Reducing mineral fertilizer inputs while maintaining crop productivity is a central challenge for sustainable grain legume production. This study evaluated whether biochar-biostimulant combinations could improve mungbean (Vigna radiata L.) performance under reduced NPK fertilization. A polytunnel pot experiment was conducted using a completely randomized 2 × 4 factorial design with two NPK levels, 100% and 50% of the recommended dose, and four treatments: biochar alone, biochar + humic acid, biochar + Bacillus amyloliquefaciens, and biochar + Pseudomonas fluorescens. Biostimulant addition to biochar improved plant growth, pigment status, and antioxidant response, with the strongest responses observed under reduced NPK supply. Under 50% NPK, biochar + P. fluorescens increased grain yield by approximately 90% compared with biochar alone and maintained grain yield (4.00 g plant⁻¹) comparable to the 100% NPK biochar-only control (3.85 g plant⁻¹). It also enhanced nodulation, increased total chlorophyll by approximately 60%, and reduced malondialdehyde by approximately 50%. Grain weight was positively associated with nodule number and ascorbic acid content and negatively associated with H₂O₂ content. These findings support biochar-assisted P. fluorescens supplementation as a promising strategy for sustaining mungbean productivity under reduced NPK input, warranting further field validation for broader applicability.
Adsorptive separation of propyne/propylene (C3H4/C3H6) using porous adsorbents offers a promising route toward energy-efficient production of polymer-grade C3H6. Currently, the prevailing adsorbents are ultramicroporous metal-organic frameworks (MOFs) that feature narrow channels and/or consist of inorganic anion pillars, which often lead to limited C3H4 uptake capacity and high isosteric enthalpy of adsorption. We report herein a highly porous and robust zirconium metal-organic framework, termed SJTU-520. This MOF incorporates shape-persistent molecular arrays in three-dimensional space derived from cyclotetrabenzoin, which function as selective sites for the preferential entrapment of C3H4 over C3H6, thus enabling high C3H4 capture capacity, record high C3H4/C3H6 uptake ratio at 1 bar and 298 K, and efficient C3H4/C3H6 separation at ambient conditions. Compared with the cyclotetrabenzoin and tetraacetate cyclotetrabenzoin-based supramolecular organic crystals, SJTU-520 exhibits significantly higher surface area (3650 m2/g versus 42 and 570 m2/g), leading to a C3H4 uptake boost by 6.1-fold and 3.7-fold at 298 K and 1 bar, without any compromise of the C3H4/C3H6 selectivity. The efficient C3H4/C3H6 separation was validated by extensive breakthrough experiments under various conditions with great recyclability and high productivity of polymer-grade C3H6 from a 10/90 C3H4/C3H6 mixture. Computational simulations revealed that the four benzene walls of the cyclotetrabenzoin macrocycle in SJTU-520 formed equidistant π-π interactions with the C≡C triple bond of encapsulated C3H4 molecule. This work illustrates a general and powerful strategy─the reticulation of intrinsically functional organic scaffolds into highly porous frameworks─toward creating bespoke materials with precisely tailored functionalities and enhanced properties.
Chlorella vulgaris is a haploid green microalga with cost-effective cultivation, high biomass productivity, and heterotrophic growth capability, making it an attractive platform for food, pharmaceutical, and recombinant protein production. However, development of efficient nuclear transformation systems has been limited by its rigid cell wall and intrinsically low homologous recombination (HR) activity. Here, we established an antibiotic-free nuclear transformation strategy targeting the endogenous nitrate reductase (NR) locus in C. vulgaris PKVL7422 using donor constructs designed to promote homologous recombination. Transformation outcomes were quantitatively evaluated by flow cytometry based on GFP-positive frequency. A codon-optimized GFP expression cassette driven by the heterologous CaMV 35S promoter and terminated by the RBCS2 3' untranslated region was flanked by NR homology arms and introduced as linear donor DNA via electroporation. GFP-positive frequency was quantified by flow cytometry. GFP-positive cells were detected at frequencies of 5.1-6.3%. Optimization of homology arm length, donor DNA amount, and electroporation voltage enabled reproducible enrichment of targeted GFP integration events. Junction PCR confirmed precise insertion at the NR locus. Compared with previous reports, the GFP-positive frequencies observed in this study were substantially higher under our experimental conditions. Disruption of the endogenous NR gene enabled antibiotic-free selection based on nitrate metabolism, while GFP fluorescence allowed rapid quantitative screening. These results provide a basis for HR-mediated nuclear genome engineering and recombinant protein expression in C. vulgaris.
