Accurate prediction of postoperative complications following radical nephrectomy is of great clinical importance for perioperative risk stratification and patient management. Although several scoring systems are used in urological surgery, there is no widely accepted, procedure-specific risk assessment tool. This study aimed to evaluate the performance of the Physiological and Operative Severity Score for the Enumeration of Mortality and Morbidity (POSSUM), Estimation of Physiologic Ability and Surgical Stress (E-PASS), and its modified version (mE-PASS) in predicting postoperative complications after radical nephrectomy. As a secondary objective, the association between modified Glasgow Prognostic Score (mGPS), Prognostic Nutritional Index (PNI), and neutrophil-to-lymphocyte ratio (NLR), which reflect systemic inflammation and nutritional status, and postoperative complications was also investigated. A total of 148 patients who underwent radical nephrectomy for renal tumors at our institution between January 2022 and March 2025 were retrospectively analyzed. Patients were divided into two groups based on the presence of postoperative complications. Postoperative complications were assessed according to the Clavien-Dindo classification, and complications of grade ≥ 2 were included in the analysis. Demographic characteristics, comorbidities, preoperative laboratory parameters, surgical variables, and postoperative outcomes were recorded. The predictive performance of the scoring systems was evaluated using the area under the receiver operating characteristic (ROC) curve (AUC). Postoperative complications were observed in 51 patients (34.5%). The POSSUM score demonstrated the highest predictive performance with an AUC of 0.810, showing high sensitivity (82.4%) and specificity (71.1%). The E-PASS score was also statistically significant but exhibited a more limited predictive performance (AUC: 0.682). In contrast, the mE-PASS score showed markedly lower predictive ability (AUC: 0.599). Patients who developed complications had significantly lower PNI values and higher NLR values (p < 0.05). Additionally, intraoperative blood loss, tumor size, and length of hospital stay were significantly greater in the complication group (p < 0.05). POSSUM and E-PASS may serve as useful tools for predicting postoperative complications following radical nephrectomy. However, given their moderate predictive performance and the limitations of the present study, these findings should be validated in larger, prospective, multicenter studies.
We have developed a versatile photocatalytic platform for the direct benzylation of diverse C(sp3)-H bonds using N-acyl carbamothioates derived from readily available alcohols as benzyl radical precursors. This protocol operates through two complementary manifolds: a consecutive photoinduced electron transfer (Con-PET) process for the benzylation of N-α-C(sp3)-H bonds and a thiol-mediated hydrogen atom transfer (HAT) cycle for more challenging substrates including alkenes, ethers, thioethers and toluenes. This deoxygenative strategy enables efficient C(sp3)-C(sp3) radical-radical cross-coupling without transition-metal-coupling catalysts, external oxidants, or radical stabilizers, delivering the desired products in moderate to good yields (up to 70%).
DNAzymes, catalytically active DNA molecules, cleave DNA through metal ion cofactors (dia- and paramagnetic cofactors). A radical pathway through which cleavage occurs has been proposed for the Radical Deoxyribozyme3 (RadDz3) system. The integrative approach proposed in this work aims to identify several radical species involved in the DNA-cleaving-DNA architecture. Furthermore, we pinpoint the fine-tuning of the catalytic activity of the paramagnetic cofactors (mainly the high-spin system of Mn2+) combined with the role of different diamagnetic salts. The identified radical species exhibit a role both in the cleavage reaction as well as in the stabilization of the oligonucleotides' architecture. The role played by the EPR multifrequency approach is crucial in delivering consistent and robust spectroscopic parameters. These parameters can contribute to optimal fitting procedures for spectra recorded under several different conditions. This protocol proved particularly effective, despite the superstoichiometric ratio (metal/DNAzyme), typical of catalytic DNAs. The impact of different salts could also be highlighted, either in stabilizing the global architecture or affecting the catalytic activity.
