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Fístula Biliar , Litotricia , Fístula Pancreática , Pancreatitis Aguda Necrotizante , Humanos , Litotricia/efectos adversos , Litotricia/métodos , Pancreatitis Aguda Necrotizante/etiología , Pancreatitis Aguda Necrotizante/terapia , Pancreatitis Aguda Necrotizante/complicaciones , Fístula Pancreática/etiología , Fístula Pancreática/terapia , Fístula Biliar/etiología , Fístula Biliar/terapia , Masculino , Colangiopancreatografia Retrógrada Endoscópica/efectos adversos , Colangiopancreatografia Retrógrada Endoscópica/métodos , Persona de Mediana EdadRESUMEN
The infiltration and cytotoxicity of chimeric antigen receptor (CAR)-T cells are crucial for effective elimination of solid tumors. While metallo-immunotherapy is a promising strategy that can activate the antitumor immunity, its role in promoting CAR-T cell therapy remains elusive. The first single-element nanomaterial based on chromium nanoparticles (Cr NPs) for cancer photo-metallo-immunotherapy has been reported previously. Herein, an extended study using biodegradable polydopamine as a versatile carrier for these nanoparticles, enabling synergistic CAR-T cell therapy, is reported. The results show that these nanocomposites with or without further encapsulation of the anticancer drug alpelisib can promote the CAR-T cell migration and antitumor effect. Upon irradiation with near-infrared light, they caused mild hyperthermia that can "warm" the "cold" tumor microenvironment (TME). The administration of B7-H3 CAR-T cells to NOD severe combined immunodeficiency gamma mice bearing a human hepatoma or PIK3CA-mutated breast tumor can significantly inhibit the tumor growth after the induction of tumor hyperthermia by the nanocomposites and promote the secretion of serum cytokines, including IL-2, IFN-γ, and TNF-α. The trivalent Cr3+ ions, which are the major degradation product of these nanocomposites, can increase the CXCL13 and CCL3 chemokine expressions to generate tertiary lymphoid structures (TLSs) in the tumor tissues, facilitating the CAR-T cell infiltration.
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The development of new recyclable and inexpensive electrochemically active species for water oxidation catalysis is the most crucial step for future utilization of renewables. Particularly, transition metal complexes containing internal multiple, cooperative metal centers to couple with redox catalysts in the inorganic Keggin-type polyoxometalate (POM) framework at high potential or under extreme pH conditions would be promising candidates. However, most reported Ni-containing POMs have been highly unstable towards hydrolytic decomposition, which precludes them from application as water oxidation catalysts (WOCs). Here, we have prepared new tri-Ni-containing POMs with variable oxidation states by charge tailored synthetic strategies for the first time and developed them as recyclable POMs for water oxidation catalysts. In addition, by implanting corresponding POM anions into the positively charged MIL-101(Cr) metal-organic framework (MOF), the entrapped Ni2+/Ni3+ species can show complete recyclability for water oxidation catalysis without encountering uncontrolled hydrolysis of the POM framework. As a result, a low onset potential of approximately 1.46 V vs. NHE for water oxidation with stable WOC performance is recorded. Based on this study, rational design and stabilization of other POM-electrocatalysts containing different multiple transition metal centres could be made possible.
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OBJECTIVES: Detection of early neoplastic lesions is crucial for improving the survival rates of patients with gastric cancer. Optical enhancement mode 2 is a new image-enhanced endoscopic technique that offers bright images and can improve the visibility of neoplastic lesions. This study aimed to compare the detection of neoplastic lesions with optical enhancement mode 2 and white-light imaging (WLI) in a high-risk population. METHODS: In this prospective multicenter randomized controlled trial, patients were randomly assigned to optical enhancement mode 2 or WLI groups. Detection of suspicious neoplastic lesions during the examinations was recorded, and pathological diagnoses served as the gold standard. RESULTS: A total of 1211 and 1219 individuals were included in the optical enhancement mode 2 and WLI groups, respectively. The detection rate of neoplastic lesions was significantly higher in the optical enhancement mode 2 group (5.1% vs. 1.9%; risk ratio, 2.656 [95% confidence interval, 1.630-4.330]; p < 0.001). The detection rate of neoplastic lesions with an atrophic gastritis background was significantly higher in the optical enhancement mode 2 group (8.6% vs. 2.6%, p < 0.001). The optical enhancement mode 2 group also had a higher detection rate among endoscopists with different experiences. CONCLUSIONS: Optical enhancement mode 2 was more effective than WLI for detecting neoplastic lesions in the stomach, and can serve as a new method for screening early gastric cancer in clinical practice. CLINICAL REGISTRY: United States National Library of Medicine (https://www. CLINICALTRIALS: gov), ID: NCT040720521.
