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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124981, 2025 Jan 05.
Artículo en Inglés | MEDLINE | ID: mdl-39154405

RESUMEN

The bimetallic nanostructure of Au and Ag can integrate two distinct properties into a novel substrate compared to single metal nanostructures. This work presents a rapid and sensitive surface-enhanced Raman scattering (SERS) substrate for detecting illegal food additives and dyes of crystal violet (CV) and alkali blue 6B (AB 6B). Au-Ag alloy nanoparticles/Ag nanowires (Au-Ag ANPs/Ag NWs) were prepared by solid-state ionics method and vacuum thermal evaporation method at 5µA direct current electric field (DCEF), the molar ratio of Au to Ag was 1:18.34. Many 40 nm-140 nm nanoparticles regularly existed on the surface of Ag NWs with the diameters from 80 nm to 150 nm. The fractal dimension of Au-Ag ANPs/Ag NWs is 1.69 due to macroscopic dendritic structures. Compared with single Ag NWs, the prepared Au-Ag ANPs/Ag NWs substrates show superior SERS performance because of higher surface roughness, the SERS active of Ag NWs and bimetallic synergistic effect caused by Au-Ag ANPs, so the limit of detections (LOD) of Au-Ag ANPs/Ag NWs SERS substrates toward detection of CV and AB 6B were as low as 10-16mol/L and 10-9mol/L, respectively. These results indicate that Au-Ag ANPs/Ag NWs substrates can be used for rapid and sensitive detection of CV and AB 6B and have great development potential for detection of illegal food additives and hazardous substances in the fields of environmental monitoring and food safety.

2.
Cell Metab ; 2024 Aug 29.
Artículo en Inglés | MEDLINE | ID: mdl-39243758

RESUMEN

During the progression of metabolic dysfunction-associated steatohepatitis (MASH), the accumulation of auto-aggressive CD8+ T cells significantly contributes to liver injury and inflammation. Empagliflozin (EMPA), a highly selective inhibitor of sodium-glucose co-transporter 2 (SGLT2), exhibits potential therapeutic benefits for liver steatosis; however, the underlying mechanism remains incompletely elucidated. Here, we found that EMPA significantly reduced the hepatic accumulation of auto-aggressive CD8+ T cells and lowered granzyme B levels in mice with MASH. Mechanistically, EMPA increased ß-hydroxybutyric acid by promoting the ketogenesis of CD8+ T cells via elevating 3-hydroxybutyrate dehydrogenase 1 (Bdh1) expression. The ß-hydroxybutyric acid subsequently inhibited interferon regulatory factor 4 (Irf4), which is crucial for CD8+ T cell activation. Furthermore, the ablation of Bdh1 in T cells aggravated the manifestation of MASH and hindered the therapeutic efficacy of EMPA. Moreover, a case-control study also showed that SGLT2 inhibitor treatment repressed CD8+ T cell infiltration and improved liver injury in patients with MASH. In summary, our study indicates that SGLT2 inhibitors can target CD8+ T cells and may be an effective strategy for treating MASH.

3.
Anal Methods ; 2024 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-39253940

RESUMEN

Determination of mercury species over solid waste from natural gas processing plants is a prerequisite for solid waste decontamination and mercury recycling. The temperature-programmed decomposition and desorption method (TPDD) is a promising technique to determine the mercury species over solid waste. Mercury species over solid wastes with complex components and similar desorption temperature, however, cannot always be determined using only the TPDD method. In the present study, the EPA 3200 method was applied to optimize the TPDD process for speciation of the mercury compound over solid wastes collected from a natural gas processing plant, including four spent adsorbents and three sludges. The mercury species with similar desorption temperatures over solid wastes were completely separated by the EPA 3200 method optimized TPDD process. The mercury species over spent adsorbents and sludges could be determined based on the fingerprints of the mercury compounds. The mercury compounds over spent adsorbents were specified to be Hg0 and/or M-Hg amalgam, HgS(black) and HgO(red), of which HgS(black) was the primary mercury compound. However, the mercury species over sludge were analyzed to be Hg0 and/or M-Hg amalgam, HgCl2(minor), HgS(black), HgO(yellow) and HgS(red). The mercury recovery rates of solid wastes ranged from 73% to 120%. With the above results, it was considered that the EPA 3200 method optimized TPDD process was a promising method to specify and semi-quantify the mercury compounds in solid waste.