PPOI is one of the common complications of intraperitoneal hyperthermic chemotherapy during laparoscopic radical resection of rectal cancer, which seriously affects the prognosis of patients. The purpose of this study is to establish a prediction system for PPOI secondary to laparoscopic radical resection of rectal cancer combined with intraperitoneal hyperthermic chemotherapy with lobaplatin. Retrospectively analyzed the clinical data of 800 patients who received laparoscopic radical rectal cancer combined with lobaplatin hyperthermia and intraperitoneal chemotherapy in three Level 3 Grade A hospitals from June 1, 2014, to June 1, 2024, and determined the predictive factors through univariate, multivariate, and Lasso regression analysis. We employ eight ML algorithms, Logistic Regression (LR), Decision Tree (DT), Random Forest (RF), Extreme gradient boosting (XGB), Support Vector Machine (SVM), Multilayer Perceptron (MLP), K-Nearest Neighbor (KNN), Gaussian Naive Bayes (GNB), to train and develop ML models using a 10x cross-validation method. The performance of the model was evaluated by a variety of indicators, including the area under the receiver operating characteristic curve (ROC), calibration curve, decision curve, PR curve, and confusion matrix. In addition, model interpretation is performed through Shapley Additive Interpretation (SHAP) analysis to clarify the importance of each feature of the model and its basis for decision-making. We identified six key predictors, including Surgical bleeding, Duration of surgery, HB, WBC, ALB and adhesiolysis, and built a prediction model based on these factors. The sensitivity, specificity, positive predictive value, and negative predictive value of different models were compared. All eight models showed good predictive performance and stability, with the RF model being the optimal model. Finally, we developed a web-based calculator based on the optimal model. These predictors and models were able to assess the potential for PPOI following laparoscopic radical curative rectal cancer combined with lobaplatin hyperthermic intraperitoneal chemotherapy. Early alerts can be provided in a clinical setting, helping medical professionals make informed judgments and select the most appropriate treatment strategy (https://zw17786325639.shinyapps.io/ppoi/).
The rapid decay of target signal strength with distance from the sensor presents a key challenge in nanoscale magnetic sensing with the nitrogen-vacancy (NV) center in diamond, limiting the scope of accessible information as well as the sensitivity and spatial resolution with which that information can be recovered. Here, we introduce a strategy to overcome these limitations by leveraging radical anions formed from rhodamine-derived organic dyes localized to the diamond surface. These radicals, generated through photoreduction, are optically identifiable and persist on time scales exceeding an hour. We experimentally demonstrate their coherent manipulation and detection using single, shallow NV centers for readout. We observe heterogeneity in the local magnetic environments of the photoactivated spins from site to site, likely due to variations in inter-radical dipolar couplings across our measurements. Looking forward, our approach enables correlative nanoscale magnetic/optical imaging and opens new pathways for single-molecule magnetic resonance spectroscopy and quantum many-body simulations in strongly interacting dipolar-coupled spin ensembles.
We report the divergent reactivities of a trisilyl-substituted alane and its radical anionic species towards isocyanides and carbon monoxide. While the neutral Al(III) species forms coordination complexes, the Al(II) radical promotes cyanide formation. Notably, the radical anion mediates CO homologation to yield a C3 fragment, which provides new insight into main-group CO homologation.
This study aimed to assess the prognostic value of preoperative peripheral blood-based inflammatory and nutritional indices in older adults diagnosed with gastric cancer (GC) undergoing radical gastrectomy and to develop a novel composite prognostic score. A retrospective single-center analysis of clinicopathologic data of 609 older adults diagnosed with GC who underwent radical gastrectomy at the Affiliated Hospital of Putian University between 2012 and 2020, was conducted. Multivariate Cox regression analysis was performed to identify independent prognostic factors. A composite score, termed the PNI-dNLR, was constructed using the prognostic nutritional index (PNI) and derived neutrophil-to-lymphocyte ratio (dNLR), and its predictive performance was assessed. Multivariate Cox regression identified both preoperative PNI (hazard ration [HR], 0.74; 95% confidence interval [CI], 0.57-0.97; p = 0.027) and dNLR (HR, 1.44; 95% CI, 1.06-1.94; p = 0.018) as independent prognostic indicators for overall survival (OS) and disease-free survival (DFS). The PNI-dNLR score, derived from these two variables, demonstrated favorable predictive performance as assessed by the Akaike information criterion, Bayesian information criterion, time-dependent concordance index, and time-dependent receiver operating characteristic curve analysis. The PNI-dNLR remained an independent predictor of OS and DFS in multivariate Cox regression models (p < 0.05). Further validation using least absolute shrinkage and selection operator-Cox regression, random survival forest, and survival tree modeling, along with intersecting features from multivariate Cox analysis, supported the prognostic significance of the PNI-dNLR score in this population. Preoperative dNLR and PNI independently predicted long-term postoperative outcomes in older adults undergoing radical gastrectomy for GC. The combined PNI-dNLR score demonstrated predictive value, which need further prospective multicenter study conducting internal and external validation to confirm before clinic application for risk stratification, personalized prognostic assessment, and treatment planning in this patient population.