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Detección Precoz del Cáncer , Gastroscopía , Aumento de la Imagen , Neoplasias Gástricas , Humanos , Neoplasias Gástricas/diagnóstico por imagen , Neoplasias Gástricas/patología , Neoplasias Gástricas/diagnóstico , Masculino , Femenino , Persona de Mediana Edad , Estudios Prospectivos , Gastroscopía/métodos , Detección Precoz del Cáncer/métodos , Anciano , Aumento de la Imagen/métodos , Gastritis Atrófica/diagnóstico , Gastritis Atrófica/patología , Gastritis Atrófica/diagnóstico por imagen , AdultoRESUMEN
Xylene exposure is known to induce toxicity in hematopoietic stem and progenitor cells (HSPCs), leading to bone marrow suppression and potential leukemogenesis. However, research on the gene expression profiles associated with xylene-induced toxicity in HSPCs, and effective therapeutic interventions, remains scarce. In our study, we employed single-cell RNA sequencing to capture the transcriptomic shifts within bone marrow HSPCs both prior to and following treatment with coniferyl ferulate (CF) in a mouse model of xylene-induced hematotoxicity. Subsequently, we pinpointed CF as a targeted agent using SPR-LC/MS analysis. This enabled us to confirm the link between the gene Mgst2 and specific cellular subtypes. Our data revealed that CF significantly countered the reduction of both monocyte and neutrophil progenitor cells, which are commonly affected by xylene toxicity. Through targeted analysis, we identified Mgst2 as a direct molecular target of CF. Notably, Mgst2 is preferentially expressed in neutrophil progenitor cells and is implicated in mitochondrial metabolic processes. By selectively inhibiting Mgst2 in bone marrow, we observed amelioration of xylene-induced hematotoxic effects. In summary, our findings suggest that coniferyl ferulate can mitigate the detrimental impact of xylene on hematopoietic stem and progenitor cells by targeting Mgst2, particularly within subpopulations of neutrophil progenitors. This discovery not only advances our comprehension of the cellular response of HSPCs to xenobiotic stressors like xylene but also identifies CF and Mgst2 as potential therapeutic targets for alleviating xylene-induced hematotoxicity.
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The electrochemical CO2 reduction reaction (CO2RR) triggered by renewable electricity provides a promising route to produce chemical feedstocks and fuels with low-carbon footprints. The intrinsic challenge for the current CO2RR electrolyzer is the carbonate issue arising from the reaction between hydroxide and CO2. Acid CO2RR electrolyzers, in principle, can effectively solve the carbonate formation, but it remains inevitable practically. In this work, we thoroughly investigated the electrode processes of the CO2RR on the benchmark Ag catalyst in mild acid. The root of the carbonate issue arises from the imbalanced supply-consumption rate of protons-the electron transfer vs. mass transport. Regulating the hydrodynamics substantially reduces the proton diffusion length by 80%, increasing the single-pass carbon utilization efficiency of CO2-to-CO to 44% at -100 mA cm-2. The fundamental difference between mass transport and electron transfer on the spatial and temporal scale still leads to unavoidable carbonate formation. Future work to design intrinsically active catalysts in strong acid or metal-cation-free media is critical to solving the carbonate issue.