4.
Biomater Sci ; 2024 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-39233608

RESUMEN

Bacterial keratitis is a common form of inflammation caused by the bacterial invasion of the corneal stroma after trauma. In extreme cases, it can lead to severe visual impairment or even blindness; therefore, timely medical intervention is imperative. Unfortunately, widespread misuse of antibiotics has led to the development of drug resistance. In recent years, organ-on-chips that integrate multiple cell co-cultures have extensive applications in fundamental research and drug screening. In this study, immortalized human corneal epithelial cells and primary human corneal fibroblasts were co-cultured on a porous polydimethylsiloxane membrane to create a cornea-on-a-chip model. The developed multilayer epithelium closely mimicked clinical conditions, demonstrating high structural resemblance and repeatability. By introducing a consistently defective epithelium and bacterial infection using the space-occupying method, we successfully established an in vitro model of bacterial keratitis using S. aureus. We validate this model by evaluating the efficacy of antibiotics, such as levofloxacin, tobramycin, and chloramphenicol, through simultaneously observing the reactions of bacteria and the two cell types to these antibiotics. Our study has revealed the barrier function of epithelium of the model and differentiated efficacy of three drugs in terms of bactericidal activity, reducing cellular apoptosis, and mitigating scar formation. Altogether, the cornea on chip enables the assessment of ocular antibiotics, distinguishing the impact on corneal cells and structural integrity. This study introduced a biomimetic in vitro disease model to evaluate drug efficacy and provided significant insights into the extensive effects of antibiotics on diverse cell populations within the cornea.

5.
Haematologica ; 2024 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-39234866

RESUMEN

Patients with relapsed or refractory (R/R) diffuse large B-cell lymphoma (DLBCL) have a poor prognosis. Loncastuximab tesirine (Lonca), an antibody conjugate targeting CD19, has demonstrated significant clinical benefit in R/R DLBCL in a global phase 2 LOTIS-2 study. In the China bridging pivotal phase 2 OL-ADCT-402-001 study, eligible patients aged ≥18 years with R/R DLBCL who had failed ≥ 2 lines of systemic therapies were enrolled and treated with Lonca every 3 week with 150 µg/kg for 2 cycles; then 75 µg/kg for subsequent cycles (up to 1 year). The primary endpoint was overall response rate (ORR) assessed by independent review committee. Primary analyses for efficacy and safety were performed on the patients who received at least one treatment and had at least 6 months of follow-up following an initial documented response. As of data-cutoff, 64 patients received Lonca (median: 4.0 cycles [range: 1 to 17]). The median number of prior lines of therapies was 3.0 (range: 2 to 12). The ORR was 51.6% (95% CI: 38.7% to 64.2%), and the complete response rate was 23.4%. Hematological events accounted for the majority of the most common (≥15%) Grade ≥3 treatment-emergent adverse events (TEAEs), in which increased gamma glutamyltransferase (25.0%), and hypokalaemia (18.8%) also were reported. Serious TEAEs were reported in 35 of 64 patients with 4 fatal TEAEs. In conclusion, Lonca monotherapy demonstrated clinically meaningful efficacy and was well-tolerated in heavily pretreated Chinese patients with R/R DLBCL, which was consistent with the results of the LOTIS-2 study in Caucasian patients.

6.
Angew Chem Int Ed Engl ; : e202414712, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39226119

RESUMEN

The asymmetric rearrangement of allylic sulfilimines is an effective route to synthetic attractive targets such as allylic sulfenamides and others. The current methods are limited to chirality transfer from chiral allylic sulfilimine precursors. Herein, we report a general and fundamentally new rearrangement route accessing optically enriched allylic sulfenamides and their derivatives. The process involves a S-alkylation and an unusual S-to-N rearrangement step. The chiral nickel complex enables the transformation of a broad scope of sulfenamides and vinyl α-diazo pyrazoleamides under mild conditions. Various allylic sulfenamides have been synthesized with excellent γ-regioselectivity and enantioselectivity, which can be efficiently converted to sulfinamide and 4-aminobutenoic acid derivatives. In addition, DFT calculations demonstrate the connection between the spin state and conformation of nickel vinyl carbenoid, as well as an unknown rearrangement process.

