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1.
Hepatol Int ; 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38622445

RESUMO

BACKGROUND: To investigate whether protein induced by vitamin K antagonist-II (PIVKA-II) combined with alpha-fetoprotein (AFP) can improve the diagnostic and differential diagnostic accuracy of childhood hepatic tumors. METHODS: A multi-center prospective observational study was performed at nine regional institutions around China. Children with hepatic mass (Group T) were divided into hepatoblastoma group (Group THB) and hemangioendothelioma group (Group THE), children with extrahepatic abdominal mass (Group C). Peripheral blood was collected from each patient prior to surgery or chemotherapy. The area under the curve (AUROC) was used to evaluate the diagnostic efficiency of PIVKA-II and the combined tumor markers with AFP. RESULTS: The mean levels of PIVKA-II and AFP were both significantly higher in Group T than Group C (p = 0.001, p < 0.001), in Group THB than Group THE (p = 0.018, p = 0.013) and in advanced HB than non-advanced HB (p = 0.001, p = 0.021). For the diagnosis of childhood hepatic tumors, AUROC of PIVKA-II (cut-off value 32.6 mAU/mL) and AFP (cut-off value 120 ng/mL) was 0.867 and 0.857. The differential diagnostic value of PIVKA-II and AFP in hepatoblastoma from hemangioendothelioma was further assessed, AUROC of PIVKA-II (cut-off value 47.1mAU/mL) and AFP (cut-off value 560 ng/mL) was 0.876 and 0.743. The combined markers showed higher AUROC (0.891, 0.895 respectively) than PIVKA-II or AFP alone. CONCLUSIONS: The serum level of PIVKA-II was significantly higher in children with hepatic tumors, especially those with malignant tumors. The combination of PIVKA-II with AFP further increased the diagnostic performance. TRIAL REGISTRATION: Clinical Trials, NCT03645655. Registered 20 August 2018, https://www. CLINICALTRIALS: gov/ct2/show/NCT03645655 .

2.
Water Sci Technol ; 89(7): 1757-1770, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38619901

RESUMO

The water reuse facilities of industrial parks face the challenge of managing a growing variety of wastewater sources as their inlet water. Typically, this clustering outcome is designed by engineers with extensive expertise. This paper presents an innovative application of unsupervised learning methods to classify inlet water in Chinese water reuse stations, aiming to reduce reliance on engineer experience. The concept of 'water quality distance' was incorporated into three unsupervised learning clustering algorithms (K-means, DBSCAN, and AGNES), which were validated through six case studies. Of the six cases, three were employed to illustrate the feasibility of the unsupervised learning clustering algorithm. The results indicated that the clustering algorithm exhibited greater stability and excellence compared to both artificial clustering and ChatGPT-based clustering. The remaining three cases were utilized to showcase the reliability of the three clustering algorithms. The findings revealed that the AGNES algorithm demonstrated superior potential application ability. The average purity in six cases of K-means, DBSCAN, and AGNES were 0.947, 0.852, and 0.955, respectively.


Assuntos
Baías , Aprendizado de Máquina não Supervisionado , Reprodutibilidade dos Testes , Algoritmos , Análise por Conglomerados
3.
Artigo em Inglês | MEDLINE | ID: mdl-38619948

RESUMO

Table tennis is a sport that demands high levels of technical proficiency and body coordination from players. Biomechanical fingerprints can provide valuable insights into players' habitual movement patterns and characteristics, allowing them to identify and improve technical weaknesses. Despite the potential, few studies have developed effective methods for generating such fingerprints. To address this gap, we propose TacPrint, a framework for generating a biomechanical fingerprint for each player. TacPrint leverages machine learning techniques to extract comprehensive features from biomechanics data collected by inertial measurement units (IMU) and employs the attention mechanism to enhance model interpretability. After generating fingerprints, TacPrint provides a visualization system to facilitate the exploration and investigation of these fingerprints. In order to validate the effectiveness of the framework, we designed an experiment to evaluate the model's performance and conducted a case study with the system. The results of our experiment demonstrated the high accuracy and effectiveness of the model. Additionally, we discussed the potential of TacPrint to be extended to other sports.

