Search

Abstract Owing to their synergistic interactions, dual-atom catalysts (DACs) with well-defined active sites are attracting increasing attention. However, more experimental research and theoretical investigations are needed to further construct explicit dual-atom sites and understand the synergy that facilitates multistep catalytic reactions. Herein, we precisely design a series of asymmetric selenium-based dual-atom catalysts that comprise heteronuclear SeN2–MN2 (M = Fe, Mn, Co, Ni, Cu, Mo, etc.) active sites for the efficient oxygen reduction reaction (ORR). Spectroscopic characterisation and theoretical calculations revealed that heteronuclear selenium atoms can efficiently polarise the charge distribution of other metal atoms through short-range regulation. In addition, compared with the Se or Fe single-atom sites, the SeFe dual-atom sites facilitate a reduction in the conversion energy barrier from *O to *OH via the coadsorption of *O intermediates. Among these designed selenium-based dual-atom catalysts, selenium-iron dual-atom catalysts achieves superior alkaline ORR performance, with a half-wave potential of 0.926 V vs. a reversible hydrogen electrode. In addition, the SeN2–FeN2-based Zn–air battery has a high specific capacity (764.8 mAh g−1) and a maximum power density (287.2 mW cm−2). This work may provide a good perspective for designing heteronuclear DACs to improve ORR efficiency.

Abstract Double-atom catalysts (DACs) have opened distinctive paradigms in the field of rapidly developing atomic catalysis owing to their great potential for promoting catalytic performance in various reaction systems. However, increasing the loading and extending the service life of metal active centres represents a considerable challenge for the efficient utilization of DACs. Here, we rationally design asymmetric nitrogen, sulfur-coordinated diatomic iron centres on highly defective nitrogen-doped carbon nanosheets (denoted A-Fe2S1N5/SNC, A: asymmetric), which possess the atomic configuration of the N2S1Fe-FeN3 moiety. The abundant defects and low-electronegativity heteroatoms in the carbon-based framework endow A-Fe2S1N5/SNC with a high loading of 6.72 wt%. Furthermore, A-Fe2S1N5/SNC has a low overpotential of 193 mV for the oxygen evolution reaction (OER) at 10 mA cm−2, outperforming commercial RuO2 catalysts. In addition, A-Fe2S1N5/SNC exhibits extraordinary stability, maintaining > 97% activity for over 2000 hours during the OER process. This work provides a practical scheme for simultaneously balancing the activity and stability of DACs towards electrocatalysis applications.

Abstract Direct oxidation of KA oil (the mixture of cyclohexanone and cyclohexanol) toward ε-caprolactone is in high demand yet hard to implement in need of juggling the activation of both methyne C-H bond of cyclohexanol and α-C-C bond of cyclohexanone. Here we demonstrate that in situ formed Cu1+δ-Oδ-• active site, which originates from relay reaction at Ni(II) and Cu(I) pairs in a metal-organic framework (known as NiCu-MOF-74) with O2 and benzaldehyde (PhCHO), efficiently oxidizes KA oil toward ɛ-caprolactone along with good stability. Mechanism investigation discloses that the auxiliary Ni(II) site first adsorbs O2 for abstracting formyl hydrogen in PhCHO followed by transfer of PhCO· to react with another O2 over the major Cu(I) site, leading to formation of Cu1+δ-Oδ-• and PhCOOH. This major-auxiliary cooperative strategy will be particularly suitable for multivariate MOFs as next generation catalysts towards complex reactions.

Barium slag (BS) is a typical chemical hazardous waste, and its ecological risks cannot be ignored. Herein, the chemical composition, mineral composition and morphological characteristics of BS were investigated. In addition, the geochemical behaviour was investigated in terms of heavy-metal-leaching toxicity as well as the bioavailability, bioaccessibility and migration of these metals. The ecological risks associated with the release of heavy metals from BS driven by its geochemical behaviour were also evaluated. The BS displayed irregular particle morphologies and distinct surface structures, with heavy metal ions predominantly present in the smaller-sized BS particles. Zn, Ni, Mn and Ba exhibited a stronger potential for migration in plants than other heavy metals. This migration potential was influenced by their total amount and occurrence form as well as the pH conditions of the surrounding environment. The findings indicated that crops should not be planted around BS yards. The bioaccessible risks associated with heavy metals in BS were low. Mn, Ba, Fe and Ni primarily existed in the form of a weak-acid soluble fraction, thereby posing a high migration risk. Thus, attention should be paid to the ecological risks that may arise from Mn, Ba, Fe and Ni during storage.

Abstract Developing high-performance Pt-based catalysts with low Pt loading is crucial but challenging for CO oxidation at temperatures below 100 °C. Herein, we report a Pt-based catalyst with only a 0.15 wt% Pt loading, which consists of Pt–Ti intermetallic single-atom alloy (ISAA) and Pt nanoparticles (NP) co-supported on a defective TiO2 support, achieving a record high turnover frequency of 11.59 s–1 at 80 °C and complete conversion of CO at 120 °C. This is because the coexistence of Pt–Ti ISAA and Pt NP significantly alleviates the competitive adsorption of CO and O2, enhancing the activation of O2. Furthermore, Pt single atom sites are stabilized by Pt–Ti ISAA, resulting in distortion of the TiO2 lattice within Pt–Ti ISAA. This distortion activates the neighboring surface lattice oxygen, allowing for the simultaneous occurrence of the Mars-van Krevelen and Langmuir–Hinshelwood reaction paths at low temperatures.

ObjectivesThis paper investigates the impact of shared lines with different materials on the dynamic response of floating wind farms in order to design a rational shared mooring system. MethodsFirst, shared mooring and traditional (without shared cables) mooring systems are designed for floating wind farms. The dynamic response and economic cost of the two mooring systems are then compared to validate the feasibility of the shared mooring system design. Second, the influence of the two types of shared mooring systems on the mooring response of floating wind farms is studied. Finally, an analysis is made of the influence of load direction and line material on the tension of the shared lines.ResultsThe results indicate that floating wind farms with shared mooring systems using different materials have nearly identical blade tension. However, there are differences in the impact of the two types of shared mooring systems on wind turbine displacement and the mean tension of mooring lines. In addition, the environmental load direction and line material affect wind turbine displacement and shared line tension.ConclusionsThis study provides useful references for selecting material for shared lines in the mooring systems of floating wind farms.

