Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms.

Tailoring materials with prescribed properties and regular structures is a critical and challenging research topic. Early transition metals were found to form supermagic M8C12 metallocarbohedrenes (Met-Cars); however, stable metal carbides are not limited to this common stoichiometry. Utilizing self-developed deep-ultraviolet laser ionization mass spectrometry, here, we report a strategy to generate new titanium carbides by reacting pure Tin clusters with acetylene. Interestingly, two products corresponding to Ti17C2 and Ti19C10 exhibit superior abundances in addition to the Ti8C12 Met-Cars. Using global-minimum search, the structures of Ti17C2 and Ti19C10 are determined to be an ellipsoidal D4d and a rod-shaped D5h geometry, respectively, both with carbon-capped Ti4C moieties and superatomic features. We illustrate the electronic structures and bonding nature in these carbon-doped superatoms concerning their enhanced stability and local aromaticity, shedding light on a new class of metal-carbide nanomaterials with atomic precision.

Polynuclear Cobalt Cluster-Based Coordination Polymers for Efficient Nitrate-to-Ammonia Electroreduction.

The electrocatalytic nitrate reduction reaction (NITRR) holds great promise for purifying wastewater and producing valuable ammonia (NH3). However, the lack of efficient electrocatalysts has impeded the achievement of highly selective NH3 synthesis from the NITRR. In this study, we report the design and synthesis of two polynuclear Co-cluster-based coordination polymers, {[Co2(TCPPDA)(H2O)5]·(H2O)9(DMF)} and {Co1.5(TCPPDA)[(CH3)2NH2]·(H2O)6(DMF)2} (namely, NJUZ-2 and NJUZ-3), which possess distinct coordination motifs with well-defined porosity, high-density catalytic sites, accessible mass transfer channels, and nanoconfined chemical environments. Benefitting from their intriguing multicore metal-organic coordination framework structures, NJUZ-2 and NJUZ-3 exhibit remarkable catalytic activities for the NITRR. At a potential of -0.8 V (vs. RHE) in an H-type cell, they achieve an optimal Faradaic efficiency of approximately 98.5% and high long-term durability for selective NH3 production. Furthermore, the electrocatalytic performance is well maintained even under strongly acidic conditions. When operated under an industrially relevant current density of 469.9 mA cm-2 in a flow cell, a high NH3 yield rate of up to 3370.6 mmol h-1 g-1cat. was observed at -0.5 V (vs. RHE), which is 20.1-fold higher than that obtained in H-type cells under the same conditions. Extensive experimental analyses, in combination with theoretical computations, reveal that the great enhancement of the NITRR activity is attributed to the preferential adsorption of NO3- and the reduction in energy input required for the hydrogenation of *NO3 and *NO2 intermediates.

The vasculogenic mimicry related signature predicts the prognosis and immunotherapy response in renal clear cell carcinoma.

BACKGROUND: Clear cell carcinoma of the kidney is a common urological malignancy characterized by poor patient prognosis and treatment outcomes. Modulation of vasculogenic mimicry in tumor cells alters the tumor microenvironment and the influx of tumor-infiltrating lymphocytes, and the combination of its inducers and immune checkpoint inhibitors plays a synergistic role in enhancing antitumor effects. METHODS: We downloaded the data from renal clear cell carcinoma samples and vasculogenic mimicry-related genes to establish a new vasculogenic mimicry-related index (VMRI) using a machine learning approach. Based on VMRI, patients with renal clear cell carcinoma were divided into high VMRI and low VMRI groups, and patients' prognosis, clinical features, tumor immune microenvironment, chemotherapeutic response, and immunotherapeutic response were systematically analyzed. Finally, the function of CDH5 was explored in renal clear cell carcinoma cells. RESULTS: VMRI can be used for prognostic and immunotherapy efficacy prediction in a variety of cancers, which consists of four vasculogenic mimicry-related genes (CDH5, MMP9, MAPK1, and MMP13), is a reliable predictor of survival and grade in patients with clear cell carcinoma of the kidney and has been validated in multiple external datasets. We found that the high VMRI group presented higher levels of immune cell infiltration, which was validated by pathological sections. We performed molecular docking prediction of vasculogenic mimicry core target proteins and identified natural small molecule drugs with the highest affinity for the target protein. Knockdown of CDH5 inhibited the proliferation and migration of renal clear cell carcinoma. CONCLUSIONS: The VMRI identified in this study allows for accurate prognosis assessment of patients with renal clear cell carcinoma and identification of patient populations that will benefit from immunotherapy, providing valuable insights for future precision treatment of patients with renal clear cell carcinoma.