4.
Eur J Immunol ; : e2250133, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38571392

RESUMO

Live-attenuated yellow fever vaccine (YF17D) was developed in the 1930s as the first ever empirically derived human vaccine. Ninety years later, it is still a benchmark for vaccines made today. YF17D triggers a particularly broad and polyfunctional response engaging multiple arms of innate, humoral and cellular immunity. This unique immunogenicity translates into an extraordinary vaccine efficacy and outstanding longevity of protection, possibly by single-dose immunization. More recently, progress in molecular virology and synthetic biology allowed engineering of YF17D as a powerful vector and promising platform for the development of novel recombinant live vaccines, including two licensed vaccines against Japanese encephalitis and dengue, even in paediatric use. Likewise, numerous chimeric and transgenic preclinical candidates have been described. These include prophylactic vaccines against emerging viral infections (e.g. Lassa, Zika and SARS-CoV-2) and parasitic diseases (e.g. malaria), as well as therapeutic applications targeting persistent infections (e.g. HIV and chronic hepatitis), and cancer. Efforts to overcome historical safety concerns and manufacturing challenges are ongoing and pave the way for wider use of YF17D-based vaccines. In this review, we summarize recent insights regarding YF17D as vaccine platform, and how YF17D-based vaccines may complement as well as differentiate from other emerging modalities in response to unmet medical needs and for pandemic preparedness.

5.
Artigo em Inglês | MEDLINE | ID: mdl-38603541

RESUMO

The urgent need for CO2 capture and hydrogen energy has attracted great attention owing to greenhouse gas emissions and global warming problems. Efficient CO2 capture and H2 purification with membrane technology will reduce greenhouse gas emissions and help reach a carbon-neutral society. Here, 4-sulfocalix[4]arene (SC), which has an intrinsic cavity, was embedded into the Matrimid membrane as a molecular gatekeeper for CO2 capture and H2 purification. The interactions between SC and the Matrimid polymer chains immobilize SC molecules into the interchain gaps of the Matrimid membrane, and the strong hydrogen and ionic bondings were able to form homogeneous mixed-matrix membranes. The incorporation of the SC molecular gatekeeper with exceptional molecular-sieving properties improved the gas separation performance of the mixed-matrix membranes. Compared with that of the Matrimid membrane, the CO2 permeability of the Matrimid-SC-3% membrane increased from 16.75 to 119.78 Barrer, the CO2/N2 selectivity increased from 29.39 to 106.95, and the CO2/CH4 selectivity increased from 29.91 to 140.92. Furthermore, when the permeability of H2 was increased to 172.20 Barrer, the H2/N2 and H2/CH4 selectivities reached approximately 153.75 and 202.59, respectively, which are far superior to those of most existing Matrimid-based materials. The mixed-matrix membranes also exhibited excellent long-term operation stability, with separation performance for several important gas pairs still overtaking the Robeson upper limit after aging for 400 days.

6.
Int J Biol Macromol ; : 131435, 2024 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-38593900

RESUMO

This study represents the inaugural investigation into the effect of cold plasma (CP) pretreatment combined with sodium periodate on the preparation of dialdehyde starch (DAS) from native maize starch and its consequent effects on the properties of DAS. The findings indicate that the maize starch underwent etching by the plasma, leading to an increase in the particle size of the starch, which in turn weakened the rigid structure of the starch and reduced its crystallinity. Concurrently, the plasma treatment induced cleavage of the starch molecular chain, resulting in a decrease in the viscosity of the starch and an enhancement of its fluidity. These alterations facilitated an increased contact area between the starch and the oxidising agent sodium periodate, thereby augmenting the efficiency of the DAS preparation reaction. Consequently, the aldehyde group content was elevated by 9.98 % compared to the conventional DAS preparation methodology. Therefore, CP could be an efficient and environmentally friendly non-thermal processing method to assist starch oxidation for DAS preparation and property enhancement.

