–/0and Ge4CH–/0clusters using anion photoelectron spectroscopy and theoretical calculations. Our calculations show that the first two low-lying isomers coexist in the experiments of Ge4C–and Ge4CH–. The first two low-lying isomers of Ge4C–have trigonal bipyramidal structures with the C atom on the equatorial plane and the top vertex, respectively. It is found that the first two low-lying isomers of Ge4CH–can be obtained by adding an H atom to the top and equatorial C atoms of Ge4C–, respectively. The AdNDP analyses reveal that the C atom in Ge4C forms one 4c-2e σ bond, two 4c-2e π bonds, and one 5c-2e σ bond with Ge atoms. The C atom in Ge4C interacts with an H–forming a C–H σ bond in Ge4CH–. AIMD simulation results indicate high dynamic stabilities of Ge4C and Ge4CH–at 300 and 500 K. Our results show that the structures and chemical bonding of Ge4B–and Ge4N+are similar to those of Ge4C, while those of Ge4BH2–and Ge4NH resemble those of Ge4CH–.

An organometallic iridium (Ir)-complex-functionalized nanographene catalyst Ir-PyPh-GCwas prepared via a two-step strategy involving amide ligand modification and metal Ir coordination. Ir-PyPh-GCshowed ultrahigh hydrogenation capability, good recyclability, and selectivity for carbonyl derivatives (ketones, aldehydes, and quinones) at a low temperature (40 °C). The as-prepared Ir-complex-based catalyst is less expensive, making it feasible for industrial application.

At present, there is a lack of real-time observations of electrical trees in opaque materials. The inverse problem was constructed to locate the charge left by partial discharge (PD) based on its electric field. Considering the complexity of the electrostatic field formula with a multilayer medium, the particle swarm optimization (PSO) algorithm was introduced to solve this inverse problem. The precision of PSO and the effects of white noise error and systematic error are calculated and analyzed. High-voltage PD experiment results with six boundary electric field measuring electrodes (MEDs) in a 1-D array were used to verify the accuracy of the PD location method. The accuracy was improved to 0.25 mm by the multilayer medium model. This model can be used to discover the overall structure of the electric tree in the pressboard, and techniques for further increasing its accuracy are proposed.

This letter proposes an efficient iterative method assisted by an artificial neural network (ANN) for pattern synthesis of arbitrary conformal arrays. Relying on a fast and accurate far-field evaluation solution based on the near-field Euler rotation and 2-D layer-wise fast Fourier transform (FFT) techniques, an ANN-ANN and an ANN-FFT iterative algorithms are constructed. The theoretical foundation, iterative process, and synthesis results are presented and analyzed. Numerical examples of synthesizing shaped, flat-top and 3-D low-sidelobe beams of different conformal arrays are provided to validate the synthesis performance of the algorithms in terms of efficiency and accuracy.

Diabetic cardiomyopathy (DCM) is a complication of diabetes mellitus characterized by heart failure and cardiac remodeling. Previous studies show that tetrahydroberberrubine (THBru) retrogrades cardiac aging by promoting PHB2-mediated mitochondrial autophagy and prevents peritoneal adhesion by suppressing inflammation. In this study we investigated whether THBru exerted protective effect against DCM in db/dbmice and potential mechanisms. Eight-week-old male db/dbmice were administered THBru (25, 50 mg·kg−1·d−1, i.g.) for 12 weeks. Cardiac function was assessed using echocardiography. We showed that THBru administration significantly improved both cardiac systolic and diastolic function, as well as attenuated cardiac remodeling in db/dbmice. In primary neonatal mouse cardiomyocytes (NMCMs), THBru (20, 40 μM) dose-dependently ameliorated high glucose (HG)-induced cell damage, hypertrophy, inflammatory cytokines release, and reactive oxygen species (ROS) production. Using Autodock, surface plasmon resonance (SPR) and DARTS analyses, we revealed that THBru bound to the domain of the receptor for advanced glycosylation end products (RAGE), subsequently leading to inactivation of the PI3K/AKT/NF-κB pathway. Importantly, overexpression of RAGE in NMCMs reversed HG-induced inactivation of the PI3K/AKT/NF-κB pathway and subsequently counteracted the beneficial effects mediated by THBru. We conclude that THBru acts as an inhibitor of RAGE, leading to inactivation of the PI3K/AKT/NF-κB pathway. This action effectively alleviates the inflammatory responses and oxidative stress in cardiomyocytes, ultimately leading to ameliorated DCM.

To analyze the hotspots, patterns, and distribution of research on the safety and risk of antibody preparations in the past 20 years. It also seeks to summarize the current status and trends of research on the safety and risk control of antibody preparations.

A linearly polarized reconfigurable 3-D frequency-selective surface (FSS) with controllable resonant behavior is proposed in this article. The reconfigurable performance relies on a kirigami-inspired deployable structure composed of crisscross substrates with mutually inverted notches. Four identical asymmetric double-split ring resonators are, respectively, positioned on the four faces of the 3-D unit cell with a parallelogram cross section. Under the normal incidence, two resonant frequencies can be seen in the transmission coefficient. At each resonant frequency, there exist two different reconfiguration mechanisms that have inverse impacts on the shift direction of the resonant frequency in the process of deploying. The type and the dominance degree of the reconfiguration mechanism that has the dominant impact can be adjusted by changing the position of the splits, which implies controllability of the shift speed and direction of the resonant frequencies when the deploying angle changes. Finally, a reconfigurable FSS with stable center frequency is proposed through the two resonant frequencies being engineered to shift at a similar speed but in opposite directions with the deploying angle. The simulation results illustrate that the proposed FSS can achieve a continuously reconfigurable bandwidth in the range of 4.8% and 30.3% and a center frequency variation of less than 2.0%, while the same level of center frequency stability is also verified by measurement results.