7.
Nanoscale ; 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39225229

RESUMEN

Theoretically determining the lowest-energy structure of a cluster has been a persistent challenge due to the inherent difficulty in accurate description of its potential energy surface (PES) and the exponentially increasing number of local minima on the PES with the cluster size. In this work, density-functional theory (DFT) calculations of Co clusters were performed to construct a dataset for training deep neural networks to deduce a deep potential (DP) model with near-DFT accuracy while significantly reducing computational consumption comparable to classic empirical potentials. Leveraging the DP model, a high-efficiency hybrid differential evolution (HDE) algorithm was employed to search for the lowest-energy structures of CoN (N = 11-50) clusters. Our results revealed 38 of these clusters superior to those recorded in the Cambridge Cluster Database and identified diverse architectures of the clusters, evolving from layered structures for N = 11-27 to Marks decahedron-like structures for N = 28-42 and to icosahedron-like structures for N = 43-50. Subsequent analyses of the atomic arrangement, structural similarity, and growth pattern further verified their hierarchical structures. Meanwhile, several highly stable clusters, i.e., Co13, Co19, Co22, Co39, and Co43, were discovered by the energetic analyses. Furthermore, the magnetic stability of the clusters was verified, and a competition between the coordination number and bond length in affecting the magnetic moment was observed. Our study provides high-accuracy and high-efficiency prediction of the optimal structures of clusters and sheds light on the growth trend of Co clusters containing tens of atoms, contributing to advancing the global optimization algorithms for effective determination of cluster structures.

8.
Adv Sci (Weinh) ; : e2405729, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39225346

RESUMEN

The therapeutic efficacy of vaccines for treating cancers in clinics remains limited. Here, a rationally designed cancer vaccine by placing immunogenically differential and clinically approved aluminum (Al) or manganese (Mn) in a 2D nanosheet (NS) architecture together with antigens is reported. Structurally optimal NS with a high molar ratio of Mn to Al (MANS-H) features distinctive immune modulation, markedly promoting the influx of heterogeneous innate immune cells at the injection site. Stimulation of multiple subsets of dendritic cells (DCs) significantly increases the levels, subtypes, and functionalities of antigen-specific T cells. MANS-H demonstrates even greater effectiveness in the production of antigen-specific antibodies than the commercial adjuvant (Alhydrogel) by priming T helper (Th)2 cells rather than T follicular helper (Tfh) cells. Beyond humoral immunity, MANS-H evokes high frequencies of antigen-specific Th1 and CD8+ cell immunity, which are comparable with Quil-A that is widely used in veterinary vaccines. Immunized mice with MANS-H adjuvanted vaccines exert strong potency in tumor regression by promoting effector T cells infiltrating at tumor and overcoming tumor resistance in multiple highly aggressive tumor models. The engineered immunogen with an intriguing NS architecture and safe immunopotentiators offers the next clinical advance in cancer immunotherapy.

9.
J Neurooncol ; 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39225955

RESUMEN

OBJECTIVE: This study aimed to develop a predictive model for cerebellar mutism syndrome (CMS) in pediatric patients with posterior fossa tumors, integrating lesion-symptom mapping (LSM) data with clinical factors, and to assess the model's performance. METHODS: A cohort of pediatric patients diagnosed with posterior fossa tumors and undergoing surgery at Beijing Children's Hospital from July 2013 to December 2023 was analyzed. Clinical variables gender, age at surgery, tumor characteristics, hydrocephalus, surgical route and pathology were collected. LSM was used to link tumor locations with CMS outcomes. Lasso regression and logistic regression were employed for feature selection and model construction, respectively. Model performance was assessed using area under the curve (AUC) and accuracy metrics. RESULTS: The study included 197 patients in total, with CMS rates consistent across training, validation, and prospective groups. Significant associations were found between CMS and gender, tumor type, hydrocephalus, paraventricular edema, surgical route, and pathology. A predictive model combining voxel location data from LSM with clinical factors achieved high predictive performance (C-index: training 0.956, validation 0.933, prospective 0.892). Gender, pathology, and voxel location were identified as key predictors for CMS. CONCLUSION: The study established an effective predictive model for CMS in pediatric posterior fossa tumor patients, leveraging LSM data and clinical factors. The model's accuracy and robustness suggest its potential utility in clinical practice for early CMS risk assessment and intervention planning.