Disruption of p53-MDM2/MDMX interaction by smaller inhibitors is a promising therapeutic intervention gaining tremendous interest. However, no MDM2/MDMX inhibitors have been marketed so far. Drug repurposing is a validated, practical approach to drug discovery. In this regard, we employed structure-based virtual screening in a reservoir of marketed drugs and identified nintedanib as a new MDM2/MDMX dual inhibitor. The computational structure analysis and biochemical experiments uncover that nintedanib binds MDM2/MDMX similarly to RO2443, a dual MDM2/MDMX inhibitor. Furthermore, the mechanistic study reveals that nintedanib disrupts the physical interaction of p53-MDM2/MDMX, enabling the transcriptional activation of p53 and the subsequent cell cycle arrest and growth inhibition in p53+/+ cancer cells. Lastly, structural minimisation of nintedanib yields H3 with the equivalent potency. In summary, this work provides a solid foundation for reshaping nintedanib as a valuable lead compound for the further design of MDM2/MDMX dual inhibitors.

Aberrant tumor blood vessels are prone to propel the malignant progression of tumors, and targeting abnormal metabolism of tumor endothelial cells emerges as a promising option to achieve vascular normalization and antagonize tumor progression. Herein, we demonstrated that salvianic acid A (SAA) played a pivotal role in contributing to vascular normalization in the tumor-bearing mice, thereby improving delivery and effectiveness of the chemotherapeutic agent. SAA was capable of inhibiting glycolysis and strengthening endothelial junctions in the human umbilical vein endothelial cells (HUVECs) exposed to hypoxia. Mechanistically, SAA was inclined to directly bind to the glycolytic enzyme PKM2, leading to a dramatic decrease in endothelial glycolysis. More importantly, SAA improved the endothelial integrity via activating the β-Catenin/Claudin-5 signaling axis in a PKM2-dependent manner. Our findings suggest that SAA may serve as a potent agent for inducing tumor vascular normalization.

Abstract Background Circulating tumor cell (CTC) clusters play a critical role in carcinoma metastasis. However, the rarity of CTC clusters and the limitations of capture techniques have retarded the research progress. In vitro CTC clusters model can help to further understand the biological properties of CTC clusters and their clinical significance. Therefore, it is necessary to establish reliable in vitro methodological models to form CTC clusters whose biological characteristics are very similar to clinical CTC clusters. Methods The assays of immunofluorescence, transmission electron microscopy, EdU incorporation, cell adhension and microfluidic chips were used. The experimental metastasis model in mice was used. Results We systematically optimized the culture methods to form in vitro CTC clusters model, and more importantly, evaluated it with reference to the biological capabilities of reported clinical CTC clusters. In vitro CTC clusters exhibited a high degree of similarity to the reported pathological characteristics of CTC clusters isolated from patients at different stages of tumor metastasis, including the appearance morphology, size, adhesive and tight junctions-associated proteins, and other indicators of CTC clusters. Furthermore, in vivo experiments also demonstrated that the CTC clusters had an enhanced ability to grow and metastasize compared to single CTC. Conclusions The study provides a reliable model to help to obtain comparatively stable and qualified CTC clusters in vitro, propelling the studies on tumor metastasis.

Abstract Seawater electrolysis offers a renewable, scalable, and economic means for green hydrogen production. However, anode corrosion by Cl- pose great challenges for its commercialization. Herein, different from conventional catalysts designed to repel Cl- adsorption, we develop an atomic Ir catalyst on cobalt iron layered double hydroxide (Ir/CoFe-LDH) to tailor Cl- adsorption and modulate the electronic structure of the Ir active center, thereby establishing a unique Ir-OH/Cl coordination for alkaline seawater electrolysis. Operando characterizations and theoretical calculations unveil the pivotal role of this coordination state to lower OER activation energy by a factor of 1.93. The Ir/CoFe-LDH exhibits a remarkable oxygen evolution reaction activity (202 mV overpotential and TOF = 7.46 O2 s−1) in 6 M NaOH+2.8 M NaCl, superior over Cl--free 6 M NaOH electrolyte (236 mV overpotential and TOF = 1.05 O2 s−1), with 100% catalytic selectivity and stability at high current densities (400-800 mA cm−2) for more than 1,000 h.

Abstract Background Cutaneous melanoma is a kind of skin malignancy with low morbidity but high mortality. Cryptotanshinone (CPT), an important component of salvia miltiorrhiza has potent anti-tumor activity and also indicates therapeutic effect on dermatosis. So we thought that CPT maybe a potential agent for therapy of cutaneous melanoma. Methods B16F10 and A375 melanoma cells were used for in vitro assay. Tumor graft models were made in C57BL/6N and BALB/c nude mice for in vivo assay. Seahorse XF Glycolysis Stress Test Kit was used to detect extracellular acidification rate and oxygen consumption rate. Si-RNAs were used for knocking down adenosine monophosphate-activated protein kinase (AMPK) expression in melanoma cells. Results CPT could inhibit the proliferation of melanoma cells. Meanwhile, CPT changed the glucose metabolism and inhibited phosphofructokinase (PFK)-mediated glycolysis in melanoma cells to a certain extent. Importantly, CPT activated AMPK and inhibited the expression of hypoxia inducible factor 1α (HIF-1α). Both AMPK inhibitor and silencing AMPK could partially reverse CPT’s effect on cell proliferation, cell apoptosis and glycolysis. Finally, in vivo experimental data demonstrated that CPT blocked the growth of melanoma, in which was dependent on the glycolysis-mediated cell proliferation. Conclusions CPT activated AMPK and then inhibited PFK-mediated aerobic glycolysis leading to inhibition of growth of cutaneous melanoma. CPT should be a promising anti-melanoma agent for clinical melanoma therapy.

Abstract Electrochemical reduction of carbon dioxide into ethylene, as opposed to traditional industrial methods, represents a more environmentally friendly and promising technical approach. However, achieving high activity of ethylene remains a huge challenge due to the numerous possible reaction pathways. Here, we construct a hierarchical nanoelectrode composed of CuO treated with dodecanethiol to achieve elevated ethylene activity with a Faradaic efficiency reaching 79.5%. Through on in situ investigations, it is observed that dodecanethiol modification not only facilitates CO2 transfer and enhances *CO coverage on the catalyst surfaces, but also stabilizes Cu(100) facet. Density functional theory calculations of activation energy barriers of the asymmetrical C–C coupling between *CO and *CHO further support that the greatly increased selectivity of ethylene is attributed to the thiol-stabilized Cu(100). Our findings not only provide an effective strategy to design and construct Cu-based catalysts for highly selective CO2 to ethylene, but also offer deep insights into the mechanism of CO2 to ethylene.