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Designing high-performance thermal catalysts with stable catalytic sites is an important challenge. Conventional wisdom holds that strong metal-support interactions can benefit the catalyst performance, but there is a knowledge gap in generalizing this effect across different metals. Here, we have successfully developed a generalizable strong metal-support interaction strategy guided by Tammann temperatures of materials, enabling functional oxide encapsulation of transition metal nanocatalysts. As an illustrative example, Co@BaAl2O4 core@shell is synthesized and tracked in real-time through in-situ microscopy and spectroscopy, revealing an unconventional strong metal-support interaction encapsulation mechanism. Notably, Co@BaAl2O4 exhibits exceptional activity relative to previously reported core@shell catalysts, displaying excellent long-term stability during high-temperature chemical reactions and overcoming the durability and reusability limitations of conventional supported catalysts. This pioneering design and widely applicable approach has been validated to guide the encapsulation of various transition metal nanoparticles for environmental tolerance functionalities, offering great potential to advance energy, catalysis, and environmental fields.
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Electrocatalysis has become increasingly attractive in aiding transformation to green chemical industries. Proper evaluation and in-depth understanding of electrocatalysts are critical to designing high-performance electrocatalysis systems. Tafel analysis is thus of great importance as it allows reliable performance comparison among different reports and provides insight into the reaction mechanism. This Tutorial discusses the Tafel analysis from experimental and theoretical perspectives. The principle of the Tafel analysis is revisited, and the procedure of mechanism investigation based on the Tafel analysis is included.
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In this study, a steady-state model is developed by combining mechanical, Navier-Stokes, Maxwell-Stefan, and Butler-Volmer equations. This model is then used to investigate the influences of diffusion layer thickness deformation under a specific assembly force on the porosity distribution as an indicator of fuel cell performance. The HT-PEM (high temperature proton exchange membrane) fuel cell model is built using COMSOL Multiphysics software, simulating the changes in diffusion layer porosity under different thicknesses of the diffusion layer, thus analyzing the trends in variation of water and oxygen concentration in the cathode diffusion layer. The battery has different current densities at different operating potentials. The influence of the working potential on the mass transfer concentration and the variation in the mass transfer concentration of the diffusion layer under the different areas of flow channel and flow ridge is discussed. The simulation results have a certain reference value for the optimization of mass transfer in a diffusion layer. The results reveal the combined effect of the assembly force and flow field, which makes the porosity distribution uneven and results in remarkable lateral current in the gas diffusion layer (GDL). The thicker the diffusion layer, the less oxygen consumed, and a large amount of oxygen is retained in the gaseous diffusion layer. It can be concluded that thicker diffusion layer is conducive to more uniform mass transfer and diffusion. These results can potentially be used to promote the performance and application of HT-PEMFC.
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The establishment of active sites as the frustrated Lewis pair (FLP) has recently attracted much attention ranging from homogeneous to heterogeneous systems in the field of catalysis. Their unquenched reactivity of Lewis acid and base pairs in close proximity that are unable to form stable adducts has been shown to activate small molecules such as dihydrogen heterolytically. Herein, we show that grafted Ru metal-organic framework-based catalysts prepared via N-containing linkers are rather catalytically inactive for H2 activation despite the application of elevated temperatures. However, upon light illumination, charge polarization of the anchored Ru bipyridine complex can form a transient Lewis acid-base pair, Ru+-N- via metal-to-ligand charge transfer, as confirmed by time-dependent density functional theory (TDDFT) calculations to carry out effective H2-D2 exchange. FTIR and 2-D NMR endorse the formation of such reactive intermediate(s) upon light irradiation.