10.
ACS Omega ; 9(36): 38217-38226, 2024 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-39281907

RESUMEN

This study introduces a novel one-pot method employing tannic acid (TA) to synthesize stable gold nanoparticles (TA-AuNPs), which are characterized using transmission electron microscopy, X-ray powder diffraction, and Fourier transform infrared spectroscopy. We apply these TA-AuNPs in a newly developed colorimetric assay for hydrogen peroxide (H2O2) detection that utilizes the oxidation of iodide (I-) on TA-AuNPs, leading to a detectable yellow color change in the solution. The reaction kinetics are captured by the rate equation R = 0.217[KI]0.61[H2O2]0.69. The possible sensing mechanism was proposed through density functional theory calculations. At the optimum conditions, the proposed TA-AuNPs/I- system demonstrated a linear relationship between H2O2 concentration and absorbance intensity (λ = 350 nm) and achieved a limit of detection (LOD) of 7.33 µM. Furthermore, we expand the utility of this approach to glucose detection by integrating glucose oxidase into the system, resulting in a LOD of 10.0 µM. Application of this method to actual urine samples yielded spiked recovery rates ranging from 96.6-102.0% and relative standard deviations between 3.00-8.34%, underscoring its efficacy and potential for real-world bioanalytical challenges.

11.
Nat Commun ; 15(1): 8048, 2024 Sep 14.
Artículo en Inglés | MEDLINE | ID: mdl-39277619

RESUMEN

White organic light-emitting diodes (WOLEDs) hold significant promise in illumination and displays, but achieving high efficiency while maintaining stability is an ongoing challenge. Here, we strategically combine a blue donor-acceptor thermally activated delayed fluorescence (TADF) emitter featuring rapid reverse intersystem crossing rate and a yellow multi-resonance TADF emitter renowned for the fast radiative transition process to achieve warm WOLEDs with exceptional power efficiency exceeding 190 lm W-1 and external quantum efficiency (EQE) of 39%, setting records for WOLEDs. Meanwhile, these devices also exhibit an extended operational lifetime (LT80) of 446 h at an initial luminance of 1000 cd m-2. Another group of blue and yellow emitters based on our strategy achieves a standard white emission and a high EQE of 35.6%, confirming the universality of our strategy. This work presents a versatile strategy to harmonize singlet exciton radiation and triplet exciton up-conversion, thus achieving a win-win situation of efficiency and stability.

12.
Inorg Chem ; 2024 Sep 16.
Artículo en Inglés | MEDLINE | ID: mdl-39285706

RESUMEN

The aim of this study was to analyze the properties of a composite that incorporates carbon black and polypyrrole within an Fe3O4/SiO2 core-shell structure, synthesized using the Stöber method under high ultrasonic irradiation conditions (120 W) for Fe3O4/SiO2 nanocomposite. The Fe3O4/SiO2 core-shell indicates magnetochromatic behavior characterized by temperature-dependent coloration and magnetic alignment. Incorporating carbon black and polypyrrole at moderate temperature (5-15 °C) enhanced the electrical conductivity. The electrical resistivity ρ was 7.30 × 106 Ω·cm for Fe3O4, 3.19 × 108 Ω·cm for Fe3O4/SiO2, and 242.56 Ω·cm for Fe3O4/SiO2/PPy-c at room temperature. When it was performed at moderate temperature (5-15 °C), the ρ of the prepared Fe3O4/SiO2 and Fe3O4/SiO2/PPy-c nanocomposite was 1.08 × 108 and 0.00799 Ω·cm, respectively. Current-voltage measurements revealed a linear relationship, with butterfly shaped curves in the forward-bias region for all samples. The Fe3O4/SiO2/PPy-c nanocomposite's tunable synergistic electrical properties at moderate temperatures make it useful for environmental applications, electrical wiring, and circuitry.