Bevacizumab is a recombinant humanized monoclonal immunoglobulin (Ig) G1 antibody of VEGF, and inhibits angiogenesis and tumor growth in hepatocellular carcinoma (HCC). Ferroptosis, a new form of regulated cell death function independently of the apoptotic machinery, has been accepted as an attractive target for pharmacological intervention; the ferroptosis pathway can enhance cell immune activity of anti-PD1 immunotherapy in HCC. In this study we investigated whether and how bevacizumab regulated ferroptosis and immune activity in liver cancer. Firstly, we performed RNA-sequencing in bevacizumab-treated human liver cancer cell line HepG2 cells, and found that bevacizumab significantly altered the expression of a number of genes including VEGF, PI3K, HAT1, SLC7A11 and IL-9 in liver cancer, bevacizumab upregulated 37 ferroptosis-related drivers, and downregulated 17 ferroptosis-related suppressors in particular. We demonstrated that bevacizumab triggered ferroptosis in liver cancer cells by driving VEGF/PI3K/HAT1/SLC7A11 axis. Clinical data confirmed that the expression levels of VEGF were positively associated with those of PI3K, HAT1 and SLC7A11 in HCC tissues. Meanwhile, we found that bevacizumab enhanced immune cell activity in tumor immune-microenvironment. We identified that HAT1 up-regulated miR-143 targeting IL-9 mRNA 3’UTR in liver cancer cells; bevacizumab treatment resulted in the increase of IL-9 levels and its secretion viaVEGF/PI3K/HAT1/miR-143/IL-9 axis, which led to the inhibition of tumor growth in vivo through increasing the release of IL-2 and Granzyme B from activated CD8+T cells. We conclude that in addition to inhibiting angiogenesis, bevacizumab induces ferroptosis and enhances CD8+T cell immune activity in liver cancer. This study provides new insight into the mechanisms by which bevacizumab synergistically modulates ferroptosis and CD8+T cell immune activity in liver cancer.

Flame temperature and spectral emissivity were the important parameters characterizing the sufficient degree of fuel combustion and the particle radiative characteristics in the Rocket Based Combined Cycle (RBCC) combustor. To investigate the combustion characteristics of the complex supersonic flame in the RBCC combustor, a new radiation thermometry combined with Levenberg-Marquardt (LM) algorithm and the least squares method was proposed to measure the temperature, emissivity and spectral radiative properties based on the flame emission spectrum. In-situ measurements of the flame temperature, emissivity and spectral radiative properties were carried out in the RBCC direct-connected test bench with laser-induced plasma combustion enhancement (LIPCE) and without LIPCE. The flame average temperatures at fuel global equivalence ratio (α) of 1.0b and 0.6 with LIPCE were 4.51% and 2.08% higher than those without LIPCE. The flame combustion oscillation of kerosene tended to be stable in the recirculation zone of cavity with the thermal and chemical effects of laser induced plasma. The differences of flame temperature at α = 1.0b and 0.6 were 503 K and 523 K with LIPCE, which were 20.07% and 42.64% lower than those without LIPCE. The flame emissivity with methane assisted ignition was 80.46% lower than that without methane assisted ignition, due to the carbon-hydrogen ratio of kerosene was higher than that of methane. The spectral emissivities at 600 nm with LIPCE were 1.25%, 22.2%, and 4.22% lower than those without LIPCE at α = 1.0a (with methane assisted ignition), 1.0b (without methane assisted ignition) and 0.6. The effect of concentration in the emissivity was removed by normalization to analyze the flame radiative properties in the RBCC combustor chamber. The maximum differences of flame normalized emissivity were 50.91% without LIPCE and 27.53% with LIPCE. The flame radiative properties were stabilized under the thermal and chemical effects of laser induced plasma at α = 0.6.

Weed resistance is a critical issue in crop production. Among the known herbicides, 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors are crucial for addressing weed resistance. HPPD inhibitors constitute a pivotal aspect of contemporary crop protection strategies. The advantages of these herbicides are their broad weed spectrum, flexible application, and excellent compatibility with other herbicides. They also exhibit satisfactory crop selectivity and low toxicity and are environmentally friendly. An increasing number of new HPPD inhibitors have been designed by combining computer-aided drug design with conventional design approaches. Herein, the molecular design and structural features of innovative HPPD inhibitors are reviewed to guide the development of new HPPD inhibitors possessing an enhanced biological efficacy.