A photocatalyst-free and electron donor-acceptor (EDA)-complex-enabled radical difluoroalkylation/cyclization of unactivated alkenes with bromodifluoroacetamides has been developed for the efficient synthesis of difluoroalkyl-containing polycyclic coumarin derivatives, affording a total of 32 target compounds. In this transformation, persulfates act as electron donors and bromodifluoroacetamides serve as electron acceptors to generate an EDA complex, enabling visible-light-induced radical processes without the need for external photocatalysts. This method features mild reaction conditions, operational simplicity, metal-free nature, and broad functional group tolerance.
Conventional in situ thermal radical polymerization of electrolytes requires elevated temperatures and typically leads to complete monomer and Li-salt consumption, which severely limits ionic transport and results in an unstable solid-electrolyte interphase (SEI) for lithium metal batteries (LMBs). Here, we propose an ambient cationic activation-radical synergy strategy (CIP), in which PF6- derived Lewis acidic species selectively activate vinylene carbonate (VC) and trigger polymerization at room temperature through a cationic-induced pathway fundamentally distinct from the traditional thermal-initiated process (TIP). Combined theoretical calculations and in situ spectroscopic analyses indicate that PF6- decomposition precedes polymer growth and lowers the activation barrier, enabling controlled polymerization while preserving a fraction of electrochemically active monomers. The resulting gel polymer electrolyte (GPE) exhibits accelerated ionic transport kinetics with an elevated transference number of 0.78 and an ionic conductivity of 6.49 × 10-3 S cm-1. When applied in LMBs, this electrolyte promotes the formation of a dense, inorganic-rich, and dynamically reinforced SEI, enabling stable lithium plating/stripping over 2000 h, sustained cycling over 1200 cycles at 0.5 C, and excellent rate capability up to 10 C, demonstrating its promise for high-performance LMBs.
Prostate cancer is the most common cancer affecting men in the United Kingdom. Single-port robot-assisted radical prostatectomy (SP-RARP) is one of the latest evolutions in the realm of minimally invasive surgery for prostate cancer. We aim to describe our institution's initial experience with single-port robot-assisted radical prostatectomy. We retrospectively reviewed all the electronic theatre records to identify all patients undergoing Single-port robot-assisted radical prostatectomy. All cases were performed using the da Vinci SP Surgical System from September 2024 to December 2025. This review was registered and carried out in line with the Trust's audit & research guidelines. A total of 50 patients underwent SP-RARP. The median patient age was 61 years, with a mean BMI of 27 kg/m² and an ASA grade distribution of 1-3. The median operative time was 120 min (86-180), and the median estimated blood loss was 100 mL (20-400). No intra-operative complications were recorded. Nerve-sparing was performed bilaterally in 25 patients, unilaterally in 22, and was not performed in 3 cases. The median initial post-operative pain score was 0.9, and the median length of stay was 1 day. At three months, 68% of patients were fully continent, and 75% achieved erectile function sufficient for intercourse with phosphodiesterase-5 inhibitors with or without vacuum device support. Final pathological staging showed pT2b disease in 3 patients, pT2c in 23, pT3a in 23, and pT3b in 1. A positive surgical margin greater than 3 mm was identified in one patient. This represents the first UK case series of SP-RARP. Early outcomes demonstrate the procedure to be feasible and safe, with operative, oncological, and functional results comparable to published international SP-RARP data. These findings support the need for further comparative studies against multi-port RARP to better define the relative advantages of the single-port platform.