Sea urchin grazing can drive kelp loss creating low productivity "barrens" with reduced biodiversity that may persist for decades. In these habitats, limited food driven by sea urchin herbivory reciprocally affects sea urchin physiology, yet the metabolic pathways enabling survival in the starvation conditions remain poorly understood. This study employed gas chromatography-mass spectrometry metabolomics to compare gonad metabolite profiles of purple sea urchins, Strongylocentrotus purpuratus, from barrens and adjacent kelp forest margins. Gonads from barren animals showed pronounced metabolic reallocations relative to kelp-margin animals, supporting energy production, redox balance, and membrane integrity. Carbohydrate metabolism was shifted towards increased glucose and gluconeogenesis with reduced alanine and glutamine as substrates for energy production. The pentose phosphate pathway fluxed towards energy production (supported by elevated sedoheptulose and mannoheptulose, and reduced glutamine and glutamate), rather than nucleotide synthesis and growth. Elevated amino acids (cysteine, cystine and lysine) reflected gonad protein catabolism, energy production and redox balance. Changes in lipid metabolism showed elevated monostearin from lipid breakdown, reduced heptanoic acid as energy substrate, and increased malonate supporting membrane integrity. This study reveals the specific metabolic adjustments purple sea urchins employ under food-limited conditions in barrens, diverting energy from reproduction to enhance long-term survival, potentially signaling challenges for kelp restoration.
Tuning the morphology and structure of Cu nanomaterials could effectively regulate their property, functions, and applications. However, it still remains challenging to directly synthesize Cu nanomaterials with an unconventional phase. Here, we report a one-pot wet-chemical synthesis of Cu nanocrystals (NCs) with a hexagonal close-packed (hcp, 2H type) phase, which is different from their thermodynamically stable face-centered cubic (fcc) phase. Compared to the conventional fcc-Cu NCs, the obtained 2H-Cu NCs exhibit enhanced catalytic activity and selectivity in the electrochemical carbon dioxide reduction reaction (CO2RR), achieving a high Faradaic efficiency (FE) of 73.1% toward multicarbon (C2+) products at 600 mA cm-2 under alkaline conditions in a flow cell. Moreover, in situ characterizations and density functional theory (DFT) calculations reveal that the 2H-Cu NCs can optimize the adsorption of the *CO intermediate, leading to a low energy barrier for the formation of C2+ products. This work not only demonstrates an improvement in CO2RR performance of Cu NCs by using the strategy of phase engineering of nanomaterials (PEN) but also opens up an avenue to explore the intrinsic properties and applications of unconventional-phase nanomaterials.
The electrochemical control of fluorescence has been extensively developed in homogeneous media, yet its implementation within electrically insulating lipid bilayers remains largely unexplored. Here we establish that an electrochemically gated fluorescence switch can be implemented in individual giant unilamellar vesicles using a rhodamine-ferrocene dyad that modulates emission through redox-controlled photoinduced electron transfer. A membrane-anchored derivative enables direct visualization of reversible fluorescence activation under electrochemical bias. Remarkably, the switching is strictly leaflet-selective and occurs only for dyads exposed to the electrode interface, highlighting the insulating nature of lipid bilayers. Furthermore, membrane surface charge critically governs the switching efficiency and induces pronounced kinetic asymmetry between oxidation and reduction processes, revealing the key role of interfacial electrostatic interactions in redox-controlled emission. These results establish electrochemical fluorescence modulation in membranes as a spatially and electrostatically gated interfacial process and define general principles for redox-responsive probes operating in soft interfaces, such as lipid membranes.