Cardiopulmonary progenitor cells (CPPs) constitute a minor subpopulation of cells that are commonly associated with heart and lung morphogenesis during embryonic development but completely subside after birth. This fact offers the possibility for the treatment of pulmonary heart disease (PHD), in which the lung and heart are both damaged. A reliable source of CPPs is urgently needed. In this study, we reprogrammed human cardiac fibroblasts (HCFs) into CPP-like cells (or induced CPPs, iCPPs) and evaluated the therapeutic potential of iCPP-derived exosomes for acute lung injury (ALI). iCPPs were created in passage 3 primary HCFs by overexpressing GLI1, WNT2, ISL1 and TBX5 (GWIT). Exosomes were isolated from the culture medium of passage 6–8 GWIT-iCPPs. A mouse ALI model was established by intratracheal instillation of LPS. Four hours after LPS instillation, ALI mice were treated with GWIT-iCPP-derived exosomes (5 × 109, 5 × 1010particles/mL) via intratracheal instillation. We showed that GWIT-iCPPs could differentiate into cell lineages, such as cardiomyocyte-like cells, endothelial cells, smooth muscle cells and alveolar epithelial cells, in vitro. Transcription analysis revealed that GWIT-iCPPs have potential for heart and lung development. Intratracheal instillation of iCPP-derived exosomes dose-dependently alleviated LPS-induced ALI in mice by attenuating lung inflammation, promoting endothelial function and restoring capillary endothelial cells and the epithelial cells barrier. This study provides a potential new method for the prevention and treatment of cardiopulmonary injury, especially lung injury, and provides a new cell model for drug screening.

Lymphocyte activation gene 3 (LAG3), an immune checkpoint molecule expressed on activated T cells, functions as a negative regulator of immune responses. Persistent antigen exposure in the tumor microenvironment results in sustained LAG3 expression on T cells, contributing to T cell dysfunction. Fibrinogen-like protein 1 (FGL1) has been identified as a major ligand of LAG3, and FGL1/LAG3 interaction forms a novel immune checkpoint pathway that results in tumor immune evasion. In addition, ubiquitin-specific peptidase 7 (USP7) plays a crucial role in cancer development. In this study we investigated the role of USP7 in modulation of FGL1-mediated liver cancer immune evasion. We showed that knockdown of USP7 or treatment with USP7 inhibitor P5091 suppressed liver cancer growth by promoting CD8+T cell activity in Hepa1-6 xenograft mice and in HepG2 or Huh7 cells co-cultured with T cells, whereas USP7 overexpression produced the opposite effect. We found that USP7 upregulated FGL1 in HepG2 and Huh7 cells by deubiquitination of transcriptional factor PR domain zinc finger protein 1 (PRDM1), which transcriptionally activated FGL1, and attenuated the CD8+T cell activity, leading to the liver cancer growth. Interestingly, USP7 could be transcriptionally stimulated by PRDM1 as well in a positive feedback loop. P5091, an inhibitor of USP7, was able to downregulate FGL1 expression, thus enhancing CD8+T cell activity. In an immunocompetent liver cancer mouse model, the dual blockade of USP7 and LAG3 resulted in a superior antitumor activity compared with anti-LAG3 therapy alone. We conclude that USP7 diminishes CD8+T cell activity by a USP7/PRDM1 positive feedback loop on FGL1 production in liver cancer; USP7 might be a promising target for liver cancer immunotherapy.

• The TiO 2 /Bi 2 S 3 S-scheme heterojunction is prepared by hydrothermal method. • The TiO 2 /Bi 2 S 3 hybrid showed wide spectrum response and good photothermal effect. • An improved CO 2 photoreduction performance was achieved by the hybrid. • DFT calculation and in-situ characterization were used to clarify the mechanism. The combination of S-scheme heterojunction and photothermal effect is a promising strategy to achieve efficient CO 2 photoreduction into solar fuel due to the boosted charge carrier separation efficiency and faster surface reaction rate. Herein, unique photothermal-coupled TiO 2 /Bi 2 S 3 S-scheme heterojunction nanofibers were fabricated and applied to a full-spectrum CO 2 photoreduction system. Density functional theory calculation and experimental analyses have confirmed the generation of the internal electric field and the S-scheme electron transfer pathway, leading to a highly efficient charge carrier separation. Thanks to the excellent photothermal conversion capacity of Bi 2 S 3 , the photogenerated electron transfer rate, and surface reaction rate were further accelerated in hybrid photocatalysts. Under the synergistic effect of S-scheme heterojunction and photothermal effects, the optimal TiO 2 /Bi 2 S 3 nanofibers achieved 7.65 μmol h–1 of CH 4 production rate, which is 5.24 times higher than that of pristine TiO 2. Moreover, the morphology reconstruction of Bi 2 S 3 in hybrids facilitates the CH 4 selectivity was significantly improved from 64.2% to 88.7%. Meanwhile, the CO 2 photoreduction reaction route over TiO 2 /Bi 2 S 3 nanofibers was investigated based on in-situ Fourier transform infrared spectra. This work provides some useful hints for designing highly efficient photothermal-coupled photocatalysts for CO 2 photoreduction. [Display omitted] [ABSTRACT FROM AUTHOR]

Thermoplastic polyimides (TPIs) can meet the requirements of advanced electronic packaging such as flexible copper clad laminate (FCCL) applied under extreme conditions, attributed to their excellent thermal stability, mechanical properties, electrical insulation and chemical resistance. With the increasing demands for electronic devices, such as applications in high‐frequency communication, it is highly desirable to develop high‐performance TPI with good thermoplasticity, thermal stability, mechanical properties and dielectric properties. However, there is a trade‐off between thermoplasticity and other properties. Herein, we introduce an effective strategy to afford TPIs with good performance by copolymerization of a diamine monomer consisted of a coplanar aromatic carbazole group and a short flexible linkage methylene group. On the one hand, short flexible linkages help improve the flexibility of polymer chains and are not too much to enable small‐scale molecular motions below Tg. On the other hand, coplanar aromatic donor groups benefit to strong charge transfer complex (CTC) interaction and π‐π stacking interaction. Based on this strategy, the resultant TPI possesses good thermoplasticity with a proper Tgof 348 °C. Meanwhile, it preserves a low coefficient thermal expansion of 48 ppm K−1, low dielectric constant/dielectric loss factor of 3.27/0.0073 at 10 GHz, and tensile strength of ca. 78 MPa.