Abstract The performances of single-atom catalysts are governed by their local coordination environments. Here, a thermal replacement strategy is developed for the synthesis of single-atom catalysts with precisely controlled and adjustable local coordination environments. A series of Co-SxN4−x (x = 0, 1, 2, 3) single-atom catalysts are successfully synthesized by thermally replacing coordinated N with S at elevated temperature, and a volcano relationship between coordinations and catalytic performances toward electrochemical CO2 reduction is observed. The Co-S1N3 catalyst has the balanced COOH*and CO* bindings, and thus locates at the apex of the volcano with the highest performance toward electrochemical CO2 reduction to CO, with the maximum CO Faradaic efficiency of 98 ± 1.8% and high turnover frequency of 4564 h−1 at an overpotential of 410 mV tested in H-cell with CO2-saturated 0.5 M KHCO3, surpassing most of the reported single-atom catalysts. This work provides a rational approach to control the local coordination environment of the single-atom catalysts, which is important for further fine-tuning the catalytic performance.

Abstract The association between capsaicin, the major natural pungent compound of chili peppers, and gastric cancer progression has engendered conflicting findings. In this work, we sought to explore the character of a high capsaicin diet in gastric cancer metastasis and its possible mechanism. The impact of high capsaicin consumption on gastric cancer metastasis was investigated in vivo (xenograft mouse and zebrafish models) and in vitro (biochemical and molecular assays). It was demonstrated that high diet of capsaicin gave rise to accelerate tumor metastasis, which was partially mediated by elevating the expression of transient receptor potential vanilloid 1 (TRPV1) in gastric cancer cells. Importantly, we found that genetic depletion of TRPV1 could reduce gastric cancer metastasis by diminishing the motility of tumor cells in vitro, but acted poorly in xenograft mouse model. Considering the distribution of capsaicin in vivo, 16S rRNA sequencing and fecal microbiota transplantation (FMT) were used to appraise whether the gut microbiota involved in the high capsaicin diet induced metastasis. It was demonstrated that the level of Firmicutes and Clostridiales was expressively boosted following the high consumption of capsaicin. This microbial shift contributed to the increased peripheral 5-hydroxytryptamine (5-HT) levels, yielding the aggravated metastatic burden. Collectively, our findings highlighted the potential risk of high capsaicin diet in promoting gastric cancer metastasis by virtue of modulating TRPV1 expression and gut microbiota composition, indicating the importance of controlled consumption of chili peppers for patients with gastric cancer. Video Abstract

The prediction of the ablation rate of silicone rubber-based composites is of great significance to accelerate the development of flexible thermal protection materials. Herein, a method which combines uniform design experimentation, active learning, and virtual sample generation was proposed to establish a prediction model of the mass ablation rate based on a small dataset. Briefly, a small number of sample points were collected using uniform design experimentation, which were marked to construct the initial dataset and primitive model. Then, data points were acquired from the sample pool and iterated using various integrated algorithms through active learning to update the above dataset and model. Finally, a large number of virtual samples were generated based on the optimal model, and a further optimized prediction model was achieved. The results showed that after introducing 300 virtual samples, the average percentage error of the gradient boosting decision tree (GBDT) prediction model on the test set decreased to 3.1%, which demonstrates the effectiveness of the proposed method in building prediction models based on a small dataset.

As global demand for sustainable biomass and need to mitigate global warming begin to rise, cultivation of seaweed has gained significant attention in recent years due to its potential for carbon recycling. However, limited availability of suitable coastal areas for large-scale seaweed cultivation has led to exploration of offshore environments as a viable alternative. The nature of many offshore environments often exposes seaweed farming systems to harsh environmental conditions, including strong waves, currents, and wind. These factors can lead to structural failures, kelp losses, and significant financial losses for seaweed farmers. The main objective of this study is to present a robust design and numerical analysis of an economically viable floating offshore kelp farm facility, and evaluate its stability and mooring system performance. A numerical method of preliminary designs of the offshore aquaculture systems were developed using the OrcaFlex software. The models were subjected to a series of dynamic environmental loading scenarios representing extreme events. These simulations aimed to forecast the overall dynamic response of an offshore kelp farm at a depth of 50m and to determine the best possible farm design with structural integrity for a selected offshore environment. Furthermore, to assess the economic feasibility of establishing offshore seaweed farms, a comprehensive capital expenses analysis was conducted. The results revealed that, in terms of the kelp farms with the same number of the kelp cultivating lines, the cost of building kelp farms will be strongly affected by the cost of mooring lines. The present study may help to understand the dynamic response and economic feasibility of offshore kelp farms.

Reactive oxygen species (ROS) have a significant part in the elimination of recalcitrant organic pollutants and commonly coexist in one advanced oxidation system. It is difficult for us to make clear the effect of the co-instantaneous generation of radicals and nonradicals, which would cover and obscure the transformation pathway. Herein, a coordinate welding process is presented for fabricating accessible Mn1 site catalysts (Mn SSCs) in order to clarify the nonradical (singlet oxygen/1O2) generated pathway and transformation in oxidative removal of contaminants. The Mn SSCs achieve nearly 100% 1O2 fabrication by activating peroxymonosulfate, which displays an excellent sulfamethoxazole elimination performance, super anti-anion interference, and extraordinary stability. As revealed by density functional theory calculations, the Mn SSCs with a special welded three-dimensional nanostructure could significantly boost the activation process by oxidizing the peroxymonosulfate at the interlayer of Mn SSCs and reducing dissolved oxygen on the surface of Mn SSCs. This design of Mn SSCs with a three-dimensional welded nanostructure might offer a potential approach for employing single site catalysts for environmental remediation.