13.
Front Pharmacol ; 15: 1462430, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-39281279

RESUMEN

Acute generalized exanthematous pustulosis, an infrequent adverse drug reaction, mainly results from drugs. Clinically, acute generalized exanthematous pustulosis manifests as a high fever, with skin lesions of small monomorphic subcorneal sterile pustules on an erythematous that presents at 1-4 days after medication exposure. The incidence of acute generalized exanthematous pustulosis varies from 3/1, 000, 000 to 5/1, 000, 000, while the mortality rate is typically around 5%. We present a case of a 69-year-old female who developed a diffuse, erythematous, pustular rash over the entire body and exhibited a fever of 38.3°C after 4 days of icotinib therapy. Considering her medication history and the appearance of the lesions, she was diagnosed with acute generalized exanthematous pustulosis and received appropriate treatment. We also conducted a literature review through PubMed to compare similarities and differences between our case and those reported in the literature.

14.
Sci Rep ; 14(1): 20347, 2024 Sep 02.
Artículo en Inglés | MEDLINE | ID: mdl-39223188

RESUMEN

The study of hydrogen concentration distribution law of hydrogen-doped methane pipeline is directly related to the safety and stability of hydrogen-doped methane pipeline network. Based on the theory of fluid dynamics, this paper established a model of hydrogen-doped methane pipeline and simulated the operation and shutdown status of hydrogen-doped methane pipeline by adopting the computational fluid dynamics method and selecting the mixture multiphase model and standard k - ε turbulence model. This paper investigates the hydrogen concentration distribution law in hydrogen-doped methane pipelines as well as the influence law of different hydrogen-doping ratios, operating flow velocities, operating pressures, shutdown time and gas usage on the hydrogen concentration distribution in gas pipeline. The results show that: under the operation condition, there is a weak uneven distribution of hydrogen in the pipeline, the hydrogen-doping ratio, flow velocity, pressure on the hydrogen volume fraction of the change in the 0.9% or less, the effect can be ignored; in the shutdown status, there is a clear stratification phenomenon, the hydrogen-doping ratio increased from 10 to 25%, the change in the volume fraction of hydrogen in the 11.2% or less, a positive correlation; with the extension of the shutdown time to 900s, the pipeline firstly appeared obvious stratification phenomenon in the branch pipe, the thickness of the gas with hydrogen volume fraction above 40% on the upper wall surface of the branch pipe increased to 0.7 mm, and after the shutdown time was extended to 10 h, obvious stratification phenomenon appeared in the main pipeline, and the volume fraction of hydrogen near the top of the main pipe of about 16.5 mm was above 30%, which was positively correlated; In the shutdown status, the shutdown time has the greatest effect on the stratification phenomenon in the pipe, followed by the hydrogen-doping ratio, and the gas usage has the least effect.

15.
J Nanobiotechnology ; 22(1): 533, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39223666

RESUMEN

The poor prognosis of hepatocellular carcinoma (HCC) is still an urgent challenge to be solved worldwide. Hence, assembling drugs and targeted short peptides together to construct a novel medicine delivery strategy is crucial for targeted and synergy therapy of HCC. Herein, a high-efficiency nanomedicine delivery strategy has been constructed by combining graphdiyne oxide (GDYO) as a drug-loaded platform, specific peptide (SP94-PEG) as a spear to target HCC cells, sorafenib, doxorubicin-Fe2+ (DOX-Fe2+), and siRNA (SLC7A11-i) as weapons to exert a three-path synergistic attack against HCC cells. In this work, SP94-PEG and GDYO form nanosheets with HCC-targeting properties, the chemotherapeutic drug DOX linked to ferrous ions increases the free iron pool in HCC cells and synergizes with sorafenib to induce cell ferroptosis. As a key gene of ferroptosis, interference with the expression of SLC7A11 makes the ferroptosis effect in HCC cells easier, stronger, and more durable. Through gene interference, drug synergy, and short peptide targeting, the toxic side effects of chemotherapy drugs are reduced. The multifunctional nanomedicine GDYO@SP94/DOX-Fe2+/sorafenib/SLC7A11-i (MNMG) possesses the advantages of strong targeting, good stability, the ability to continuously induce tumor cell ferroptosis and has potential clinical application value, which is different from traditional drugs.