7.
Ying Yong Sheng Tai Xue Bao ; 35(3): 817-826, 2024 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-38646770

RESUMO

To explore the causes of red tides in Qinhuangdao coastal water, we conducted surveys on both water quality and red tides during April to September of 2022 and analyzed the relationships between main environmental factors and red tide organisms through the factor analysis and canonical correspondence analysis. The results showed that there were eight red tides along the coast of Qinhuangdao in 2022, with a cumulative blooming area of 716.1 km2. The red tides could be divided into three kinds based on the major blooming organisms and occurrence time, Noctiluca scintillans bloom, diatom-euglena (Skeletonema costatum, Eutreptiella gymnastica, Pseudo-nitzschia spp.) bloom, and dinoflagellate (Scrippsiella trochoidea and Ceratium furca) bloom. Seasonal factor played roles mainly during July to September, while inorganic nutrients including nitrogen and phosphorus influenced the blooms mainly in April and July. The canonical correspondence analysis suggested that N. scintillans preferred low temperature, and often bloomed with high concentrations of ammonium nitrogen and dissolved inorganic phosphorus. S. costatum, E. gymnastica, and Pseudo-nitzschia spp. could tolerate broad ranges of various environmental factors, but favored high temperature and nitrogen-rich seawater. C. furca and S. trochoidea had higher survival rate and competitiveness in phosphate-poor waters. Combined the results from both analyses, we concluded that the causes for the three kinds of red tide processes in Qinhuangdao coastal areas in 2022 were different. Adequate diet algae and appropriate water temperature were important factors triggering and maintaining the N. scintillans bloom. Suitable temperature, salinity and eutrophication were the main reasons for the diatom-euglena bloom. The abundant nutrients and seawater disturbance promoted the germination of S. trochoidea cysts, while phosphorus limitation caused the blooming organism switched to C. furca and maintained the bloom hereafter.

8.
Artigo em Inglês | MEDLINE | ID: mdl-38584217

RESUMO

PURPOSE: To establish two nomograms to quantify the risk of lung metastasis (LM) in laryngeal carcinoma (LC) and predict the overall survival of LC patients with LM. METHODS: Totally 9515 LC patients diagnosed histologically from 2000 to 2019 were collected from the Surveillance, Epidemiology, and End Results database. The independent diagnostic factors for LM in LC patients and prognostic factors for LC patients with LM were identified by logistic and Cox regression analysis, respectively. Nomograms were established based on regression coefficients and evaluated by receiver operating characteristic curve, calibration curves, and decision curve analysis. RESULTS: Patients with supraglottis, higher pathological grade, higher N stage, and distant metastasis (bone, brain, or liver) were more likely to have LM (P < 0.05). Chemotherapy, surgery and radiotherapy were independent factors of the overall survival of LC patients with LM (P < 0.05). The area under curve of diagnostic nomogram were 0.834 and 0.816 in the training and validation cohort respectively. For the prognostic nomogram, the area under curves of 1-, 2-, and 3-years were 0.735, 0.734, and 0.709 in the training cohort and 0.705, 0.803, and 0.809 in the validation cohort. The calibration curves and decision curve analysis indicated good performance of the nomograms. CONCLUSION: Distant metastasis (bone, brain, or liver) and N stage should be considered for prediction of LM in LC patients. Chemotherapy is the most significant influencing prognostic factor improving the survival of LC patients with LM. Two nomograms may benefit for providing better precautionary measures and treatment decision.

9.
Nat Commun ; 15(1): 2985, 2024 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-38582761

RESUMO

Carbon nanomaterials are expected to be bright and efficient emitters, but structural disorder, intermolecular interactions and the intrinsic presence of dark states suppress their photoluminescence. Here, we study synthetically-made graphene nanoribbons with atomically precise edges and which are designed to suppress intermolecular interactions to demonstrate strong photoluminescence in both solutions and thin films. The resulting high spectral resolution reveals strong vibron-electron coupling from the radial-breathing-like mode of the ribbons. In addition, their cove-edge structure produces inter-valley mixing, which brightens conventionally-dark states to generate hitherto-unrecognised twilight states as predicted by theory. The coupling of these states to the nanoribbon phonon modes affects absorption and emission differently, suggesting a complex interaction with both Herzberg-Teller and Franck- Condon coupling present. Detailed understanding of the fundamental electronic processes governing the optical response will help the tailored chemical design of nanocarbon optical devices, via gap tuning and side-chain functionalisation.

10.
BMC Microbiol ; 24(1): 90, 2024 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-38493114

RESUMO

BACKGROUND: To investigate the differences in bacterial and fungal community structure and diversity in conjunctival tissue of healthy and diabetic mice. METHODS: RNA-seq assays and high-throughput sequencing of bacterial 16 S rDNA and fungal internal transcribed spacer (ITS) gene sequences were used to identify differentially expressed host genes and fungal composition profiles in conjunctival tissues of diabetic BKS-db/db mice and BKS (control) mice. Functional enrichment analysis of differentially expressed genes and the correlation between the relative abundance of bacterial and fungal taxa in the intestinal mucosa were also performed. RESULTS: Totally, 449 differential up-regulated genes and 1,006 down-regulated genes were identified in the conjunctival tissues of diabetic mice. The differentially expressed genes were mainly enriched in metabolism-related functions and pathways. A decrease in conjunctival bacterial species diversity and abundance in diabetic mice compared to control mice. In contrast, fungal species richness and diversity were not affected by diabetes. The microbial colonies were mainly associated with cellular process pathways regulating carbohydrate and lipid metabolism, as well as cell growth and death. Additionally, some interactions between bacteria and fungi at different taxonomic levels were also observed. CONCLUSION: The present study revealed significant differences in the abundance and composition of bacterial and fungal communities in the conjunctival tissue of diabetic mice compared to control mice. The study also highlighted interactions between bacteria and fungi at different taxonomic levels. These findings may have implications for the diagnosis and treatment of diabetes.