Microplastic-derived dissolved organic matter (MP-DOM) plays an important role in aquatic environments; however, its influence on the photodegradation of plastic additives remains unclear. In this study, bisphenol A (BPA) was selected as a representative plastic additive to investigate the effects of polystyrene-derived DOM (PS-DOM) on the photodegradation kinetics and mechanisms of BPA at different concentrations. PS-DOM significantly enhanced the photodegradation of BPA, with the promoting effect becoming more pronounced at lower BPA concentrations. Kinetic modeling revealed that as BPA levels decrease from high to low, the dominant contributor to BPA photodegradation shifts from the excited triplet state of PS-DOM (generated via photosensitization) to long-lived organic radicals (LLORs). This finding highlights the indispensable role of LLORs in the photodegradation of trace-level BPA (nM-μM) in surface waters. Probe experiments revealed that the one-electron reduction potentials of LLORs generated by various MP-DOM are around 1.50 V, indicating that LLORs have the potential to degrade plastic additives with oxidation potentials below this range. Furthermore, correlation analysis revealed that variations in unsaturated functional groups and electron-donating moieties (e.g., tannins and lignins) within MP-DOM were key factors controlling the quantum yield coefficients of LLORs across different MP-DOM types. This study provides novel insights into the photochemical reactivity of MP-DOM and its potential role in regulating the environmental transformation of plastic additives.
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Schisandra chinensis, a traditional Chinese medicine-food homologous plant, is widely used for alleviating oxidative stress induced damage in hepatocytes and neurons due to its antioxidant activity. However, significant gaps remain in the research regarding the sequence, structure, and antioxidant mechanism of its bioactive peptides. Herein, we aimed to evaluate the antioxidant capacity of S. chinensis peptides (SCP), screen the optimal bioactive peptide sequences, and elucidate underlying antioxidant mechanisms. The results demonstrated that SCP exhibited potent free radical scavenging activity, with scavenging rates of over 90% and 50% against DPPH and ABTS radicals at 10 mg/mL, respectively. At 100 μg/mL, SCP restored the levels of ROS and MDA in UVB-induced HaCaT to those of the undamaged control group. Meanwhile, SCP maintained over 65% DPPH radical scavenging activity under various physicochemical conditions and exhibited excellent biosafety with a hemolysis rate below 0.8% at a high concentration of 8 mg/mL. In total, 63 bioactive peptides were identified through peptidome and bioinformatics analyses, and 8 high affinity peptides for DPPH and ABTS were further screened out. FF4, FW4, and IL6 were capable of forming stable complexes with Keap1, primarily driven by hydrogen bonds and hydrophobic interactions, as revealed by molecular docking and molecular dynamics simulations. Specifically, the Keap1-IL6 complex showed the most stable conformation, with DPPH and ABTS radical scavenging rates above 50% at 10 mg/mL and hemolytic activity below 10%. Collectively, these findings provide a scientific basis for clarifying the molecular mechanism of SCP in regulating antioxidant pathway and facilitating its subsequent industrialization.
To address the problem of low efficiency in activating peroxymonosulfate (PMS) by ordinary copper slag for degrading organic pollutants, doping modification is the key to improving its activity. In this study, an in-situ synthesis method was used to prepare a nitrogen-doped mesoporous material from waste copper slag (Fe-N1/8), which can effectively degrade Rhodamine B (RhB). Single-factor experiments showed that Fe-N1/8 exhibited excellent catalytic performance at a low PMS concentration (0.25 mM - 1 mM), achieving 100% degradation of RhB (50 mg/L) within 15 minutes. Stability tests revealed that Fe-N1/8 maintained its significant PMS activation effect, strong magnetism, excellent acid-base tolerance (pH = 3 - 11), and good anion interference resistance (Cl-, NO3-, H2PO4-, etc.) during three degradation cycles. Meanwhile, VSM tests indicated that Fe-Ni/e has strong magnetism, which is beneficial for the recovery and reuse of the catalyst. Free radical scavenging experiments and ROS identification analysis confirmed that in the Fe-N1/8/PMS system, there is a synergistic effect between non-radical pathways (1O2, electron transfer) and radicals (SO4-·, ·OH), along with an effective cycle of Fe(II) and Fe(III), among which 1O2 is the main active substance driving rapid degradation. LC-MS analysis identified the intermediate products during the degradation process, and the degradation pathways and mechanisms were proposed. Additionally, the toxicity of the intermediate products was analyzed using ECOSAR software and seed germination tests. This study successfully developed an environmentally friendly functional material using industrial solid waste, achieving the goal of "treating waste with waste" and providing a new perspective for the high-value utilization of copper slag and the purification of dye-containing wastewater.