Lead-free halide perovskite semiconductors show great promise for light-emitting diodes (LEDs), benefiting from tunable optoelectronic properties and solution processability. However, their practical applications in high-current-density LEDs are fundamentally constrained by severe efficiency roll-off, primarily caused by nonradiative recombination and carrier-induced structural instabilities. In this study, we introduce a molecular N,N'-diphenylthiourea (DPTA)-engineered tin perovskite semiconductor (CsSnI3) that achieves a photoluminescence quantum efficiency (PLQE) of 36% at a carrier concentration of 1018 cm-3. Our approach enables precise control over the charge-carrier concentration and lattice growth. High-resolution transmission electron microscopy further demonstrates that the uniform local strain distribution in the doped films enhances carrier wave-function overlap, leading to a substantial boost in PLQE. Leveraging the enhanced optoelectronic properties of DPTA-treated CsSnI3, we fabricate near-infrared LEDs that exhibit an external quantum efficiency (EQE) of 13.4% and an unprecedented peak radiance of 1248 W sr-1 m-2, with minimal efficiency roll-off even at high current densities exceeding 3500 mA cm-2 in pulse-mode operation. This work introduces a new material-doping strategy for lead-free perovskites, demonstrating their potential for high-power optoelectronic applications and advancing the feasibility of electrically pumped perovskite laser diodes.
Large language models (LLMs) are increasingly explored in radiology, yet concerns persist regarding hallucination and lack of factual grounding. Retrieval-augmented generation (RAG) seeks to address these limitations by coupling generative models with external knowledge retrieval. We conducted a scoping review to characterize how RAG systems have been applied in radiology and medical imaging. A systematic search of PubMed, Embase, Scopus, IEEE Xplore, and arXiv identified 45 studies implementing RAG-based approaches in radiology-related tasks. In terms of clinical tasks, RAG was most commonly applied to radiology report generation and question answering. Dense retrieval strategies predominated, while sparse, hybrid and proprietary retrieval approaches were less frequent. External knowledge sources most frequently comprised biomedical literature databases and clinical guidelines. Applications were heavily skewed toward chest radiography and X-ray-based tasks, with relatively few studies addressing CT, MRI, PET, ultrasound, or under-represented subspecialties such as pediatric radiology and neuroradiology. Most comparative studies reported task-specific performance gains with RAG over non-retrieval baselines, and a small subset reported performance comparable to trained radiologists or state-of-the-art models. However, hallucinations and errors persisted, and heterogeneity across studies limited the generalizability of these findings. Evaluation practices largely relied on automated accuracy or text-overlap metrics, with limited use of standardized expert evaluation and minimal assessment of safety, bias, computational efficiency, or clinical utility. Overall, while RAG shows promise for improving factual grounding in radiology AI, current evaluation paradigms likely overestimate real-world clinical readiness. Future work should prioritize retrieval quality, clinically grounded evaluation, safety-critical error analysis, bias assessment, and deployment-relevant efficiency metrics to enable responsible clinical translation.
Persulfidation of sulfhydryl functional group (-SH) in protein and nonprotein thiols is a physiologically important process and generally involves the reduction of a partially oxidized sulfur by a fully reduced sulfur. In the present work, two dicobalt(II)-nitrito complexes, [Co2(PhBIMP)(μ-NO2)(DMF)]2+ (2) and [Co2(PhBIMP)(μ-NO2)2]1+ (3), have been demonstrated to react with RC(O)SH (R = Me, Ph) to generate the persulfidated complexes, [Co2(PhBIMP)(μ-SSC(O)R)]2+ (R = Me, 5a; Ph, 5b) in high yields (65-72%) along with nitric oxide (71-80%). Characterization of all the products and intermediates by structural and spectroscopic methods, and comparison of the results with those obtained from control experiments, established the generation of [Co2(PhBIMP)(μ-SC(O)R)(MeCN)]2+ (R = Me, 4a; Ph, 4b) and perthionitrite (SSNO-) in the reactions of 2/3 with RC(O)SH, followed by persulfidation of the coordinated thiocarboxylate (RC(O)S-) in 4a and 4b by the in situ generated SSNO- to produce the persulfidated complexes, 5a and 5b, respectively. The present work thus demonstrates, for the first time, that SSNO-, a physiologically relevant S/N-crosstalk species, can effectively mediate the persulfidation of sulfhydryl functional groups and may implicate a similar, but hitherto unknown, role of SSNO- in biological persulfidation processes.