Assuntos
Diabetes Mellitus Experimental , Diabetes Mellitus Tipo 2 , Microbiota , Animais , Camundongos , Fungos/genética , Bactérias/genética , Sequenciamento de Nucleotídeos em Larga Escala
11.
Se Pu ; 42(3): 264-274, 2024 Mar 08.
Artigo em Chinês | MEDLINE | ID: mdl-38503703

RESUMO

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 µm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 µg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 µg/L and 0.03-0.42 µg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 µg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.


Assuntos
Estruturas Metalorgânicas , Fenóis , Ácidos Ftálicos , Espectrometria de Massas em Tandem , Água , Cromatografia Líquida de Alta Pressão , Porosidade , Cromatografia Líquida , Esqueleto , Metais , Extração em Fase Sólida
12.
Food Chem ; 448: 139078, 2024 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-38527403

RESUMO

A fluorescent sensor array (FSA) combined with deep learning (DL) techniques was developed for meat freshness real-time monitoring from development to deployment. The array was made up of copper metal nanoclusters (CuNCs) and fluorescent dyes, having a good ability in the quantitative and qualitative detection of ammonia, dimethylamine, and trimethylamine gases with a low limit of detection (as low as 131.56 ppb) in range of 5 âˆ¼ 1000 ppm and visually monitoring the freshness of various meats stored at 4 °C. Moreover, SqueezeNet was applied to automatically identify the fresh level of meat based on FSA images with high accuracy (98.17 %) and further deployed in various production environments such as personal computers, mobile devices, and websites by using open neural network exchange (ONNX) technique. The entire meat freshness recognition process only takes 5 âˆ¼ 7 s. Furthermore, gradient-weighted class activation mapping (Grad-CAM) and uniform manifold approximation and projection (UMAP) explanatory algorithms were used to improve the interpretability and transparency of SqueezeNet. Thus, this study shows a new idea for FSA assisted with DL in meat freshness intelligent monitoring from development to deployment.

14.
Clin Neuroradiol ; 2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38451269

RESUMO

OBJECTIVE: To investigate the safety and efficacy of LVIS Jr stent-assisted coiling (SAC) of intracranial aneurysms (IAs) in small-diameter parent arteries and determine the factors influencing incomplete aneurysm occlusion. MATERIAL AND METHODS: Clinical and imaging data of 130 patients with IAs in small-diameter parent arteries that were treated with LVIS Jr SAC were retrospectively analyzed. Stent apposition was evaluated by high-resolution flat detector CT, and aneurysm embolization density was evaluated using 2D-DSA. Perioperative complications were recorded. Multivariate logistic regression analyses were performed to determine possible factors for incomplete aneurysm occlusion. RESULTS: In this study, 130 patients (60 and 70 patients with ruptured and unruptured aneurysms, respectively) were successfully treated with LVIS Jr SAC. Immediate digital subtraction angiography (DSA) showed that the aneurysm occlusion was Raymond-Roy class I, II, IIIa, and IIIb in 93 (71.5%), 24 (18.5%), 8 (6.2%), and 5 (3.8%) cases, respectively. There were three cases of acute in-stent thrombosis and two cases of severe vasospasm observed during the perioperative period. The 6­month follow-up angiograms indicated that complete aneurysm occlusion in 122 patients was 79.5% (97/122). Multivariate logistic regression analyses showed that an aneurysm size > 10.0 mm, parent artery mean diameter < 2.0 mm, and incomplete stent apposition at the aneurysm neck were possible risk factors for incomplete aneurysm occlusion. CONCLUSION: The LVIS Jr SAC is effective for managing IAs in small-diameter parent arteries. An aneurysm size > 10.0 mm, parent artery mean diameter < 2.0 mm, and incomplete stent apposition at the aneurysm neck are possible risk factors for incomplete aneurysm occlusion.