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Background: Centromere protein I (CENPI) has been shown to affect the tumorigenesis of breast and colorectal cancers. However, its biological role and prognostic value in other kinds of cancer, especially adrenocortical carcinoma (ACC), remained to be further investigated. Methods: Various bioinformatics tools were adopted for exploring the significance of differential expression of CENPI in several malignant tumors from databases such as Depmap portal, GTEx, and TCGA. ACC was selected for further analyzed, and information such as clinicopathological features, the prognostic outcome of diverse subgroups, differentially expressed genes (DEGs), co-expression genes, as well as levels of tumor-infiltrating immune cells (TIIC), was extracted from multiple databases. To verify the possibility of CENPI as a therapeutic target in ACC, drug sensitivity assay and si-RNA mediate knockdown of CENPI were carried out. Results: The pan-cancer analyses showed that the CENPI mRNA expression levels differed significantly among most cancer types. Additionally, a high precision in cancer prediction and close relation with cancer survival indicated that CENPI could be a potential candidate biomarker to diagnose and predict cancer prognosis. In ACC, CENPI was closely related to multiple clinical characteristics, such as pathological stage and primary therapy outcome. High CENPI levels predicted poor overall survival (OS), progression-free interval (PFI), and disease-specific survival (DSS) of ACC patients, particularly for different clinical subgroups. Moreover, the expression of CENPI showed positive relationship to Th2 cells but negatively related to most of the TIICs. Furthermore, drug sensitivity assay showed that vorinostat inhibit CENPI expression and ACC cell growth. Additionally, si-RNA mediated knockdown of CENPI inhibited ACC cell growth and invasion and showed synergistic anti-proliferation effect with AURKB inhibitor barasertib. Conclusion: Pan-cancer analysis demonstrated that CENPI is a potential diagnostic and prognostic biomarker in various cancers as well as an anti-ACC therapeutic target.
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In recent years, . the rapid development of the Yangtze River Delta in China has led to increasingly serious regional eco-environmental problems. Therefore, it is of great significance for the construction of ecological civilization to study the ecosystem health in the Yangtze River Delta. In this paper, the assessment framework of "Vigor-Organization-Resilience" was used to assess the ecosystem health index (EHI) of the Yangtze River Delta from 2000 to 2020, and then the spatial autocorrelation method was used to analyze the agglomeration of EHI in 314 counties in this region. Finally, the eXtreme Gradient Boosting (XGBoost) model and the SHapley Additive exPlanation (SHAP) model were combined to explore the synergistic impact of EHI driving factors. The results show that (1) from 2000 to 2020, the EHI in the Yangtze River Delta is at the level of ordinary health, and gradually decreased; (2) the EHI has significant spatial positive correlation and aggregation; (3) the driving factors in descending order of importance are urbanization level (UL), precipitation (PRE), PM2.5 (PM), normalized difference vegetation index (NDVI), and temperature (TEMP); and (4) the relationship between UL and EHI is logarithmic; PRE and EHI are quartic polynomial; PM, NDVI, TEMP, and EHI are quadratic polynomial. The results of this paper are of great significance to the management and restoration of the ecosystem in this region.
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Ecosistema , Ríos , Urbanización , Temperatura , China , CiudadesRESUMEN
Catalytic NH3 synthesis and decomposition offer a new promising way to store and transport renewable energy in the form of NH3 from remote or offshore sites to industrial plants. To use NH3 as a hydrogen carrier, it is important to understand the catalytic functionality of NH3 decomposition reactions at an atomic level. Here, we report for the first time that Ru species confined in a 13X zeolite cavity display the highest specific catalytic activity of over 4000 h-1 for the NH3 decomposition with a lower activation barrier, compared to most reported catalytic materials in the literature. Mechanistic and modeling studies clearly indicate that the N-H bond of NH3 is ruptured heterolytically by the frustrated Lewis pair of Ruδ+-Oδ- in the zeolite identified by synchrotron X-rays and neutron powder diffraction with Rietveld refinement as well as other characterization techniques including solid-state nuclear magnetic resonance spectroscopy, in situ diffuse reflectance infrared transform spectroscopy, and temperature-programmed analysis. This contrasts with the homolytic cleavage of N-H displayed by metal nanoparticles. Our work reveals the unprecedented unique behavior of cooperative frustrated Lewis pairs created by the metal species on the internal zeolite surface, resulting in a dynamic hydrogen shuttling from NH3 to regenerate framework Brønsted acid sites that eventually are converted to molecular hydrogen.