Sandwiched Epitaxy Growth of 2D Single-Crystalline Hexagonal Bismuthene Nanoflakes for Electrocatalytic CO2 Reduction.

Two-dimensional (2D) bismuthene is predicted to possess intriguing physical properties, but its preparation remains challenging due to the high surface energy constraint. Herein, we report a sandwiched epitaxy growth strategy for the controllable preparation of 2D bismuthene between a Cu foil substrate and a h-BN covering layer. The top h-BN layer plays a crucial role in suppressing the structural transformation of bismuthene and compensating for the charge transfer from the bismuthene to the Cu(111) surface. The bismuthene nanoflakes present a superior thermal stability up to 500 °C in air, attributed to the passivation effect of the h-BN layer. Moreover, the bismuthene nanoflakes demonstrate an ultrahigh faradaic efficiency of 96.3% for formate production in the electrochemical CO2 reduction reaction, which is among the highest reported for Bi-based electrocatalysts. This study offers a promising approach to simultaneously synthesize and protect 2D bismuthene nanoflakes, which can be extended to other 2D materials with a high surface energy.

A Self-Templated Design Approach toward Multivariate Metal-Organic Frameworks for Enhanced Oxygen Evolution.

Multivariate metal-organic framework (MOF) is an ideal electrocatalytic material due to the synergistic effect of multiple metal active sites. In this study, a series of ternary M-NiMOF (M = Co, Cu) through a simple self-templated strategy that the Co/Cu MOF isomorphically grows in situ on the surface of NiMOF is designed. Owing to the electron rearrange of adjacent metals, the ternary CoCu-NiMOFs demonstrate the improved intrinsic electrocatalytic activity. At optimized conditions, the ternary Co3 Cu-Ni2 MOFs nanosheets give the excellent oxygen evolution reaction (OER) performance of current density of 10 mA cm-2 at low overpotential of 288 mV with a Tafel slope of 87 mV dec-1 , which is superior to that of bimetallic nanosheet and ternary microflowers. The low free energy change of potential-determining step identifies that the OER process is favorable at Cu-Co concerted sites along with strong synergistic effect of Ni nodes. Partially oxidized metal sites also reduce the electron density, thus accelerating the OER catalytic rate. The self-templated strategy provides a universal tool to design multivariate MOF electrocatalysts for highly efficient energy transduction.

Highly Efficient Electrochemical Nitrate Reduction to Ammonia in Strong Acid Conditions with Fe2 M-Trinuclear-Cluster Metal-Organic Frameworks.

Nitrate-containing industrial wastewater poses a serious threat to the global food security and public health safety. As compared to the traditional microbial denitrification, electrocatalytic nitrate reduction shows better sustainability with ultrahigh energy efficiency and the production of high-value ammonia (NH3 ). However, nitrate-containing wastewater from most industrial processes, such as mining, metallurgy, and petrochemical engineering, is generally acidic, which contradicts the typical neutral/alkaline working conditions for both denitrifying bacteria and the state-of-the-art inorganic electrocatalysts, leading to the demand for pre-neutralization and the problematic hydrogen evaluation reaction (HER) competition and catalyst dissolution. Here, we report a series of Fe2 M (M=Fe, Co, Ni, Zn) trinuclear cluster metal-organic frameworks (MOFs) that enable the highly efficient electrocatalytic nitrate reduction to ammonium under strong acidic conditions with excellent stability. In pH=1 electrolyte, the Fe2 Co-MOF demonstrates the NH3 yield rate of 20653.5 µg h-1 mg-1 site with 90.55 % NH3 -Faradaic efficiency (FE), 98.5 % NH3 -selectivity and up to 75 hr of electrocatalytic stability. Additionally, successful nitrate reduction in high-acidic conditions directly produce the ammonium sulfate as nitrogen fertilizer, avoiding the subsequent aqueous ammonia extraction and preventing the ammonia spillage loss. This series of cluster-based MOF structures provide new insights into the design principles of high-performance nitrate reduction catalysts under environmentally-relevant wastewater conditions.