15.
Cell Mol Biol (Noisy-le-grand) ; 70(2): 44-50, 2024 Feb 29.
Artigo em Inglês | MEDLINE | ID: mdl-38430041

RESUMO

Molecular pathology and clinical characteristics play a crucial role in guiding treatment selection and predicting the prognosis of diffuse large B-cell lymphoma (DLBCL). The programmed cell death protein 1 (PD-1) and its ligand (PD-L1), have emerged as pivotal regulators of immune checkpoints in cancer. The objectives of this study are to investigate the correlation between the expression levels of PD-1 and soluble PD-L1 (sPD-L1) in the peripheral blood of DLBCL patients, analyze their clinicopathological characteristics, and identify the optimal beneficiary group for PD-1/PD-L1 blockade. Peripheral blood samples were collected from 36 DLBCL patients before their initial treatment at Shandong Cancer Hospital between December 2018 and July 2019. The expression levels of PD-1 and sPD-L1 were measured using flow cytometry and enzyme-linked immunosorbent assay (ELISA), respectively. The clinicopathological characteristics, including age, sex, Ann Arbor stage, International Prognostic Index (IPI) score, response to treatment, etc., were recorded for each patient. The surface expression of PD-1 on peripheral blood T cells was significantly higher in DLBCL patients compared to healthy controls. There was a significant association between elevated PD-1 expression levels and the advanced Ann Arbor stage (P=0.0153) as well as the B group (P=0.0184). Higher sPD-L1 levels were associated with the GCB subtype according to Hans's classification (P=0.0435). The expression levels of PD-1 and sPD-L1 in the peripheral blood of DLBCL patients are significantly correlated with advanced disease stage, B group, and GCB subtype according to Hans's classification. This suggests that the PD-1/PD-L1 axis play a critical role in specific subgroups of DLBCL. Targeting this axis could serve as a potential therapeutic strategy to enhance the clinical outcomes of DLBCL patients. Further studies are necessary to explore the prognostic implications of PD-1 and sPD-L1 expression levels in DLBCL patients.


Assuntos
Antígeno B7-H1 , Linfoma Difuso de Grandes Células B , Humanos , Antígeno B7-H1/genética , Receptor de Morte Celular Programada 1/genética , Linfoma Difuso de Grandes Células B/genética , Ensaio de Imunoadsorção Enzimática , Citometria de Fluxo
16.
Biomed Pharmacother ; 172: 116233, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38308971

RESUMO

Acute lung injury (ALI) is characterized by pulmonary diffusion abnormalities that may progress to multiple-organ failure in severe cases. There are limited effective treatments for ALI, which makes the search for new therapeutic avenues critically important. Macrophages play a pivotal role in the pathogenesis of ALI. The degree of macrophage polarization is closely related to the severity and prognosis of ALI, and S100A9 promotes M1 polarization of macrophages. The present study assessed the effects of S100A9-gene deficiency on macrophage polarization and acute lung injury. Our cohort study showed that plasma S100A8/A9 levels had significant diagnostic value for pediatric pneumonia and primarily correlated with monocyte-macrophages and neutrophils. We established a lipopolysaccharide (LPS)-induced mouse model of acute lung injury and demonstrated that knockout of the S100A9 gene mitigated inflammation by suppressing the secretion of pro-inflammatory cytokines, reducing the number of inflammatory cells in the bronchoalveolar lavage fluid, and inhibiting cell apoptosis, which ameliorated acute lung injury in mice. The in vitro and in vivo mechanistic studies demonstrated that S100A9-gene deficiency inhibited macrophage M1 polarization and reduced the levels of pulmonary macrophage chemotactic factors and inflammatory cytokines by suppressing the TLR4/MyD88/NF-κB signaling pathway and reversing the expression of the NLRP3 pyroptosis pathway, which reduced cell death. In conclusion, S100A9-gene deficiency alleviated LPS-induced acute lung injury by inhibiting macrophage M1 polarization and pyroptosis via the TLR4/MyD88/NFκB pathway, which suggests a potential therapeutic strategy for the treatment of ALI.