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At present, the remote sensing (RS) thermal infrared (TIR) images that are commonly used to obtain land surface temperature (LST) are contaminated by clouds and thus cannot obtain spatiotemporal integrity of LST. To solve this problem, this study combined a physical model with strong interpretability with a data-driven model with high data adaptability. First, the physical model (Weather Research and Forecast (WRF) model) was used to generate LST source data. Then, combined with multisource RS data, a data-driven method (random forest (RF)) was used to improve the accuracy of the LST, and a model framework for a data-driven auxiliary physical model was formed. Finally, all-weather MODIS-like data with a spatial resolution of 1 km were generated. Beijing, China, was used as the study area. The results showed that in cases of more clouds and fewer clouds, the reconstructed all-weather LST had a high spatial continuity and could restore the spatial distribution details of the LST well. The mean absolute error (MAE), root mean square error (RMSE), and correlation coefficient (ρ) in the case of more (fewer) clouds were ranked as follows: MAE < 1 K (< 2 K), RMSE < 2 K (< 2 K), and ρ > 0.9. The errors obeyed an approximately normal distribution. The total MAE, RMSE, and ρ were 0.80 K, 1.09 K, and 0.94 K, respectively. Generally, the LST reconstructed in this paper had a high accuracy, and the model could provide all-weather MODIS-like LST to compensate for the disadvantages of satellite TIR images (i.e., contamination by clouds and inability to obtain complete LST values).
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Monitoreo del Ambiente , Modelos Teóricos , Temperatura , Monitoreo del Ambiente/métodos , Beijing , ChinaRESUMEN
Self-cleaning, antimicrobial ultrafiltration membranes are urgently needed to alleviate the low flux problems caused by membrane fouling in water treatment processes. In this study, in situ generated nano-TiO2 MXene lamellar materials were synthesized and then 2D membranes were fabricated using vacuum filtration. The presence of nano TiO2 particles as an interlayer support layer widened the interlayer channels, and also improved the membrane permeability. The TiO2/MXene composite on the surface also showed an excellent photocatalytic property, resulting in enhanced self-cleaning properties and improved long-term membrane operational stability. The best overall performance of the TiO2/MXene membrane at 0.24 mg cm-2 loading was optimal, with 87.9% retention and 211.5 L m-2 h-1 bar-1 flux at a filtration of 1.0 g L-1 bovine serum albumin solution. Noticeably, the TiO2/MXene membranes showed a very high flux recovery under UV irradiation with a flux recovery ratio (FRR) of 80% as compared to the non-photocatalytic MXene membranes. Moreover, the TiO2/MXene membranes demonstrated over 95% resistance against E. coli. And the XDLVO theory also showed that the loading of TiO2/MXene slowed down the fouling of the membrane surface by protein-based contaminants.
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The viability of using ammonia as a hydrogen storage vector is contingent on the development of catalytic systems active for ammonia decomposition at low temperatures. Zeolite-supported metal catalysts, unlike systems based on supports like MgO or carbon nanotubes (CNTs), are crystalline and lend themselves to analytic techniques like synchrotron X-ray powder diffraction (SXRD) and Rietveld refinement, allowing precise characterisation of catalytic active sites, and therefore mechanistic elucidation. This study focuses on characterising and optimising novel zeolite-supported Ru catalysts for ammonia decomposition, with a focus on the effects of N-substitution on catalyst structure and activity. Characterisation focuses on an unsubstituted and N-substituted Ru-zeolite Y pair with NMR, FTIR, TEM, XRD, XAS, ICP, and BET, demonstrating the successful incorporation of N into the zeolite framework and an enhancement in metal dispersion upon N-substitution. A series of 18 monometallic and bimetallic catalysts is then synthesised on X and USY supports and screened for catalytic activity. Ru is identified as the most active metal for ammonia decomposition. Observed trends suggest catalyst dispersion can be increased with substantially lower metal loadings, and in particular via the formation of stably anchored oligonuclear metal clusters within the zeolite framework, as opposed to much larger nanoparticles (NPs) on its exterior, following N-substitution of the framework. DFT modelling proposes a prismatic Ru6N6 cluster fitted to XAS data. High-activity catalyst Ru-ß (N) 2.4% demonstrates comparable or better ammonia conversion by Ru wt% than recently reported catalysts in the literature at 450 °C and 30 000 WHSV.