Bipyramidal structures featuring planar rings serve as potential building blocks for one-dimensional (1D) nanostructures. Pure Ge atoms typically prefer to form three-dimensional rather than planar structures. Although a few-metal-doped bipyramids with pure Ge planar rings are predicted for constructing Ge-based 1D nanostructures, there is limited knowledge about those with both Ge and doped atoms on the same planar rings. Here, we report a hexagonal bipyramidal Mn3Ge5cluster containing a Mn3Ge3six-membered ring with the potential to construct a 1D germanium-based nanostructure. We investigated the structures and properties of Mn3Ge5–/0using anion photoelectron spectroscopy and theoretical calculations. Mn3Ge5–has a C3vsymmetric distorted hexagonal bipyramidal structure, while Mn3Ge5has a C2vsymmetric hexagonal bipyramidal structure. Chemical bonding analyses show that Mn3Ge5–could be considered as a [Mn3]V[Ge5]6–complex. First-principles calculations indicate that Mn3Ge5may be used to construct a 1D ferrimagnetic [Mn3Ge5]∞nanostructure.

Amyloid-β oligomers (AβOs), crucial toxic proteins in early Alzheimer’s disease (AD), precede the formation of Aβ plaques and cognitive impairment. In this context, we present our iterative process for developing novel near-infrared fluorescent (NIRF) probes specifically targeting AβOs, aimed at early AD diagnosis. An initial screening identified compound 18as being highly selective for AβOs. Subsequent analysis revealed that compound 20improved serum stability while retaining affinity for AβOs. The most promising iteration, compound 37, demonstrated exceptional qualities: a high affinity for AβOs, emission in the near-infrared region, and good biocompatibility. Significantly, ex vivodouble staining indicated that compound 37detected AβOs in AD mouse brain and in vivoimaging experiments showed that compound 37could differentiate between 4-month-old AD mice and age-matched wild-type mice. Therefore, compound 37has emerged as a valuable NIRF probe for early detection of AD and a useful tool in exploring AD’s pathological mechanisms.

Pyroptosis, a form of programmed cell death, drives inflammation in the context of cerebral ischemia/reperfusion. The molecular mechanism of pyroptosis underlying ischemia/reperfusion, however, is not fully understood. The transient middle cerebral artery occlusion was applied to wild-type and caspase-1 knockout mice. 2,3,5-Triphenyltetrazolium chloride-staining and immunohistochemistry were used to identify the ischemic region, and western blot and immunofluorescence for the examination of neuronal pyroptosis. The expression of inflammatory factors and the behavioral function assessments were further conducted to examine the effects of caspase-1 knockout on protection against ischemia/reperfusion injury. Ischemia/reperfusion injury increased pyroptosis-related signals represented by the overexpression of pyroptosis-related proteins including caspase-1 and gasdermin D (GSDMD). Meanwhile, the number of GSDMD positive neurons increased in penumbra by immunofluorescence staining. Compared with wild-type mice, those with caspase-1 knockout exhibited decreased levels of pyroptosis-related proteins following ischemia/reperfusion. Furthermore, ischemia/reperfusion attack-induced brain infarction, cerebral edema, inflammatory factors, and neurological outcomes were partially improved in caspase-1 knockout mice. The data indicate that pyroptosis participates in ischemia/reperfusion induced-damage, and the caspase-1 might be involved, it provides some new insights into the molecular mechanism of ischemia.

Polymer agglomeration is a useful way to enlarge the particle size of polybutadiene latex (PBL). However, the agglomeration process is very complex and is affected by many factors. Therefore, it is difficult to predict the mean particle size and distribution of agglomerated PBL. This study proposed a novel simulation method based on the artificial neural network (ANN) model. Firstly, the influence of agglomeration conditions on the particle size of agglomerated PBL were investigated, including the particle size of pre‐agglomerate PBL, the amount, the α‐methacrylic acid (α‐MAA) content, the solid content and the particle size of agglomerating agent. It is found that these factors have a close nonlinear relationship with the mean particle size and polydispersion index (PDI) of agglomerated PBL. Then, a model containing 236 data points was built using ANN including these properties as input with mean particle size and PDI of agglomerated PBL as output. The coefficient of determination (R2) values predicted by ANN for training, validation, test and total data are 0.9879, 0.9964, 0.9930, and 0.9902, respectively. It indicates that there is a good agreement between experimental data and predicted results by ANN. This study demonstrates that a simple machine learning method has good performance in predicting the particle size of agglomerated PBL, which further improves the development efficiency of PBL polymer agglomeration.