To assess impurity profiles/potential immunogenicity of multiple samples of follow-on or compounded products for two glucagon-like peptide-1 receptor agonists (GLP-1 RAs): semaglutide and liraglutide. Major histocompatibility complex-II-associated peptide proteomics assay (MAPPs), liquid chromatography-mass spectrometry analysis, photostability testing, and fibrillation assay were performed. For semaglutide and liraglutide, various potentially immunogenic peptides (distinct number/distribution vs originators) were presented on impurity-stimulated monocyte-derived dendritic cells from healthy donors. The follow-on drug substance and follow-on or compounded products had distinct impurity profiles (amino acid deletions/additions and unidentified impurities) versus the originators. Significant disparity in strength, impurity sum, and high-molecular-weight protein level were observed between compounded semaglutide and originator products when exposed to light. The liraglutide follow-ons had reduced physical stability versus the originator. The tested peptide impurities pose increased immunogenicity potential. Follow-on or compounded products also had different impurity profiles, which could be affected by the sourcing of the active pharmaceutical ingredient, manufacturing process, and degradation during storage. The distinct impurity profiles of follow-on and compounded products could lead to an undesirable immune response in patients. These results underscore the importance of in vitro immunogenicity assays/clinical immunogenicity studies for GLP-1 RA follow-on or compounded products.
Cell-to-cell signaling between niche and stem cells regulates tissue renewal. While the identity of many mediating factors is known, it is largely unknown whether stem cells optimize their receptiveness to niche signals according to the niche organization. Here, we show that Lgr5+ small intestinal stem cells (ISCs) regulate the morphology and orientation of their secretory apparatus to match the niche architecture, and to increase transport efficiency of niche signal receptors. ISCs orient their Golgi apparatus laterally towards Paneth cells of the epithelial niche, and divide Golgi into multiple stacks. Stem cells with multiple lateral Golgi transport stem cell receptors with a higher efficiency than cells with one single Golgi. The lateral Golgi orientation and enhanced receptor transport requires A-kinase anchor protein 9 (Akap9), and is necessary for normal renewal capacity. Moreover, reduced Akap9 in aged ISCs renders ISCs insensitive to niche-dependent modulation of Golgi stack number and transport efficiency. Our results reveal a stem cell-specific Golgi complex configuration that facilitates efficient niche signal reception and tissue renewal, which is compromised in the aged epithelium.
The 3D-4K exoscope is an emerging digital technology in microneurosurgery. While feasible, its specific impact on surgical efficiency and diagnostic precision during microvascular decompression (MVD) remains under-researched. This study evaluates clinical outcomes, technical nuances, and the technical learning curve of 3D-4K exoscopic MVD for classic trigeminal neuralgia (TN1). A retrospective, longitudinal, single-center study of 37 consecutive patients with refractory TN1 was conducted in 2024. Procedures used a retrosigmoid infra-asterional approach with a robotic 3D-4K exoscope. Outcomes included pain relief, via Visual Analog Scale and Barrow Neurological Institute (BNI) Pain Scale, and surgical efficiency (total operative time). Chronological tertile analysis modeled the learning curve. Mean operative time was 48 ± 13 minutes, a ~ 50% reduction compared to international benchmarks. Chronological analysis showed a significant reduction in operative duration from the early (53.2 min) to the late tertile (40.5 min) (p = 0.017) without added complications. Intraoperative 4K visualization identified additional venous conflicts in 16.2% of cases that were occult on preoperative 3T-MRI. At 6-month follow-up, successful pain relief (BNI I-II) reached 89.2%, with a significant median BNI score improvement from 4 (IQR 4-4) to 2 (IQR 1-4) (p < 0.001). The complication rate was 2.7%, consisting of a single incidental transverse sinus injury successfully managed. 3D-4K exoscopic MVD is safe, and effective. By providing depth perception and a shared real-time visual axis, it enhances diagnostic accuracy for hidden venous conflicts, allowing a rapid technical transition without compromising traditional microscopic standards.