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Highly uniformly dense garnet type solid-state electrolyte plays a significant role in determining the performance of solid-state lithium batteries. Herein, a rational powder-covering sintering strategy is proposed and demonstrated, in which narrow-particle-size-distribution fine powder and uniform sintering temperature distribution are considered as very significant factors. It is suggested that powder materials with wider particle size distribution dramatically decrease the densified level of electrolytes. Slow temperature elevating rate and the overhead structure of bearing table are found to be beneficial to uniform densification. Moreover, the uniform densification process of sintering solid-state electrolyte is studied both microscopically and macroscopically, which can be divided into three phases according to the grain growing evolution and linear shrinkage patterns. The ionic conductivity of the as-prepared Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) garnet electrolyte is determined to be 0.73 mS cm-1 at 303 K with an activation energy of 0.37 eV. The Li/LLZTO/Li symmetric cell exhibits a small interfacial impedance of 8.49 Ω cm2 and a high apparent critical current density of 2.15 mA cm-2 and also can be cycled for 1000 h continuously without short-circuit. Such results indicate the good feasibility of as-proposed sintering strategy to prepare uniformly dense garnet type solid-state electrolytes for solid-state lithium batteries.
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Laminar membranes comprising graphene oxide (GO) and metal-organic framework (MOF) nanosheets benefit from the regular in-plane pores of MOF nanosheets and thus can support rapid water transport. However, the restacking and agglomeration of MOF nanosheets during typical vacuum filtration disturb the stacking of GO sheets, thus deteriorating the membrane selectivity. Therefore, to fabricate highly permeable MOF nanosheets/reduced GO (rGO) membranes, a two-step method is applied. First, using a facile solvothermal method, ZnO nanoparticles are introduced into the rGO laminate to stabilize and enlarge the interlayer spacing. Subsequently, the ZnO/rGO membrane is immersed in a solution of tetrakis(4-carboxyphenyl)porphyrin (H2 TCPP) to realize in situ transformation of ZnO into Zn-TCPP in the confined interlayer space of rGO. By optimizing the transformation time and mass loading of ZnO, the obtained Zn-TCPP/rGO laminar membrane exhibits preferential orientation of Zn-TCPP, which reduces the pathway tortuosity for small molecules. As a result, the composite membrane achieves a high water permeance of 19.0 L m-2 h-1 bar-1 and high anionic dye rejection (>99% for methyl blue).
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Since multiple myeloma (MM) remains a cureless malignancy of plasma cells to date, it becomes imperative to develop novel drugs and therapeutic targets for MM. We screened a small molecule library comprising 3633 natural product drugs, which demonstrated that Nitidine Chloride (NC), an extract from traditional Chinese medicine Zanthoxylum nitidum. We used Surface Plasmon Resonance-High Performance Liquid Chromatography-Protein Mass Spectrometry (SPR-HPLC-MS), Cellular Thermal Shift Assay (CETSA), molecular docking, and SPR assay to identify the potential targets of NC, in which ABCB6 was the unique target of NC. The effects of ABCB6 on cellular proliferation and drug resistance were determined by CCK8, western blot, flow cytometry, site-mutation cells, transmission electron microscopy, immunohistochemistry staining and xenograft model in vitro and in vivo. NC induced MM cell death by promoting ferroptosis. ABCB6 is the direct target of NC. ABCB6 expression was increased in MM samples compared to normal controls, which was significantly associated with MM relapse and poor outcomes. VGSK was the inferred binding epitope of NC on the ABCB6 protein. In the ABCB6-mutated MM cells, NC did not display cancer resistance, implying the vital role of ABCB6 in NC's bioactivity. Moreover, the silencing of ABCB6 significantly inhibited MM cell growth. Mechanistically, the direct binding of NC to ABCB6 suppressed PI3K/AKT signaling pathway to promote ferroptosis. In conclusion, ABCB6 can be a potential therapeutic target and prognostic biomarker in MM, while NC can be considered a novel drug for MM treatment.