Asunto(s)
Carcinoma Hepatocelular , Doxorrubicina , Ferroptosis , Neoplasias Hepáticas , Nanomedicina , Péptidos , Sorafenib , Ferroptosis/efectos de los fármacos , Carcinoma Hepatocelular/tratamiento farmacológico , Humanos , Neoplasias Hepáticas/tratamiento farmacológico , Doxorrubicina/farmacología , Doxorrubicina/química , Nanomedicina/métodos , Sorafenib/farmacología , Sorafenib/química , Línea Celular Tumoral , Animales , Péptidos/química , Péptidos/farmacología , Ratones , Antineoplásicos/farmacología , Antineoplásicos/química , Sinergismo Farmacológico , Sistema de Transporte de Aminoácidos y+/metabolismo , Ratones Desnudos , ARN Interferente Pequeño , Ratones Endogámicos BALB C , Sistemas de Liberación de Medicamentos/métodos
16.
BMC Geriatr ; 24(1): 730, 2024 Sep 03.
Artículo en Inglés | MEDLINE | ID: mdl-39227765

RESUMEN

BACKGROUND: Formal home and community-based care are often considered as the preferable option to institutional care, offering older individuals the convenience of receiving care in their homes. Although research has found that these services may alleviate the burden on informal caregivers, there is a lack of research on which specific types of formal home and community-based care influence informal care provision. METHODS: Employing fixed-effects and quantile regression models, this study seeks to explore the effects that various formal home and community-based care services have on reducing the burden of informal care. This study draws data from the Chinese Longitudinal Healthy Longevity Survey 2005, 2008, 2011, 2014, and 2018. RESULTS: Our findings indicate that two types of formal care substantially influence the provision of informal care. The availability of daily living assistance services correlates with reduced informal caregiving hours, especially for those with extensive care needs. The availability of community-based health care services is linked to a reduction in the direct expenses incurred from informal caregiving, especially for those incurring greater direct caregiving costs. These effects are more prominent among urban residents. Other services, such as mental health support and legal advice services, do not demonstrate significant effects on reducing informal care hours and costs. CONCLUSIONS: Daily living assistance and community-based health care services play a crucial role in benefiting informal caregivers. It is important to prioritize the expansion of these services, especially among those with greater care needs.


Asunto(s)
Cuidadores , Servicios de Salud Comunitaria , Servicios de Atención de Salud a Domicilio , Humanos , Masculino , Femenino , Estudios Longitudinales , Anciano , China/epidemiología , Servicios de Salud Comunitaria/economía , Anciano de 80 o más Años , Longevidad , Persona de Mediana Edad , Pueblos del Este de Asia
17.
Heliyon ; 10(16): e35528, 2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39229502

RESUMEN

Rationale and objectives: We constructed a dual-energy computed tomography (DECT)-based model to assess cervical lymph node metastasis (LNM) in patients with laryngeal squamous cell carcinoma (LSCC). Materials and methods: We retrospectively analysed 164 patients with LSCC who underwent preoperative DECT from May 2019 to May 2023. The patients were randomly divided into training (n = 115) and validation (n = 49) cohorts. Quantitative DECT parameters of the primary tumours and their clinical characteristics were collected. A logistic regression model was used to determine independent predictors of LNM, and a nomogram was constructed along with a corresponding online model. Model performance was assessed using the area under the curve (AUC) and the calibration curve, and the clinical value was evaluated using decision curve analysis (DCA). Results: In total, 64/164 (39.0 %) patients with LSCC had cervical LNM. Independent predictors of LNM included normalized iodine concentration in the arterial phase (odds ratio [OR]: 8.332, 95 % confidence interval [CI]: 2.813-24.678, P < 0.001), normalized effective atomic number in the arterial phase (OR: 5.518, 95 % CI: 1.095-27.818, P = 0.002), clinical T3-4 stage (OR: 5.684, 95 % CI: 1.701-18.989, P = 0.005), and poor histological grade (OR: 5.011, 95 % CI: 1.003-25.026, P = 0.049). These predictors were incorporated into the DECT-based nomogram and the corresponding online model, showing good calibration and favourable performance (training AUC: 0.910, validation AUC: 0.918). The DCA indicated a significant clinical benefit of the nomogram for estimating LNM. Conclusions: DECT parameters may be useful independent predictors of LNM in patients with LSCC, and a DECT-based nomogram may be helpful in clinical decision-making.