Engineering symmetry breaking in thermoelectric materials holds promise for achieving an optimal thermoelectric efficiency. van der Waals (vdW) layered transition metal dichalcogenides (TMDCs) provide critical opportunities for manipulating the intrinsic symmetry through in-plane symmetry breaking interlayer twists and out-of-plane symmetry breaking heterostructures. Herein, the symmetry-dependent thermoelectric properties of MoS2and MoSe2obtained via first-principles calculations are reported, yielding an advanced ZT of 2.96 at 700 K. The underlying mechanisms reveal that the in-plane symmetry breaking results in a lowest thermal conductivity of 1.96 W·m–1·K–1. Additionally, the electric properties can be significantly modulated through band flattening and bandgap alteration, stemming directly from the modified interlayer electronic coupling strength owing to spatial repulsion effects. In addition, out-of-plane symmetry breaking induces band splitting, leading to a decrease in the degeneracy and complex band structures. Consequently, the power factor experiences a notable enhancement from ∼1.32 to 1.71 × 10–2W·m–1·K–2, which is attributed to the intricate spatial configuration of charge densities and the resulting intensified intralayer electronic coupling. Upon simultaneous implementation of in-plane and out-of-plane symmetry breaking, the TMDCs exhibit an indirect bandgap to direct bandgap transition compared to the pristine structure. This work demonstrates an avenue for optimizing thermoelectric performance of TMDCs through the implementation of symmetry breaking.

Supported lipid bilayers (SLBs), two-dimensional lipid films formed on a solid-supporting substrate, serve as models for biomembranes and exhibit remarkable potential in chemistry, biology, and medicine. However, preparing SLBs with highly negatively charged contents on the negatively charged surface by overcoming electrostatic repulsion remains a challenge. Here, a creative bicelle-mediated and divalent cation-free SLB preparation method with the assistance of phosphate-buffered saline (PBS) solution was proposed, which can form the SLBs containing 50% DOPS or 30% CL on the silica surface monitored by a quartz crystal microbalance with dissipation (QCM-D). Results of molecular dynamics (MD) simulation indicate that electrostatic repulsion can be overcome by the increased number of hydrogen bonds caused by the adsorption of dihydrogen phosphate ions onto the headgroups of lipids. In addition, the negatively charged SLB formation was identified to be a three-step kinetic process, which differs from a two-step mechanism in the case of amphoteric SLB. The extra kinetic step can be attributed to the reduction in the number of intermolecular hydrogen bonds and the ordering of water molecules in the hydration layer. This investigation resolves the challenge of fabricating SLB over negatively charged surfaces and offers a fresh perspective on the SLB assembly methodology.

The alkyl chain length of hydrophobic monomers significantly influences the properties of hydrophobic associative polymers. In this study, four hydrophobic monomers with varying chain lengths were copolymerized with acrylamide, using the inverse emulsion polymerization method. Four hydrophobic associative polyacrylamides were successfully synthesized and characterized using infrared spectroscopy, nuclear magnetic resonance (NMR), and radius of gyration detection, and they were compared with polyacrylamides (PAMs) (without hydrophobic monomers). Polymer morphology was analyzed using scanning electron microscopy, while rheological properties were assessed using a rheometer. Emulsion stability was determined by measuring conductivity. Investigation indicate a direct correlation between the rheological properties of the polymer and the stability of the emulsion with the alkyl chain length of the hydrophobic monomer. The longer the alkyl chain of the hydrophobic monomer, the higher the rheology and emulsion stability of the polymer by increasing hydrophobic association and droplet encapsulation.

Human-specific insertions play important roles in human phenotypes and diseases. Here we reported a 446-bp insertion (Insert-446) in intron 11 of the TBC1D8Bgene, located on chromosome X, and traced its origin to a portion of intron 6 of the EBF1gene on chromosome 5. Interestingly, Insert-446 was present in the human Neanderthal and Denisovans genomes, and was fixed in humans after human-chimpanzee divergence. We have demonstrated that Insert-446 acts as an enhancer through binding transcript factors that promotes a higher expression of human TBC1D8Bgene as compared with orthologs in macaques. In addition, over-expression TBC1D8Bpromoted cell proliferation and migration through “a dual finger” catalytic mechanism (Arg538 and Gln573) in the TBC domain in vitroand knockdown of TBC1D8Battenuated tumorigenesis in vivo.Knockout of Insert-446 prevented cell proliferation and migration in cancer and normal cells. Our results reveal that the human-specific Insert-446 promotes cell proliferation and migration by upregulating the expression of TBC1D8Bgene. These findings provide a significant insight into the effects of human-specific insertions on evolution.