Football coaches commonly provide verbal encouragement and exercise end-point feedback to sustain players' effort by enhancing motivation during fitness training such as high-intensity interval training (HIIT). However, the influence of such cues on the prefrontal cortex (PFC), a region involved in exercise cessation decisions, remains unclear. Therefore, this study aimed to compare the effect of motivational cues on PFC activation during HIIT using functional near-infrared spectroscopy, alongside physiological and perceptual responses. Twenty-two male elite footballers completed two randomised crossover HIIT sessions on a cycle ergometer, with and without motivational cues. Each session consisted of 12 repetitions of 30-s high-intensity bouts, each interspersed with a 30-s active recovery bout. Heart rate, lactate concentration, rating of perceived exertion (RPE), motivation-related questionnaires and oxygenated haemoglobin (HbO2) concentration in the PFC were measured throughout HIIT. Although physiological responses were similar between conditions, perceived difficulty, assessed every three HIIT bouts, was significantly lower under the motivational condition, with lower RPE (p = 0.038) and higher motivation (p = 0.049), engagement (p = 0.038) and mood (p = 0.009) scores, particularly after the 9th repetition. From the 10th to 12th repetition of HIIT, the HbO2 concentrations of the orbitofrontal cortex and frontopolar PFC were significantly lower under the motivational condition (p = 0.040 and p = 0.036, respectively), whereas the dorsolateral and ventrolateral PFC showed no significant difference between conditions. In conclusion, motivational cues reduce central PFC activity during the most fatiguing phases of HIIT, reflecting enhanced neural efficiency under motivation despite equivalent physical workloads.
To estimate the societal costs of Type 1 diabetes (T1D) in France, including direct and indirect costs. We conducted a descriptive retrospective cross-sectional study on all adult patients (aged 18 and over) with T1D identified in the SFDT1 cohort and compared them to a matched cohort of patients without diabetes considering age, gender, deprivation status and geographical area. An Insurance claim data analysis was conducted for the year 2023 individually and then extrapolated to all of France. Costs were broken down by expense categories and insulin delivery devices. The average individual societal cost of T1D in France in 2023 compared with the absence of diabetes was estimated at €9940 (€9340 when considering direct costs only). Nearly half of the identified costs were attributable to the use of medical devices. An analysis stratifying patients by treatment modality (closed-loop, pump or multiple daily injections) highlighted the significant costs associated with the use of the most advanced technologies for delivering insulin (average costs were respectively €13 557, €11 062, and €7004, respectively). The total cost of T1D in France was estimated at between €1.59 and €1.79 billion in 2023 excluding undiagnosed cases and premature mortality associated with the disease. Our results suggest that the most advanced insulin delivery devices have a significant short-term economic impact. Although this paper does not cover the research, model-based studies do suggest that there are some advantages to using such devices, including potential future savings due to lower complication rates.
Mosquitoes transmit arboviruses that represent major global public health challenges. Increasing insecticide resistance and absence of effective antiviral therapies underscore the need for novel vector control strategies. Insect-specific viruses have emerged as candidates for biological control, however, the cellular mechanisms underlying their interactions with mosquito hosts remain poorly understood. Here, we examined the immune response of Aedes albopictus U4.4 cells to Kamiti River virus (KRV) infection, an insect-specific flavivirus. Cells were infected with KRV, and transcriptomic and small RNA profiles were analyzed at 24, 48 and 72 h post-infection. KRV infection induced production of virus-derived small interfering RNAs (vsiRNAs) and virus-derived PIWI-interacting RNA (vpiRNAs) from 24 to 72 h. The vsiRNAs predominantly mapped to the 3' untranslated region of the KRV genome, whereas vpiRNAs formed distinct hotspots in regions encoding the NS1, NS3, NS4A/B and NS5 proteins. Transcriptomic analysis revealed upregulation of genes associated with the humoral immune response, including defensin, cecropin, and glutathione S-transferase, and downregulation of Toll-like receptors and ecdysone-induced transcripts at later stages of infection. These gene expression patterns suggest an early activation followed by suppression of key immune signaling pathways. Collectively, the findings indicate that KRV leads to coordinated modulation of antiviral RNAi and host transcriptional responses, consistent with a balanced, commensal-like interaction in mosquito cells.