ABSTRACT Necrotizing enterocolitis (NEC) is a challenging gastrointestinal disease that disproportionately affects premature neonates, with high incidence and case-fatality rates. Despite extensive research efforts, the pathogenesis and mechanisms of NEC remain unclear, making it difficult to effectively eradicate. However, it has been established that dysbiosis of gut microbes occurs before the onset of NEC, providing compelling evidence for the potential use of probiotic therapy. As such, we have focused our attention on two probiotics in particular: Clostridium butyricum and Clostridium tyrobutyricum, especially in light of recent breakthroughs that have linked several Clostridia species with NEC. To determine whether C. butyricum and C. tyrobutyricum are pathogenic or probiotic, we conducted a comparison of the phenotypic traits of NEC mice treated with each bacterium. Our results confirm that treatment with C. tyrobutyricum restores intestinal barrier integrity and alleviates inflammatory immune responses associated with NEC. In contrast, treatment with C. butyricum exacerbates intestinal barrier damage and promotes immune disorder, including increased numbers of macrophages, monocytes, and neutrophils in the intestinal lamina propria. Further analysis of the gut microbiome suggests that the positive effects of C. tyrobutyricum treatment are associated with an increase in Akkermansia muciniphila, while C. butyricum treatment decreases the level of A. muciniphila, which accounts for its negative effect on NEC. This study sheds light on the fact that treatment with C. tyrobutyricum, but not C. butyricum, has the potential to protect against NEC development. The opposite effects of these two probiotics on NEC may result from their different modulation of the level of A. muciniphila, a gut microbe that is closely associated with intestinal homeostasis. In summary, by improving the abundance of A. muciniphila to alleviate intestinal inflammation and enhance intestinal barrier integrity, supplementation with C. tyrobutyricum may become a promising therapy for NEC.IMPORTANCEThis study sheds light on that treatment with Clostridium tyrobutyricum but not Clostridium butyricum is entitled to protect against necrotizing enterocolitis (NEC) development potentially. The mechanisms behind the opposite effect on NEC may result in different modulation on the level of Akkermansia muciniphila, which is deeply associated with intestinal homoeostasis. Briefly, through improving the abundance of A. muciniphila to alleviate intestinal inflammation and enhance intestinal barrier integrity, C. tyrobutyricum supplement may become a promising therapy for NEC.

Abstract Despite the desirability of metal–organic frameworks (MOFs) as heterogeneous photocatalysts, current strategies available to enhance the performance of MOF photocatalysts are complicated and expensive. Herein, a simple strategy is presented for improving the activity of MOF photocatalysts by regulating the atomic interface structure of the metal active sites on the MOF. In this study, MOF (PCN‐222) is hybridized with cellulose acetate (CA@PCN‐222) through an optimized atomic interface strategy, which lowers the average valence state of Zr ions. The electronic metal‐support interaction mechanism of CA@PCN‐222 is revealed by evaluating the photocatalytic CO2 reduction reaction (CO2RR). The experimental results suggested that the electron migration efficiency at the atomic interface of the MOFs strongly coupled with cellulose is significantly improved. In particular, the CO2RR to formate activity of CA@PCN‐222 photocatalyst greatly increased from 778.2 to 2816.0 µmol g−1 compared with pristine PCN‐222 without cellulose acetate. The findings suggest that the strongly coupled metal–ligand moiety at the atomic interface of MOFs may play a synergistic role in heterogeneous catalysts.

To address the requirements of sonar imaging, such as high receiving sensitivity, a wide bandwidth, and a wide receiving angle, an AlN PMUT with an optimized ratio of 0.6 for the piezoelectric layer diameter to backside cavity diameter is proposed in this paper. A sample AlN PMUT is designed and fabricated with the SOI substrate-based bulk MEMS process. The characterization test result of the sample demonstrates a −6 dB bandwidth of approximately 500 kHz and a measured receiving sensitivity per unit area of 1.37 V/μPa/mm2, which significantly surpasses the performance of previously reported PMUTs. The −6 dB horizontal angles of the AlN PMUT at 300 kHz and 500 kHz are measured as 68.30° and 54.24°, respectively. To achieve an accurate prediction of its characteristics when being packaged and assembled in a receive array, numerical simulations with the consideration of film stress are conducted. The numerical result shows a maximum deviation of ±7% in the underwater receiving sensitivity across the frequency range of 200 kHz to 1000 kHz and a deviation of about 0.33% in the peak of underwater receiving sensitivity compared to the experimental data. By such good agreement, the simulation method reveals its capability of providing theoretical foundation for enhancing the uniformity of AlN PMUTs in future studies.

The main units of persimmon proanthocyanidins (PAs) are composed of flavan-3-ols including epigallocatechin gallate (EGCG) and gallocatechin gallate (GCG). Precise quantification of GCG is challenging due to its trace amounts in persimmon. In this study, to establish the optimal UHPLC-Q-Exactive Orbitrap/MS technique for the determination of PAs monomer composition in persimmon fruit flesh of different astringency types, mass spectrometry and chromatographic conditions were optimized. The results showed that when operating in negative ion mode, using a T3 chromatographic column (a type of C18 column with high-strength silica), acetonitrile as the organic phase, a 0.1% mobile phase acid content, and a mobile phase flow rate of 0.2 mL/min, the chromatographic peak shape and resolution of the PAs monomer composition improved. Additionally, there was no tailing phenomenon observed in the chromatographic peaks. At the same time, the intra-day and inter-day precision, stability, and recovery of the procedure were good. The relative standard deviation (RSD) of stability was less than 5%. The intra-day precision was in the range of 1.14% to 2.36%, and the inter-day precision ranged from 1.03% to 2.92%, both of which were less than 5%. The recovery rate ranged from 94.43% to 98.59% with an RSD less than 5%. The results showed that the UHPLC-Q-Exactive Orbitrap/MS technique established in this study can not only be used for the quantification of EGCG and GCG in persimmon fruit flesh but also be suitable for analyzing other PAs monomer compositions, providing robust support for the related research on persimmon PAs.

Copper-based materials can convert carbon dioxide into multi-carbon products but suffer from poor activity and selectivity. Here, the authors report CuO clusters supported on nitrogen-doped carbon nanosheets for the reduction CO2-to-ethanol, and investigate the change in the catalytic sites while in operation.