Despite its high theoretical capacities, Sn4P3anodes in alkali-ion batteries (AIBs) have been plagued by electrode damage and capacity decay during cycling, mainly rooted in the huge volume changes and irreversible phase segregation. However, few reports endeavor to ascertain whether these causes bear relevance to phase evolution upon cycling. Moreover, the phase evolution mechanism for alkali-ion intercalation remains imprecise. Herein, the structural transformations and detailed mechanisms upon various alkali-ion intercalation processes are systematically revealed, utilizing both experimental techniques and theoretical simulations. The results reveal that the energy storage of Sn4P3occurs in a two-stage process, starting from an insertion process, followed by a transition process. As the cycle proceeds, the final delithiated/desodiated/depotassiated components gradually trap alkali ions (Li+, Na+, and K+), which is attributed to the incomplete electrochemical transition and difficulty in Sn4P3regeneration due to the kinetic limitations in removing M (M = Li, Na, and K). Furthermore, Sn4P3anode obeys the “shrinking core mechanism” in potassium-ion batteries (KIBs), wherein a minor fraction of Sn4P3in the outer layer of the particles is initially involved in the potassiation/depotassiation processes, followed by a gradual participation of the inner parts until the entire particle is involved. It is worth mentioning that K–Sn alloys are not found to exist during the transition process of KIBs; instead, K–Sn–P phases are found, which makes it differ from that in lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs). These findings are expected to deepen the understanding of the reaction mechanism of Sn4P3and enlighten the material designs for improved performance.

Pyrolysis is a promising thermochemical conversion technology, which can convert biomass and cellulose into value-added products. Herein, a new approach of oxalic acid-assisted staged fast pyrolysis (OASFP) of cellulose was developed, achieving the coproduction of 1,4:3,6-dianhydro-α-d-glucopyranose (DGP), furfural (FF), and formic acid (FA) in separated pyrolysis stages. The lab-scale tests demonstrated that a selectivity of 71.6% and a yield of 31.5 wt % for FA in the aqueous phase, as well as a selectivity of 55.6% and a yield of 1.2 wt % for FF in the organic phase, were achieved in the primary pyrolysis stage under the optimized conditions (primary pyrolysis temperature of 220 °C and cellulose-to-oxalic acid (OA) ratio of 1:3). During the subsequent secondary pyrolysis process at 400 °C, the decomposition of the solid residue achieved a yield of 7.2 wt % and a selectivity of 32.7% for DGP. The interaction between OA and cellulose during the primary pyrolysis stage was essential for DGP generation. The formation mechanism of major products and the role of OA were revealed based on experiments and density functional theory calculations. In total, the OASFP of cellulose offers new possibilities and opportunities for biomass utilization.

The musculoskeletal system contains an extensive network of lymphatic vessels. Decreased lymph flow of the draining collecting lymphatics usually occurs in clinic after traumatic fractures. However, whether defects in lymphatic drainage can affect fracture healing is unclear.

The poor dispersion stability and susceptibility to oxidation significantly restrict the practical application of MoS2as a lubricant additive. Here, MoS2nanocomposite powders with magnesium silicate hydroxide (MSH) reinforcement and amorphous carbon protection were prepared via a straightforward two-step procedure. Detailed studies of the structure, phase composition, tribological properties, and lubrication mechanism of the composite powder have been conducted. The results demonstrated that the morphology of the composite powders was rod-shaped MSH coated with amorphous carbon and layered MoS2. The introduction of amorphous carbon into the MSH/MoS2composite powders results in enhanced dispersion and a reduction in corrosion to copper sheets. Furthermore, the addition of 1.0 wt% MSH/MoS2/C nanoparticles to PAO-6 led to a decrease in the COF of the lubricating oil from 0.104 to 0.063. Meanwhile, the wear rate of the friction pair decreased from 5.91 × 10−7 mm3 N−1 m−1to 2.22 × 10−7 mm3 N−1 m−1. The excellent performance could be attributed to the introduction of amorphous carbon effectively prevents the oxidation of MoS2within the additive, leading to improved friction and wear resistance. The tribo-film, composed of MSH, Fe2O3, FeS, MoS2, graphite, and amorphous carbon, demonstrates remarkable capabilities in reducing friction and wear.

C16H14BrN3O2Pd, triclinic, P1‾$P\overline{1}$ (no. 2), a= 7.5162(5) Å, b= 12.5437(9) Å, c= 17.7525(12) Å, α= 73.149(2)°, β= 82.186(2)°, γ= 73.616(2)°, V= 1534.13(18) Å3, Z= 4, T= 100(2) K, Rgt(F) = 0.0208, wRref(F2) = 0.0573.

Due to the beam-pointing and polarization diversities of carrier-mounted elements, it is widely recognized that the principle of pattern multiplication is not applicable to conformal arrays, particularly when coupling effects are considered. This article proposes a near-field Euler rotation-based technique to transform the far-field calculation of arbitrary conformal arrays into the pattern-multiplication form. Specifically, this technique involves rotating and transforming the electric and magnetic field vectors, along with the position vectors on the near-field sampling surface in the local coordinate system (LCS), to a unified sampling surface encompassing all elements in the global coordinate system (GCS). Based on the Schelkunoff’s equivalence principle, the equivalent electric and magnetic currents, which are referred to as equivalent sources, are determined. Consequently, the far fields of the conformal array can be regarded as equivalent to those of arrays composed of these equivalent sources, with the radiation fields of each equivalent-source array conforming to the pattern-multiplication form. Furthermore, the equivalent-source arrays are transformed into 3-D uniform arrays through a virtual expansion operation. To expedite the far-field calculation, the technique incorporates the layer-wise 2-D fast Fourier transform (2D FFT) technique. This is achieved by analyzing the relationship between the array factor of these 3-D arrays and the layer-wise 2D FFT. Finally, several numerical examples, which involve cylindrical and hemispherical–conical arrays and take the mutual coupling (MC) effects into consideration, are provided to validate the advantages of the proposed technique in terms of calculation efficiency and accuracy.