Hyaluronate-coated novasomes as an eco-innovative delivery system to enhance the antimicrobial and antioxidant efficacy of Beta vulgaris subsp. cicla (BV) aerial parts extracts were developed and characterised in this study. The phytochemical profile was established using GC-MS and LC-MS/MS, along with the isolation of key biomarkers. Two novasome formulations (BV1 and BV2) were synthesized, and the optimized BV1 was subjected to comprehensive characterization, including encapsulation efficiency (EE), particle size, zeta potential, FTIR, and TEM. The biological activities were evaluated via DPPH radical scavenging and agar well assays against Staphylococcus aureus, Escherichia coli, and Candida albicans. GC-MS analysis of the dichloromethane fraction identified 15 compounds (89.64%), dominated by fatty acids: oleic acid (30.52%), palmitic acid (21.92%), and stearic acid (10.50%). LC-MS/MS analysis of the ethanolic extract revealed 33 metabolites, primarily flavonoids and phenolic acids. The isolated compounds included oleanolic acid, campesterol, isovitexin, and apigenin-O-hexoside. While the crude extract exhibited limited antimicrobial activity (effective only against C. albicans), encapsulation within hyaluronate-coated novasomes significantly enhanced its biopotency. BV1 exhibited some inhibitory trends against all tested microorganisms, whereas BV2 was effective only against bacterial strains. Regarding radical scavenging activity, BV1 exhibited significantly higher antioxidant activity (IC50 33.4 µL/mL) than the crude extract (IC50 55.2 µL/mL) and BV2 (IC50 82.6 µL/mL). The results demonstrate that hyaluronate-coated novasomes serve as a superior delivery vehicle, expanding the limited antimicrobial profile of Beta vulgaris extract and preserving its antioxidant capacity.
Agro-industrial byproducts are recognized as sustainable sources of bioactive compounds with potential applications in functional foods. Pomegranate peel and coarse powdered date seeds are among the most abundant fruit processing residues, yet remain underutilized despite their rich in polyphenols, organic acids and other phytochemicals composition. This study aimed to comparatively evaluate the antioxidant, cytoprotective, acetylcholinesterase inhibitory, and anti-arthritic activities of pomegranate peel powder (PPP) and coarse powdered date seeds (CPDS) using a panel of in vitro assays. Antioxidant capacity was assessed by DPPH radical scavenging and reducing power methods, while cytoprotective activity was evaluated using erythrocyte membrane stabilization and protective against oxidative DNA damage methods. Anti-arthritic potential was determined using protein denaturation and proteinase inhibition methods, and acetylcholinesterase inhibitory activity was also examined. PPP exhibited significantly higher activity compared to CPDS across most assays. PPP demonstrated stronger DPPH radical scavenging activity (IC50 = 6.73 µg/mL) compared to CPDS (IC50 = 19.18 µg/mL), along with enhanced anti-hemolytic activity (IC50 = 155.14 ± 1.58 µg/mL vs. 287.02 ± 2.93 µg/mL for CPDS) and stronger protein denaturation inhibition (44.73% vs. 35.78%, p < 0.05). These findings suggest that the superior biological activity of PPP may be attributed to its higher phenolic content . This supports the idea of using chemicals from pomegranate peel in functional foods and nutraceutical formulas that aim to make cells stronger and lower the health risks associated with inflammation.