Abstract Background Tanshinone II A is an effective component extracted from Salvia miltiorrhiza and the roles of Tanshinone IIA in regulating the stemness of tumor cells remain unclear. This work aims to explore the roles and underlying mechanisms of Tanshinone IIA in breast cancer stemness. Methods In vitro mammary spheroid formation, flow cytometry assay on CD24−/CD44+ sub-population, ALDH activity detection, cell viability assay and western blot analysis, and in vivo tumor-initiating analysis were performed to examine the effects of Tanshinone IIA on the stemness of breast cancer cells. MiRNAs-based transcriptome sequencing and data analysis, online dataset analysis, luciferase reporter assay combined with rescuing experiments were constructed to explore the underlying mechanisms. Results Tanshinone IIA attenuated the stemness of breast cancer cells, evident by downregulating the expression of stemness markers, hindering the capacity of spheroid formation, decreasing the CD24−/CD44+ sub-population in a concentration-dependent manner and reducing the tumor-initiating ability of breast cancer cells. Additionally, Tanshinone IIA enhanced adriamycin sensitivity and attenuated adriamycin resistance of breast cancer cells. Combined with miRNAs-based transcriptome sequencing assay, it was found that Tanshinone IIA downregulated miR-125b level and upregulated its target gene STARD13 (StAR-related lipid transfer protein 13) level, thus inactivating the miR-125b/STARD13 axis, which had been previously confirmed to promote breast cancer progression. Notably, miR-125b overexpression enhanced the stemness of breast cancer cells, and miR-125b overexpression or STARD13 knockdown impaired the inhibitory effects of Tanshinone IIA on the stemness of breast cancer cells. Conclusions Tanshinone IIA could attenuate the stemness of breast cancer cells via targeting the miR-125b/STARD13 axis.

Single‐atom catalysts (SACs) are highly attractive in many surface‐dependent reactions due to their extraordinary reactivity and maximum atomic efficiency. However, in a practical catalytic system, guiding and transferring the reactant molecules to target single‐atom sites are crucial processes for achieving high‐efficient reactions. Herein, gas‐microchannels on TiO2 nanorod‐supported Pt single‐atom catalyst by in situ growing derivative TiO2 nanosheets are constructed. Those perpendicular‐grown TiO2 nanosheets can guide gas molecules to the reactive single Pt sites and thus realize an intact system of guidance‐transfer‐reaction. Experimentally, the local coordination and electronic states of Pt species decrease with the growth of nanosheets, which could significantly strengthen the adsorption and activation of oxygen molecules toward the acetone sensing. The final Pt1/TiO2 catalysts exhibit a high sensing response (13.6–50 ppm) to acetone gas, which are approximately three times higher than that of catalysts without scaly shell (4.8–50 ppm).

The influence of mooring systems with lines of different material on the dynamic response of a floating wind turbine is studied using a 5 MW OC4-DeepCwind semi-submersible wind turbine as a representative prototype in this study. Two types of mooring systems were designed using the MoorDyn module in OpenFAST software (v3.1.0): one uses chains, and the other uses a hybrid mooring line composed of chains and high-strength polyethylene (HMPE) ropes. A wind turbine with two types of mooring systems was simulated using the OpenFAST software. The results show that the floating wind turbine moored with the hybrid lines exhibited a larger heave and pitch motion than that moored using chains alone. At the same time, the surge displacement was smaller than that of the wind turbine using chains alone. In terms of mooring line tension, the mean and amplitude values of the hybrid mooring system at the location examined were smaller than those of the chain mooring system. Thus, using HMPE ropes in the mooring system can significantly reduce line loads. In addition, the HMPE ropes used in the floating wind turbine mooring system did not affect the power generation of the wind turbine. This study provides promising support data and observations for applying high-strength polyethylene (HMPE) ropes in mooring systems for floating wind turbines.

Immunotherapy has been recognized as an effective and important therapeutic modality for multiple types of cancer. Nevertheless, it has been increasing recognized that clinical benefits of immunotherapy are less than expected as evidenced by the fact that only a small population of cancer patients respond favorably to immunotherapy. The structurally and functionally abnormal tumor vasculature is a hallmark of most solid tumors and contributes to an immunosuppressive microenvironment, which poses a major challenge to immunotherapy. In turn, multiple immune cell subsets have profound consequences on promoting neovascularization. Vascular normalization, a promising anti-angiogenic strategy, can enhance vascular perfusion and promote the infiltration of immune effector cells into tumors via correcting aberrant tumor blood vessels, resulting in the potentiation of immunotherapy. More interestingly, immunotherapies are prone to boost the efficacy of various anti-angiogenic therapies and/or promote the morphological and functional alterations in tumor vasculature. Therefore, immune reprograming and vascular normalization appear to be reciprocally regulated. In this review, we mainly summarize how tumor vasculature propels an immunosuppressive phenotype and how innate and adaptive immune cells modulate angiogenesis during tumor progression. We further highlight recent advances of anti-angiogenic immunotherapies in preclinical and clinical settings to solidify the concept that targeting both tumor blood vessels and immune suppressive cells provides an efficacious approach for the treatment of cancer.

Abstract Background Proanthocyanidins (PAs) are important plant secondary metabolites that confer flavor, nutritional value, and resistance to pathogens. Persimmon is one of the PA richest crops. Mature fruits can be inedible because of the astringency caused by high PA levels and need to go through a de-astringency treatment before consumption. The molecular basis for PA accumulation is poorly known, particularly transcriptional regulators. We characterised three genotypes (‘Luotiantianshi’ (LT), ‘Mopanshi’ (MP), and ‘Youhou’ (YH)) with different PA accumulation patterns using an approach that combined PacBio full-length sequencing and Illumina-based RNA sequencing to build high-quality full-length transcriptomes. Additionally, we analysed transcriptome dynamics of the three genotypes (LT, MP, and YH) at four key fruit developmental stages. Results A total of 96,463 transcripts were obtained. We identified 80,075 protein-coding sequences (CDSs), 71,137 simple sequence repeats (SSRs), and 27,845 long noncoding RNAs (lncRNAs). Pearson correlation coefficient (PCC), principal component analysis (PCA), and differentially expressed transcripts (DETs) analyses indicated that the four different developmental stages within a genotype exhibited similar transcriptome activities. A total of 2,164 transcripts specific to each fruit developmental stage were detected. The transcripts specific to early stages were attributed to phenylpropanoid and flavonoid biosynthesis. Co-expression network analyses revealed MEbrown and MEblue modules were strongly associated to PA accumulation. From these two modules, 20 hub TFs are potential regulators for PA accumulation. Among them, Cluster_78388 (SBP protein), Cluster_63454 (bZIP protein), and Cluster_66595 (MYB protein) appear to involve in the PA biosynthesis in Chinese genotypes. Conclusions This is the first high-quality reference transcriptome for commercial persimmon. Our work provides insights into the molecular pathways underlying PA accumulation and enhances our global understanding of transcriptome dynamics throughout fruit development.