The monkeypox virus (MPXV) has triggered a current outbreak globally. Genome sequencing of MPXV and rapid tracing of genetic variants will benefit disease diagnosis and control. It is a significant challenge but necessary to optimize the strategy and application of rapid full-length genome identification and to track variations of MPXV in clinical specimens with low viral loads, as it is one of the DNA viruses with the largest genome and the most AT-biased, and has a significant number of tandem repeats. Here we evaluated the performance of metagenomic and amplicon sequencing techniques, and three sequencing platforms in MPXV genome sequencing based on multiple clinical specimens of five mpox cases in Chinese mainland. We rapidly identified the full-length genome of MPXV with the assembly of accurate tandem repeats in multiple clinical specimens. Amplicon sequencing enables cost-effective and rapid sequencing of clinical specimens to obtain high-quality MPXV genomes. Third-generation sequencing facilitates the assembly of the terminal tandem repeat regions in the monkeypox virus genome and corrects a common misassembly in published sequences. Besides, several intra-host single nucleotide variations were identified in the first imported mpox case. This study offers an evaluation of various strategies aimed at identifying the complete genome of MPXV in clinical specimens. The findings of this study will significantly enhance the surveillance of MPXV.

From the perspective of wireless transmission distance in the terahertz-band (THz-band), the 10–100 m, 100–1000 m, and ≥1000 m ranges are recommended for indoor communications, medium-distance communications, and long-distance communications, respectively. However, most existing photonic terahertz communication demonstrations reported in previous studies have a distance of less than 100 m, with some being even shorter at 10 m or 1 m. In this study, by combining high-gain and high-sensitivity terahertz modules, as well as signal processing technology, we have successfully demonstrated transmission over 850 m with a net rate of 50 Gbit/s at a 320 GHz carrier frequency through outdoor field experimental verification. This particular demonstration represents the most significant distance-rate product, as well as the longest wireless distance achieved so far for photonic terahertz wireless communication. The results demonstrate that the integration of terahertz photonics, electronics, and cutting-edge DSP algorithms, has the potential to enable long-distance and high-speed wireless communication for frequencies ≥300 GHz. Our work represents another significant stride towards achieving our goal of realizing the world's first photonic terahertz-wave communication over kilometer-level distances.

The recycling of spent lithium-ion batteries is in urgent demand, while organic binders hinder the recovery of electrode materials. In this study, a pyrolysis-coupled mechanical milling method was proposed to recover electrode materials from a spent lithium-ion battery. The results showed that pyrolysis removed the organic binders inside the spent battery, and after the mechanical milling, the total recovery ratio of electrode materials increased from 38.91 to 93.70% under the conditions with a pyrolysis temperature of 650 °C, milling duration of 15 min, and grinding ball ratio of 2:3. Meanwhile, the recovery ratios of cathode metals and anode graphite reached 97.89 and 86.90%, respectively. On the basis of the characterization results, it was determined that the chemical valences of the recovered metals were reduced by the reductive pyrolysis gases, whereas the graphitization degree of the recovered graphite decreased dramatically as a result of the presence of pyrolysis char. The findings presented herein offered a simple and eco-friendly option for the recovery of electrode materials from a spent lithium-ion battery as well as recycling noble metals and graphite resources.

Excellent thermoelectric materials can be obtained by various synthesis procedures and optimization strategies, and the elaborately designed composition and microstructure benefit thermoelectric parameter decoupling. Herein, a high-performance mixed natural mineral (CQB), composed by chalcocite, quartz, and bismuthinite, enables direct thermoelectric energy conversion. The network of quartz layers is embedded into the matrix and blocks Cu ion long-range migration by producing the natural rheostat and voltage division circuit. The thermoelectric performance, mechanical strength, and electrical stability of natural minerals are found to be highly superior to the artificially synthesized Cu2S material. Learning from nature, a strategy for blocking mobile Cu+ions in Cu-based superionic conductors is proposed. Various Cu-based superionic conductors, composited with insulating macroscale glass sheets, have been designed and fabricated, showing highly enhanced electrical stability while maintaining good thermoelectric properties. These findings provide a deep understanding of the role of macroscopic insulating materials in improving the electrical stability of superionic conductors.

Hepatocellular carcinoma (HCC) is a concerning liver cancer with rising incidence and mortality rates worldwide. The effectiveness of traditional therapies in managing advanced HCC is limited, necessitating the development of new therapeutic strategies. Immune checkpoint inhibitors (ICIs) have emerged as a promising strategy for HCC management. By preventing tumor cells from evading immune surveillance through immunological checkpoints, ICIs can restore the immune system’s ability to target and eliminate tumors. While ICIs show promise in enhancing the immune response against malignancies, challenges such as drug resistance and adverse reactions hinder their efficacy. To address these challenges, developing individualized ICI treatment strategies is critical. Combining targeted therapy and immunotherapy holds the potential for comprehensive therapeutic effects. Additionally, biomarker-based individualized ICI treatment strategies offer promise in predicting treatment response and guiding personalized patient care. Future research should explore emerging ICI treatment methods to optimize HCC immunotherapy. This review provides an overview of ICIs as a new treatment for HCC, demonstrating some success in promoting the tumor immune response. However, drug resistance and adverse reactions remain important considerations that must be addressed. As tailored treatment plans evolve, the prospect of immunotherapy for HCC is expected to grow, offering new opportunities for improved patient outcomes.