This study aimed to investigate the anti-obesity properties of Komagataeibacter rhaeticus SLAM-JS1B derived metabolites, a bacterial strain isolated from kombucha. The effects were assessed in mice with obesity induced by a high-fat diet. Supplementation with K. rhaeticus SLAM-JS1B derived metabolites significantly attenuated body weight gain without altering food intake. Serum total cholesterol, triglyceride, and low-density lipoprotein levels were significantly reduced, together with improved indicators of hepatic damage. In addition, hepatic steatosis and adipose tissue accumulation were markedly attenuated. These metabolic improvements were linked to lower hepatic expression of genes related to lipogenesis and cholesterol production. In the colon, supplementation with K. rhaeticus SLAM-JS1B derived metabolites increased the expression of genes related to intestinal barrier integrity and lowered the expression of pro-inflammatory cytokine genes. Fecal metabolomic analysis further revealed increased fecal cholesterol excretion following K. rhaeticus SLAM-JS1B derived metabolites supplementation. Moreover, gut microbial composition was altered in a manner consistent with improved metabolic status. Collectively, these findings suggest that K. rhaeticus SLAM-JS1B derived metabolites may represent a promising dietary strategy for the prevention or management of obesity and related metabolic disorders, particularly in contexts where the use of live microorganisms is undesirable.
Supramolecular confinement is widely used to control molecular architecture, but its use to direct excited-state reaction pathways remains underexplored. This limitation is particularly evident for spin-forbidden processes such as intersystem crossing (ISC), which are difficult to regulate through supramolecular design. The heavy-atom effect, although central to promoting ISC, is typically regarded as an intrinsic substituent property rather than a geometry-dependent supramolecular parameter. Here we show that macrocycle-directed supramolecular predisposition can deliberately enforce intramolecular heavy-atom effects to activate latent spin-forbidden transitions, enabling efficient self-sensitized oxidation. Encapsulation of a flexible aldehyde- and bromine-substituted guest within cucurbit[8]uril (CB[8]) enforces a folded geometry that juxtaposes the heavy atom and reactive aldehyde, as established by solution studies and single-crystal analysis. Under white-light irradiation, this predisposed complex undergoes selective oxidation of the aldehyde to the corresponding carboxylic acid. Control experiments varying heavy-atom identity, cavity size, and guest binding modes define CB[8]-enforced spatial juxtaposition as the critical structural requirement, while scavenger and EPR studies support triplet-oxygen energy transfer to generate singlet oxygen as the operative pathway. Preferential binding of CB[8] to the substrate over the product mitigates product inhibition and allows catalytic turnover under substoichiometric host loadings. These results show that macrocyclic encapsulation does more than statically stabilize a host-guest complex: it transforms spatial geometry into a structurally gated switch for spin-forbidden pathways, establishing supramolecular predisposition as a versatile design principle for developing switchable photocatalysts and conformationally responsive smart materials.
The innovation of a therapeutic agent with dual anti-inflammatory, anticancer and reversing the dynamic of microtubules like colchicine was crucial. VEGFR2 inhibition has been established as a therapeutic approach for managing cancer, the colchicine site, situated on ß-tubulin and α-tubulin was also considered in cancer development, and metastasis. Moreover, uncontrolled inflammation predisposes to pleiotropic effects leading to cancer development and promoting all stages of tumorigenesis. A polymeric state of a novel one-dimensional palladium-based metal-organic framework (1D Pd-MOF), resulting from the coordination of pyrazine with palladium nuclei to achieve the more pronounced effect of polynuclear characteristics of palladium compared to mononuclear compounds, was designed, synthesized, and screened for its anticancer activity against the A549 lung cancer cell line, with comparison to normal cells. The characterization was performed using different techniques and supported by DFT investigations. The 1D Pd MOF exhibited a potent cytotoxic effect, with an IC50 value of 78.21 ± 0.41 µg/mL against the A549 lung cancer cell line, while showing minimal toxicity toward the normal WI-38 cell line. To investigate the inhibitory activity of the 