Designing atomically monodispersed heterogeneous catalysts with uniform active sites and high atom utilization efficiency is of fundamental and practical interest. Here, the authors report a Pt2/mpg-C3N4 catalyst showing enhanced catalytic performance toward the selective hydrogenation and epoxidation

Circulating tumor cells (CTCs) that survive in the blood are playing an important role in the metastasis process of tumor. In addition, they have become a tool for tumor diagnosis, prognosis and recurrence monitoring. CTCs can exist in the blood as individual cells or as clumps of aggregated cells. In recent years, more and more studies have shown that clustered CTCs have stronger metastasis ability compared to single CTCs. With the deepening of studies, scholars have found that cancer cells can combine not only with each other, but also with non-tumor cells present in the blood, such as neutrophils, platelets, etc. At the same time, it was confirmed that non-tumor cells bound to CTCs maintain the survival and proliferation of cancer cells through a variety of ways, thus promoting the occurrence and development of tumor. In this review, we collected information on tumorigenesis induced by CTC clusters to make a summary and a discussion about them. Although CTC clusters have recently been considered as a key role in the transition process, many characteristics of them remain to be deeply explored. A detailed understanding of their vulnerability can prospectively pave the way for new inhibitors for metastasis.

Bridging the biocatalytic repertoire and the effective environmental remediation remains a great challenge. Here, inspired by the dehalogenases, the authors designed a single atom Co catalyst on carbon doped boron nitride that exhibits high stability and selectivity in dechlorination.

Background: Radix et Rhizoma Ginseng (thereafter called ginseng) has been used as a medicinal herb for thousands of years to maintain people's physical vitality and is also a non–organ-specific cancer preventive and therapeutic traditional medicine in several epidemiologic and preclinical studies. Owing to few toxic side effects and strong enhancement on body immunity, ginseng has admirable application potential and value in cancer chemoprevention. The study aims at investigating the chemopreventive effects of ginseng on cutaneous carcinoma and the underlying mechanisms. Methods: The mouse skin cancer model was induced by 7,12-dimethylbenz[a]anthracene/12-O-tetradecanoylphorbol-13-acetate. Ultraperformance liquid chromatography/mass spectrometry was used for identifying various ginsenosides, the main active ingredients of ginseng. Comprehensive approaches (including network pharmacology, bioinformatics, and experimental verification) were used to explore the potential targets of ginseng. Results: Ginseng treatment inhibited cutaneous carcinoma in terms of initiation and promotion. The content of Rb1, Rb2, Rc, and Rd ginsenosides was the highest in both mouse blood and skin tissues. Ginseng and its active components well maintained the redox homeostasis and modulated the immune response in the model. Specifically, ginseng treatment inhibited the initiation of skin cancer by enhancing T-cell–mediated immune response through upregulating HSP27 expression and inhibited the promotion of skin cancer by maintaining cellular redox homeostasis through promoting nuclear translocation of Nrf2. Conclusion: According to the study results, ginseng can be potentially used for cutaneous carcinoma as a chemopreventive agent by enhancing cell-mediated immunity and maintaining redox homeostasis with multiple components, targets, and links.

Engineering the coordination environment of single atom catalysts offers to opportunity to optimize electrocatalytic activity. In this work, the authors prepare an unsymmetrical Cu-S1N3 single atom site on porous carbon with high performance in the oxygen reduction reaction.

The monitoring of nitric oxide is important to a number of disease states and biomedical applications. Here, the authors report on a single nickel atom catalyst based sensor for detecting nitric oxide production from cells.

Methods for carbon sequestration are warranted to tackle climate change caused by greenhouse gases released from anthropogenic activities. Seaweed is a type of marine plant that utilizes carbon dioxide for photosynthesis and has a substantial capacity to sequestrate carbon. Despite the huge potential, the long-lasting carbon sequestration (LLCS) of seaweed has never been calculated throughout its whole life cycle (nursery, temporary rearing, maturation, harvesting, and processing). In this paper, we use a life cycle assessment (LCA) approach to calculate the LLCS of seaweed, which can be understood as the difference between carbon fixation and released carbon throughout the life cycle of seaweed. Using kelp ( Laminaria japonica ) as an example of seaweed, the present study validates the procedure of calculating the LLCS of seaweed throughout its whole life cycle in Ailian Bay from nursery to processing into biochar (fertilizer) as the final product. The results showed that the carbon sequestration (full life cycle) of kelp in Ailian Bay was 97.73 g C m ^−2 year. Biomass carbon accounts for approximately 86% of the total value (982.53 g C m ^−2 year) of carbon absorption source of kelp in Ailian Bay, with the remaining 14% consisting of recalcitrant dissolved organic carbon and sedimentary carbon. Moreover, we calculated the amount of biomass carbon that was sequestrated by seaweed production in China from 2010 to 2020. Thus, the present study demonstrates that the mass production of seaweed can be utilized as an efficient method to sequestrate carbon and a feasible method for evaluating the effect of kelp farms on climate change.

While noble metal usage in catalysis is ubiquitous, the metals’ scarcity necessitates new materials designs for efficient utilization. Here, authors report a general strategy to prepare amorphous noble metal nanosheets and find the nanomaterials to act as efficient water-splitting electrocatalysts.

Single-atom catalysts attract lots of attention, but direct transformation of bulk metal oxide into single atoms remains challenging. Here the authors report a gas-transport route to transform monolithic copper (I) oxide into copper single-atoms catalyst with a high activity for oxygen reduction.

Noble metals play a momentous role in heterogeneous catalysis but still face a huge challenge in selectivity control. Herein, the authors demonstrate that isolating contiguous Pt atoms and forming Pt-Zn intermetallic nanoparticles is an effective strategy to optimize the selectivity of Pt catalysts.