Assuntos
Lesão Pulmonar Aguda , Lipopolissacarídeos , Humanos , Criança , Camundongos , Animais , Lipopolissacarídeos/efeitos adversos , Fator 88 de Diferenciação Mieloide/genética , Fator 88 de Diferenciação Mieloide/metabolismo , Receptor 4 Toll-Like/genética , Receptor 4 Toll-Like/metabolismo , Piroptose , Estudos de Coortes , Transdução de Sinais , Lesão Pulmonar Aguda/metabolismo , Macrófagos/metabolismo , Citocinas/metabolismo , Calgranulina B/genética , Calgranulina B/metabolismo
17.
Phys Rev Lett ; 132(4): 046201, 2024 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-38335341

RESUMO

Atomically precise graphene nanoflakes called nanographenes have emerged as a promising platform to realize carbon magnetism. Their ground state spin configuration can be anticipated by Ovchinnikov-Lieb rules based on the mismatch of π electrons from two sublattices. While rational geometrical design achieves specific spin configurations, further direct control over the π electrons offers a desirable extension for efficient spin manipulations and potential quantum device operations. To this end, we apply a site-specific dehydrogenation using a scanning tunneling microscope tip to nanographenes deposited on a Au(111) substrate, which shows the capability of precisely tailoring the underlying π-electron system and therefore efficiently manipulating their magnetism. Through first-principles calculations and tight-binding mean-field-Hubbard modeling, we demonstrate that the dehydrogenation-induced Au-C bond formation along with the resulting hybridization between frontier π orbitals and Au substrate states effectively eliminate the unpaired π electron. Our results establish an efficient technique for controlling the magnetism of nanographenes.

18.
Angew Chem Int Ed Engl ; 63(13): e202318185, 2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38299925

RESUMO

The incorporation of non-benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon-based electronics. However, understanding how specific non-benzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on-surface synthetic strategy toward fabricating non-benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa-a embeds two azulene units formed through oxidative ring-closure of methyl substituents, while Aa-s contains one azulene unit and one Stone-Wales defect, formed by the combination of oxidative ring-closure and skeletal ring-rearrangement reactions. Aa-a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non-benzenoid containing nanographene, coexisting with side-products with closed shell configurations resulted from the combination of ring-closure and ring-rearragement reactions (Ba-a , Ba-s , Bs-a and Bs-s ). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing non-benzenoid motifs and their tailored electronic/magnetic properties.

19.
Angew Chem Int Ed Engl ; : e202319874, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38372180

RESUMO

Helical nanographenes with high quantum yields and strong chiroptical responses are pivotal for developing circularly polarized luminescence (CPL) materials. Here, we present the successful synthesis of novel π-extended double [7]helicenes (ED7Hs) where two helicene units are fused at the meta- or para-position of the middle benzene ring, respectively, as the structural isomers of the reported ortho-fused ED7H. The structural geometry of these ED7Hs is clearly characterized by single-crystal X-ray analysis. Notably, this class of ED7Hs exhibits bright luminescence with high quantum yields exceeding 40 %. Through geometric regulation of two embedded [7]helicene units from ortho-, meta- to para-position, these ED7Hs display exceptional amplification in chiroptical responses. This enhancement is evident in a remarkable approximate fivefold increase in the absorbance and luminescence dissymmetry factors (gabs and glum), respectively, along with a boosted CPL brightness up to 176 M-1 cm-1, surpassing the performance of most helicene-based chiral NGs. Furthermore, DFT calculations elucidate that the geometric adjustment of two [7]helicene units allows the precise alignment of electric and magnetic transition dipole moments, leading to the observed enhancement of their chiroptical responses. This study offers an effective strategy for magnifying the CPL performance in chiral NGs, promoting their expanded application as CPL emitters.

20.
Angew Chem Int Ed Engl ; 63(14): e202319117, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38305848

RESUMO

Functional imaging (FI) techniques have revolutionized tumor imaging by providing information on specific tumor functions, such as glycometabolism. However, tumor cells lack unique molecular characteristics at the molecular level and metabolic pathways, resulting in limited metabolic differences compared to normal cells and increased background signals from FI. To address this limitation, we developed a novel imaging technique termed proximity-enhanced functional imaging (PEFI) for accurate visualization of tumors. By using "two adjacent chemically labeled glycoproteins" as output signals, we significantly enhance the metabolic differences between tumor and normal cells by PEFI, thereby reducing the background signals for analysis and improving the accuracy of tumor functional imaging. Our results demonstrate that PEFI can accurately identify tumors at the cellular, tissue, and animal level, and has potential value in clinical identification and analysis of tumor cells and tissues, as well as in the guidance of clinical tumor resection surgery.


Assuntos
Neoplasias Encefálicas , Diagnóstico por Imagem , Animais
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