Breast cancer remains a major global health challenge, necessitating the exploration of safer and effective plant-derived therapeutics. Thalictrum foliolosum DC. (Pili Jadi), a medicinal herb widely used in Himalayan traditional medicine, is known to contain bioactive alkaloids and phenolic compounds with potential pharmacological properties. The present study investigated the phytochemical composition, antioxidant potential, HPTLC fingerprinting, and In-vitro cytotoxic activity of marketed T. foliolosum root extract against MCF-7 breast cancer cells. Preliminary phytochemical screening revealed the presence of alkaloids, flavonoids, phenolics, tannins, saponins, and terpenoids. The total phenolic content of the ethanolic root extract was determined as 16.80 ± 1.82 mg GAE/g dry weight using the Folin-Ciocalteu assay. Antioxidant activity evaluated by the DPPH radical scavenging assay demonstrated concentration-dependent activity, with the aqueous fraction exhibiting the strongest antioxidant potential (82% radical scavenging activity at 800 µg/mL; IC₅₀ = 313.5 µg/mL), followed by the ethyl acetate fraction. HPTLC fingerprinting confirmed the presence of characteristic phytochemical markers, including quercetin (Rf ≈ 0.51) and berberine (Rf ≈ 0.12). Cytotoxic evaluation using the MTT assay showed a mild dose-dependent reduction in MCF-7 cell viability, with 91.03% viability observed at 100 µg/mL and IC₅₀ > 100 µg/mL. The findings indicate that marketed T. foliolosum roots possess significant antioxidant phytochemicals and identifiable bioactive constituents supporting their traditional therapeutic claims. Further studies involving phytochemical isolation, mechanistic investigations, and in vivo validation are warranted to explore their full anticancer potential.
The formation of carbonate radicals (·CO3-) via carbonate-hydroxyl radicals (·OH) reaction is the cornerstone of environmental oxidative cycles, yet its molecular mechanism has long been limited to homogeneous bulk-phase paradigms, a view that conflicts with enhanced reactivity in interfacial-rich systems. Characterizing these processes is hindered by the transience of ·OH, system heterogeneity, and the inability to resolve in situ pathways. Herein, we combine ab initio molecular dynamics and machine learning molecular dynamics to redefine ·CO3- formation chemistry. We reveal that the gas-liquid interfacial reaction dominates ·CO3- generation, mediated by two proton-coupled electron transfer pathways (concerted proton-electron transfer and stepwise proton-transfer followed by electron-transfer). Critical to this reactivity are Zundel/Zundel-like hydrogen-bonded configurations, which act as "molecular switches" to trigger rapid reactions, enabled by the intrinsic interfacial enrichment of ·OH (85.2%) and HCO3- (92.2%). The interfacial pathway outperforms bulk reactions in ·CO3- formation, with (90 ± 6.13)% yield [vs (80 ± 8.94)% in bulk] and approximately 100-fold faster rate [(1.15 ± 0.01) × 1011 M-1 s-1 vs (9.63 ± 0.03) × 108 M-1 s-1], attributed to the partial solvation of ·OH at the interface. Additionally, ·OH reacts with bulk-phase CO32- via heterogeneous electron transfer (bulk → interface), yielding a rate approximately 10-fold faster ·CO3- formation than homogeneous bulk reactions. These findings challenge bulk-centric paradigms, establish the interface as the dominant ·CO3- source, and provide actionable insights for optimizing advanced oxidation processes, water remediation, and catalyst design by leveraging interfacial microenvironments.
Given the high incidence of postoperative cognitive decline and reduced self-efficacy in lung cancer patients undergoing radical thoracoscopic surgery, this study aimed to investigate the effect of evidence-based nursing combined with health empowerment intervention on self-efficacy and cognitive function in this patient population. A total of 516 patients who underwent thoracoscopic radical lung cancer surgery between February 2021 and June 2025 in The First People's Hospital of Zunyi were included. The patients were divided into an observation group (232 cases, who received evidence-based nursing combined with health empowerment intervention) and a control group (284 cases, who received conventional nursing). General data of the patients, along with their visual analogue scale (VAS) scores, forced vital capacity (FVC), maximal voluntary ventilation (MVV), forced expiratory volume in 1 second to FVC ratio (FEV1/FVC), General Self-Efficacy Scale (GSES) score, and Mini-Mental State Examination (MMSE) score, were collected. There was no significant difference between the two groups in terms of baseline characteristics (p > 0.05). After the intervention, the observation group achieved significantly greater improvement than the control group in terms of VAS pain scores, pulmonary function indices (FVC, MVV, FEV1/FVC), GSES scores and MMSE scores (p < 0.001). In addition, the total incidence of postoperative adverse reactions was significantly lower in the observation group than in the control group (7.76% vs. 13.73%, p = 0.031). Evidence-based nursing combined with health empowerment intervention significantly relieves postoperative pain, promotes recovery of lung function, enhances self-efficacy and cognitive function, and reduces the incidence of postoperative adverse events.