The role of gut microbiota in the development of various tumors has been a rising topic of public interest, and in recent years, many studies have reported a close relationship between microbial groups and tumor development. Gut microbiota play a role in host metabolism, and the positive and negative alterations of these microbiota have an effect on tumor treatment. The microbiota directly promote, eliminate, and coordinate the efficacy of chemotherapy drugs and the toxicity of adjuvant drugs, and enhance the ability of patients to respond to tumors in adjuvant immunotherapy. In this review, we outline the significance of gut microbiota in tumor development, reveal its impacts on chemotherapy and immunotherapy, and discover various potential mechanisms whereby they influence tumor treatment. This review demonstrates the importance of intestinal microbiota-related research for clinical tumor treatment and provides additional strategy for clinical assistance in cancer treatment.

Palladium nanoparticles supported on low-melting polyester (Pd/LMPET) fabric were prepared through a microwave irradiation assisted method. In this way, in situ growth of Pd nanoparticles onto an easy to handle material was initiated and proceeded. The results of the characterization revealed that the palladium nanoparticles were well-dispersed on the surfaces of the polyester fibers. The Pd/LMPET fabrics were then employed in the Suzuki-Miyaura coupling. They exhibited excellent catalytic activity in ethanol/water under air atmosphere at 50 °C. Importantly, the Pd/LMPET fabrics could be separated from reaction mixture conveniently and they can still maintain good activity after 8 cycles without Pd leaching.

Abstract Hydrogen is the most preferred choice as an energy source to replace the nonrenewable energy resources such as fossil fuels due to its beneficial features of abundance, ecofriendly, and outstanding gravimetric energy density. Splitting water through a proton exchange membrane (PEM) electrolyzer is a well‐known method of hydrogen production. But the major impediment is the sluggish kinetics of oxygen evolution reaction (OER). Currently, scientists are struggling to build out an acid‐stable electrocatalyst for OER with low overpotential and excellent stability. In this review, the reaction mechanism and characterization parameters of OER are introduced, and then the improvement method of metal nanocatalysts (noble metal catalysts and noble metal‐free catalysts) in acidic media is discussed. Particularly, the application of single‐atom catalysts in acidic OER is summarized, which is current researching focus. At the same time, we also briefly introduced the cluster phenomenon, which is easy to occur in the preparation of single‐atom catalysts. More importantly, we summarized the in situ characterization methods such as in situ X‐ray absorption spectroscopy, in situ X‐ray photoelectron spectroscopy, and so forth, which are conducive to further understanding of OER reaction intermediates and active sites. Finally, we put forward some opinions on the development of acidic OER.

Both long-term anti-estrogen therapy and estrogen receptor-negative breast cancer contribute to drug resistance, causing poor prognosis in breast cancer patients. Breast cancer resistance protein (BCRP) plays an important role in multidrug resistance. Here, we show that cryptotanshinone (CPT), an anti-estrogen compound, inhibited the oligomer formation of BCRP on the cell membrane, thus blocking its efflux function. The inhibitory effect of CPT on BCRP was dependent on the expression level of estrogen receptor α (ERα) in ERα-positive breast cancer cells. Furthermore, ERα-negative breast cancer cells with high expression of BCRP were also sensitive to CPT because CPT was able to bind to BCRP and inhibit its oligomer formation on the cell membrane, suggesting that the high level of BCRP expression is crucial for CPT to reverse drug resistance. The combination of CPT and chemotherapeutic agents displayed enhanced anticancer effects. The results suggest that CPT is a novel BCRP inhibitor via blocking the oligomer formation of BCRP on the cell membrane. CPT is able to inhibit the activity of BCRP in an ERα-dependent and -independent manner, sensitizing breast cancer cells to chemotherapy.

New energy is the focus of attention all over the world, and research into new energy can inject new vitality into the industrial system. Hydrogen fuel cells are not only environmentally friendly, but also rich in reserves that can be used as a strategic resource for the entire country. The difficulty lies in the safe design of application equipment and the batch generation and storage of hydrogen. In addition, fuel cells have the disadvantage of a slow start-up. Based on the above problems, this paper proposes a hybrid-element method to solve the thermal-mechanical coupling model of fuel cell plate, which can effectively solve the thermal stress change, temperature field distribution and displacement change of the battery plate when working. Firstly, the hybrid-element algorithm is given for 2D plate deformation. Then, the deformation application of a 3D fuel cell plate is given. The 2D numerical results show that the hybrid finite element method (FEM) is more flexible for realizing the flexible combination of sub-mesh and finite element basis functions, and has a better mesh quality compared to the traditional constant strain triangular element (CST) adaptive FEM and quadrilateral isoparametric element (Q4) adaptive FEM. This method achieves a balance between numerical accuracy and solving efficiency for the multi-porous elastic plate. In addition, a deformation control formula is given which can display the displacement deformation and stress merge to same graph, since it is convenient to quickly compare the regions where the displacement and stress extremum appear. In short, the hybrid finite element method proposed in this paper has good mesh evaluation results, and when the number of discrete elements is equivalent, the hybrid element converges faster and the solution efficiency is higher. This paper also provides a good numerical theory and simulation reference for industrial mechanics and new energy applications.

Persimmon (Diospyros kaki Thunb.) is an important fruit crop in East Asia and has great commercial potential due to the high demand for fresh edible fruits or processed dried persimmon, as well as its being a source of raw materials for the chemical industry. Genetic engineering has shown great potential in persimmon fruit improvement and compensated for the limitations of conventional breeding. In this study, we developed an efficient transformation system and in vivo regeneration protocol by using the leaf disc culture of ‘Gongcheng Shuishi’ persimmon through the optimization of different basic media and hormone combinations. Based on the secondary induction system on 1/2DKW (DKW medium) + ZT (2.0 mg/L) + TDZ (0.5 mg/L) and MS (1/2 N) + ZT (2.0 mg/L) + IAA (0.1 mg/L), the callus induction rate and adventitious bud induction rate were 96.0% and 94.0%, respectively, and RNA interference of DkANR (ANR, anthocyanidin reductase) was achieved after transformation, thus resulting in a reduction in proanthocyanidin accumulation. The GFP (green fluorescent protein) fluorescence signal was visualized in the transgenic seedlings with GFP gene cotransformation. A total of 17.9% of the positive regenerated transgenic seedlings with empty vector were confirmed by both hyg gene and 35S promoter PCR analysis. Southern blotting assays showed that 20 positive transgenic persimmon seedlings were obtained from 135 regenerated transformants derived from DkANRi. Altogether, a reliable and highly efficient transformation system was achieved in persimmon, which may contribute to gene function identification and genetic improvement in the future.