In order to study the mechanical properties and microscopic damage of red sandstone by dry and wet cycling, this paper establishes a 3-dimensional uniaxial compression model of red sandstone by using PFC3D software. On this basis, microscopic cracks were introduced to analyze the influence of different cracks on the mesoscopic cracking of the model. The results show that the error between the simulation results and the test results is less than 10% for the model established by PFC3D software. Based on the discrete element model, displacement and velocity maps were obtained, and the values are larger at the contact with the load and smaller at the distance from the load. With the increase of the initial crack angle, the peak stress gradually increases, and with the decrease of the crack size, the peak stress gradually decreases, and the contact force also decreases.

The production of ferroalloys is a resource-intensive and energy-consuming process. To mitigate its adverse environmental effects, steel companies should implement a range of measures aiming at enhancing the utilization rate of ferroalloys. Therefore, a comprehensive ferroalloy model was proposed, incorporating a prediction model for alloying element yield based on case-based reasoning and support vector machine (CBR–SVM), along with a ferroalloy batching model employing an integral linear programming algorithm. In simulation calculations, the prediction model exhibited exceptional predictive performance, with a hit rate of 96.05% within 5%. The linear programming ingredient model proved effective in reducing costs by 20.7%, which was achieved through accurate adjustments to the types and quantities of ferroalloys. The proposed method and system were successfully implemented in the actual production environment of a specific steel plant, operating seamlessly for six months. This implementation has notably increased the product quality of the enterprise, with the control rate of high-quality products increasing from 46% to 79%, effectively diminishing the consumption and expenses associated with ferroalloys. The reduced usage of ferroalloys simultaneously reduces energy consumption and mitigates the adverse environmental impact of the steel industry.

Defects in meiotic prophase can cause meiotic chromosome missegregation and aneuploid gamete formation. Meiotic checkpoints are activated in germ cells with meiotic defects, and cells with unfixed errors are eliminated by apoptosis. How such a surveillance process is regulated remains elusive. Here, we report that a chromosome-coupled ubiquitin-proteasome pathway (UPP) regulates meiotic checkpoint activation and promotes germ cell apoptosis in C. elegansmeiosis-defective mutants. We identified an F-box protein, FBXL-2, that functions as a core component within the pathway. This chromosome-coupled UPP regulates meiotic DSB repair kinetics and chromosome dynamic behaviors in synapsis defective mutants. Disrupted UPP impairs the axial recruitment of the HORMA domain protein HIM-3, which is required for efficient germ cell apoptosis in synapsis defective mutants. Our data suggest that an efficient chromosome-coupled UPP functions as a part of the meiotic surveillance system by enhancing the integrity of the meiotic chromosome axis.

Currently, most experts only focus on the surface failure characteristics of material structures. Moreover, previous damage constitutive models were unable to simulate the nonlinear deformation characteristics of cement crushed stone during the initial compaction stage. To study the microdamage of cement crushed stone after freeze–thaw cycles and uniaxial compression, further exploration was conducted on the changes in displacement, number of microcracks, relationship between acoustic emission events and microcrack development after freeze–thaw cement gravel loading, as well as the number of force chains before and after loading. Based on the theory of damage mechanics, this article establishes a damage constitutive model that can simulate the entire deformation process of cement crushed stone under uniaxial compression conditions using a particle flow program. Based on the numerical model created by the discrete element method, this article reproduces the entire process of internal fracture of cement crushed stone from a microscopic perspective, which has certain advantages in studying the complex mechanical behavior of cement crushed stone. After freeze–thaw treatment, irreversible damage occurs inside the cement-stabilized crushed stone. The more freeze–thaw cycles, the lower the compressive strength of cement-stabilized crushed stone.

Abstract: An innovative route is reported to fabricate nano-particles in aqueous solution from oxyfluoride glass by the thermal induction and corrosion treatment in this letter. The investigations of X-ray diffraction and transmission electron microscope based on nano-particles in glass ceramics (GCs) and aqueous solution indicate that the nano-particles formed in glass matrix during the thermal induction process are released to aqueous solution and their structure, shape and luminescent properties in glass host can be kept. Owing to the designable composition of the nano-particles during glass preparation process, the method is a novel way to obtain nano-particles in aqueous solution from GCs.

Rapeseed (Brassica napusL.) is grown extensively worldwide, including in areas with saline soils. In this study, sorbitol-chelated calcium was applied to rapeseed plants to investigate its effects on the tolerance of plants and soil quality under salt stress. We conducted a pot experiment to explore the effects of sorbitol-chelated calcium on the physiological parameters, plant nutritional status, soil quality, and rhizosphere bacterial community of rapeseed. Sorbitol-chelated calcium application increased the biomass and soluble sugar content, and decreased the malondialdehyde, proline, and soluble protein contents of rapeseed plants under salt stress. Sorbitol-chelated calcium application increased the calcium concentrations and reduced the sodium concentrations of plants and soil. Additionally, sorbitol-chelated calcium altered the soil enzyme activity and the rhizosphere microbial community composition. The exogenous application of sorbitol-chelated calcium shows promise in improving plant growth and soil properties while alleviating salt stress.