18.
J Am Chem Soc ; 146(36): 25328-25342, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39223083

RESUMEN

Our knowledge about endohedral metallofullerenes (EMFs) is restricted to the structures with sufficient kinetic stability to be extracted from the arc-discharge soot and processed by chromatographic and structural techniques. For the most abundant rare-earth monometallofullerene MIII@C82, experimental studies repeatedly demonstrated C2v(9) and Cs(6) carbon cage isomers, while computations predicted equal stability of the "missing" C3v(8) isomer. Here we report that this isomer is indeed formed but has not been recovered from soot using standard protocols. Using a combination of redox extraction and subsequent benzylation and trifluoromethylation with single-crystal XRD analysis of CF3 adduct, we prove that Dy@C3v(8)-C82 is one of the most abundantly produced metallofullerenes, which was not identified in earlier studies because of the low kinetic stability. Further, using the Dy@C3v(8)-C82(CF3) and Dy@C3v(8)-C82(CH2Ph) monoadducts for the case study, we analyzed the role of metal-fullerene bonding on the single-ion magnetic anisotropy of Dy in EMFs. The multitechnique approach, combining ab initio calculations, EPR spectroscopy, and SQUID magnetometry, demonstrated that coordination of the Dy ion to the fullerene cage induces moderate, nonaxial, and very fluid magnetic anisotropy, which strongly varies with small alterations in the Dy-fullerene coordination geometry. As a result, Dy@C3v(8)-C82(CH2Ph) is a weak field-induced single-molecule magnet (SMM), whose signatures of magnetic relaxation are detectable only below 3 K. Our results demonstrate that metal-cage interactions should have a detrimental effect on the SMM performance of EMFs. At the same time, the strong variability of the magnetic anisotropy with metal position suggests tunability and offers strategies for future progress.

19.
Stat Med ; 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39248697

RESUMEN

Clustering functional data aims to identify unique functional patterns in the entire domain, but this can be challenging due to phase variability that distorts the observed patterns. Curve registration can be used to remove this variability, but determining the appropriate level of warping flexibility can be complicated. Curve registration also requires a target to which a functional object is aligned, typically the cross-sectional mean of functional objects within the same cluster. However, this mean is unknown prior to clustering. Furthermore, there is a trade-off between flexible warping and the number of resulting clusters. Removing more phase variability through curve registration can lead to fewer remaining variations in the functional data, resulting in a smaller number of clusters. Thus, the optimal number of clusters and warping flexibility cannot be uniquely identified. We propose to use external information to solve the identification issue. We define a cross validated Kullback-Leibler information criterion to select the number of clusters and the warping penalty. The criterion is derived from the predictive classification likelihood considering the joint distribution of both the functional data and external variable and penalizes the uncertainty in the cluster membership. We evaluate our method through simulation and apply it to electrocardiographic data collected in the Chronic Renal Insufficiency Cohort study. We identify two distinct clusters of electrocardiogram (ECG) profiles, with the second cluster exhibiting ST segment depression, an indication of cardiac ischemia, compared to the normal ECG profiles in the first cluster.

20.
J Hazard Mater ; 480: 135713, 2024 Sep 02.
Artículo en Inglés | MEDLINE | ID: mdl-39278035

RESUMEN

Radioactive nuclides and highly toxic organophosphates are typical deadly threats. Materials with the function of radioactive substances adsorption and organophosphates degradation provide double protection. Herein, dual-functional polyamide (PA)/polyethyleneimine (PEI)@Zr-MOF fiber composite membranes, fabricated by in-situ solvothermal growth of Zr-MOF on PA/PEI electrospun fiber membranes, are designed for protection against two typical model compounds of iodine and dimethyl 4-nitrophenyl phosphate (DMNP). Benefiting from the unique core-sheath structure composed of inner nitrogen-rich fibers and outer porous Zr-MOF, the composite membranes rapidly enrich iodine through abundant active sites of the outer sheath and form complexes with the amine of inner PEI, exhibiting a highly competitive adsorption capacity of 609 mg g-1. Moreover, it can adsorb and degrade DMNP with the synergy of PEI component and Zr-MOF, achieving an 80 % removal of DMNP within 7 min without any additional co-catalyst. This work provides a feasible strategy to fabricate dual-functional materials that protect against radioactive and organophosphorus contaminants.

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