Elastic materials include metal plates, rubber, foam, airbags and so on, which have a good buffer effect, toughness and strong recovery ability. In this paper, the deformation and thermal diffusion of 2D and 3D thin plates are studied. Two models are established for the deformation of 2D thin plates. The bending deformation equation of rectangular and circular plates is derived, and the semi-analytical solution of the deflection function w(x,y) is found through the Fourier series approximation in the polar coordinate. The consistencies of the numerical solution and the theoretical solution are verified by numerical method. Then, we find that the factors affecting the deformation are related to the Young’s modulus, load, plate length and deformation factor α of the material. In a separate temperature physics field, we establish a heat conduction model of 2D graphene film. Three numerical schemes of the transient heat conduction equation of FDM-FEM are given. In contrast, this paper uses the implicit Euler method to discrete the time term. Furthermore, we compared the difference between the adiabatic condition and the convection condition by the graphical method and the curve trend. The results show that the temperature near the adiabatic boundary is higher. Finally, we proposed a 3D dynamic thermal–mechanical coupling model (3D-DTMCM) that has been established. A laser heating monocrystalline silicon sheet with periodic motion formula is given. The temperature radiation of the laser heat source has Gaussian distribution characteristics. Our proposed model can dynamically determine Young’s modulus with a variable temperature. The numerical results show that the higher the temperature is, the higher the strain energy density of the plate is. In addition, the deformation amplitude of the plates in the coupling field is larger than that in the single mechanical field. Finally, we also discussed the stress field distribution of mixed cracks under high temperature and high load. Our research provides theoretical support for the deformation of different plates, and also reflects the value of the coupled model in practical applications.

The development of the world cannot be separated from energy: the energy crisis has become a major challenge in this era, and nuclear energy has been applied to many fields. This paper mainly studies the stress change of reaction pressure vessels (RPV). We established several different physical models to solve the same mechanical problem. Numerical methods range from 1D to 3D; the 1D model is mainly based on the mechanical equilibrium equations established by the internal pressure of RPV, the hoop stress, and the axial stress. We found that the hoop stress is twice the axial stress; this model is a rough estimate. For 2D RPV mechanical simulation, we proposed a new method, which combined the continuum damage dynamic model with the transient cross-section finite element method (CDDM-TCFEM). The advantage is that the temperature and shear strain can be linked by the damage factor effect on the elastic model and Poission ratio. The results show that with the increase of temperature (damage factor μ^,d^), the Young’s modulus decreases point by point, and the Poisson’s ratio increases with the increase of temperature (damage factor μ^,Et). The advantage of the CDDM-TCFEM is that the calculation efficiency is high. However, it is unable to obtain the overall mechanical cloud map. In order to solve this problem, we established the axisymmetric finite element model, and the results show that the stress value at both ends of RPV is significantly greater than that in the middle of the container. Meanwhile, the shape changes of 2D and 3D RPV are calculated and visualized. Finally, a 3D thermal–mechanical coupling model is established, and the cloud map of strain and displacement are also visualized. We found that the stress of the vessel wall near the nozzle decreases gradually from the inside surface to the outside, and the hoop stress is slightly larger than the axial stress. The main contribution of this paper is to establish a CDDM-TCFEM model considering the influence of temperature on elastic modulus and Poission ratio. It can dynamically describe the stress change of RPV; we have given the fitting formula of the internal temperature and pressure of RPV changing with time. We also establish a 3D coupling model and use the adaptive mesh to discretize the pipe. The numerical discrete theory of FDM-FEM is given, and the numerical results are visualized well. In addition, we have given error estimation for h-type and p-type adaptive meshes. So, our research can provide mechanical theoretical support for nuclear energy safety applications and RPV design.

Development of fuel cells and metal-air batteries is hindered by electrocatalyst performance, which can be enhanced with uniform and atomically dispersed active sites. Here the authors report an iron-based electrocatalyst for oxygen reduction in cathodes for a zinc-air battery and a hydrogen-air fuel cell.

Water splitting provides an appealing route to generating carbon-neutral fuel, however the scarcity and cost of platinum, often used as a catalyst, necessitates a search for alternatives. Here, authors show cobalt atoms in ruthenium nanosheets to afford excellent hydrogen production activities.

Background/Aims: Metastasis is the leading cause resulting in high mortality in triple negative breast cancer (TNBC) patients. Cancer cells are skilled at utilizing thioredoxin (Trx) system as an efficient antioxidant system to counteract oxidative damage, facilitating the occurrence of metastasis. Here, we identified an organosulfur compound named DATS isolated from garlic, that inhibits the expression of Trx-1 and the enzyme activity of Trx reductase in breast cancer cells. Methods: Tissue microarray of breast cancer patients and immunohistochemical method were used to analyze the role of Trx-1 in breast cancer metastasis. Spotaneous metastasis model and experimental metastasis model combined with HE staining, immunohistochemistry were used to verify in vivo anti-metastatic effect of DATS as well as its regulation on thioredoxin. Western blot, immunofluorescence, redox state assessment and detection of enzyme activity were employed to determine the effect of DATS on thioredoxin system. Trx-1 siRNA interference was used to investigate the conclusive evidence that Trx-1 was the target of DATS. Results: In agreement with reduced Trx-1 nuclear translocation from cytoplasm by DATS, the production of reduced form of Trx-1 was dramatically decreased. Furthermore, in vivo, DATS administration was observed to significantly suppress spontaneous and experimental metastasis in nude mice. Delivery of DATS also resulted in decreased expression of Trx-1 as the direct target, as well as expression of NF-κB and MMP2/9 in primary tumor and lung tissue. Notably, the effects of DATS on the expression of downstream metastasis-associated genes were mediated by Trx-1, as demonstrated by the combination use of DATS and Trx-1 siRNA. Conclusion: Collectively, this present study indicates that targeting Trx system with DATS may provide a promising strategy for treating metastasis of TNBC.

Single-site catalysts supported by ultrathin two-dimensional (2D) porous matrix are desirable for catalytic reactions, yet their synthesis remains a great challenge. Herein the authors report a cocoon silk chemistry strategy to synthesize isolated metal single-site catalysts embedded in ultrathin 2D porous N-doped carbon nanosheets.