1D Pd-MOF towards VEGFR2 kinase and to confirm itseffective molecular target, VEGFR2 kinase inhibition was evaluated. The results demonstrated promising VEGFR2 inhibitory activity with a moderate IC50 value of 0.658 ± 0.023 µg/mL, compared with an IC50 value of 0.079 ± 0.003 µg/mL for sorafenib, the reference drug. This activity was further supported by significant inhibition of VEGFR2 gene expression and protein levels compared with untreated control cells. Our results revealed that 1D Pd-MOF is a promising tubulin-interacting compound, as it binds to the colchicine-binding site on tubulin and competes with colchicine in vitro, with an IC50 value of 3.350 ± 0.21 µg/mL. These findings confirm tubulin as a molecular target of the 1D Pd-MOF and support its observed cytotoxic activity. Furthermore, the 1D Pd-MOF significantly upregulated the expression levels of BAX, P53, and caspase-3 genes, while downregulating CDK4, cyclin D1, and BCL2 genes relative to the control group, suggesting growth inhibition and induction of apoptosis in treated lung carcinoma cells. These findings confirm that the 1D Pd-MOF exerts a clear anticancer effect by triggering programmed cell death through apoptosis. In addition, treatment with the 1D Pd-MOF resulted in substantial accumulation of cells in the sub-G1 fraction, accompanied by a corresponding reduction in the G2/M phase, indicating that its cytotoxic efficacy is primarily mediated through apoptosis induction rather than cell cycle arrest at a specific checkpoint. The anti-inflammatory activity of the 1D Pd-MOF was established by its inhibition of nitric oxide (NO) production in LPS-stimulated RAW cells. Molecular docking studies showed good agreement with the experimental biological findings.
We report a direct ortho-dihydroxylation protocol of benzoic acids using a Pd/Mo bimetallic catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant. The Mo component significantly promotes the dihydroxylation reaction, especially the second hydroxylation step, by boosting the oxidative capacity of TBHP and presumably facilitating the oxidative addition process of Pd-Ar σ-intermediate. Mechanistic studies, including radical inhibition experiments, spectroscopic analyses, and substituent effect evaluations, reveal that Mo most likely facilitates the conventional Pd-catalyzed pathway by introducing a radical-generating step. Notably, this dual-metal-mediated method can be readily tuned to afford monohydroxylation products by simply reducing the amount of TBHP. Gram-scale reactions and subsequent derivatizations further confirm the practicality of this method. Since the directing carboxyl group can be easily removed via catalytic or thermal decarboxylation, this Pd/Mo bimetallic catalytic system offers a concise synthetic route to meta-diphenolic compounds, the vital fine chemicals conventionally synthesized via multistep industrial processes.
For physically demanding job standards, simple anthropometric screening tools are useful. Using military personnel as a model, this study evaluated waist-to-height ratio (WHtR) for its relationship with health and performance indicators. Data were analyzed from 2153 active-duty U.S. Marines (1421 men; 732 women). Relationships were assessed between WHtR, a circumference-based "tape test" (TT), body mass index (BMI), and a criterion measure of dual-energy X-ray absorptiometry (DXA)-derived percent body fat (%BF). Associations between WHtR and physical readiness were evaluated using composite scores from the Physical and Combat Fitness Tests (PFT, CFT), and individual performance metrics (pull-ups, crunches, 880-yard sprint time, 3-mile run time, ammo can overhead lifts). WHtR was strongly correlated with DXA %BF (r = 0.754, p < 0.001, men; r = 0.677, p < 0.001, women) and moderately negatively with PFT (r = -0.33, p < 0.001) and CFT (r = -0.30, p < 0.001) scores for men. A graded decline in physical fitness scores was observed with increasing WHtR, with a clear inflection in performance outcomes occurring between WHtR values of approximately 0.48-0.50. Receiver Operating Characteristic (ROC) analysis to identify high %BF showed the TT (AUC: 0.889 men, 0.876 women) performed better than WHtR (AUC: 0.851 men, 0.848 women) and BMI. WHtR is a simple and effective screening tool to identify personnel at potential risk for poor performance outcomes. These findings support use of WHtR as a screening metric and a potential replacement for traditional height-weight screening tables, with a pragmatic threshold of 0.50 to identify individuals who may benefit from secondary assessment, such as from multi-frequency bioelectrical impedance analysis.