Discovery of Electronic Structure and Interfacial Interaction Features in Catalytic Activity.

The selective transformation of inert bonds (C-H, C-O, C-C, C-F, etc.) via various catalysts is one of the most challenging areas, with applications in organic synthesis, materials science, and biological and pharmaceutical chemistry. The catalytic performance of homogeneous and heterogeneous catalysts can be rationally controlled in two ways: (i) electronic structure modulation of the active site, such as the metal center, ligands, and coordination modes, to improve the catalytic activity and stability and (ii) tuning intermolecular or interfacial interactions to promoting the reaction kinetics by accelerating the transmission of electrons between the catalyst and solvents or support. The rational design of catalysts based on adjustable features, such as metal (monometallic or bimetallic) active sites, crystal phase, ligands, solvents, and supports for inert bond activation under mild conditions remains a challenge. This Perspective summarizes the features of electronic structures, interfacial interactions, and their effects on molecular catalysis, metal-organic frameworks (MOFs), and natural mineral catalysis. The discovery of efficient catalysts could be promoted using machine-learning methods with high-performance descriptors. More attention should be paid to high-throughput quantum-chemical computations and experiments, automatic searches of chemical reaction pathways, and efficient machine-learning or deep-learning methods to accelerate catalyst design and synthesis in the future.

Batch-Scale Synthesis of Nanoparticle-Agminated Three-Dimensional Porous Cu@Cu2O Microspheres for Highly Selective Electrocatalysis of Nitrate to Ammonia.

The electrochemical nitrate reduction reaction (NITRR), which converts nitrate to ammonia, is promising for artificial ammonia synthesis at mild conditions. However, the lack of favorable electrocatalysts has hampered its large-scale applications. Herein, we report the batch-scale synthesis of three-dimensional (3D) porous Cu@Cu2O microspheres (Cu@Cu2O MSs) composed of fine Cu@Cu2O nanoparticles (NPs) using a convenient electric explosion method with outstanding activity and stability for the electrochemical reduction of nitrate to ammonia. Density functional theory (DFT) calculations revealed that the Cu2O (111) facets could facilitate the formation of *NO3H and *NO2H intermediates and suppress the hydrogen evolution reaction (HER), resulting in high selectivity for the NITRR. Moreover, the 3D porous structure of Cu@Cu2O MSs facilitates electrolyte penetration and increases the localized concentration of reactive species for the NITRR. As expected, the obtained Cu@Cu2O MSs exhibited an ultrahigh NH3 production rate of 327.6 mmol·h-1·g-1cat. (which is superior to that of the Haber-Bosch process with a typical NH3 yield <200 mmol h-1g-1cat.), a maximum Faradaic efficiency of 80.57%, and remarkable stability for the NITRR under ambient conditions. Quantitative 15N isotope labeling experiments indicated that the synthesized ammonia originated from the electrochemical reduction of nitrate. Achieving the batch-scale and low-cost production of high-performance Cu@Cu2O MSs electrocatalysts using the electric explosion method is promising for the large-scale realization of selective electrochemical reduction of nitrate toward artificial ammonia synthesis.

In(III) Metal-Organic Framework Incorporated with Enzyme-Mimicking Nickel Bis(dithiolene) Ligand for Highly Selective CO2 Electroreduction.

Inspired by the exciting physical/chemical properties in metal-organic frameworks (MOFs) of the redox-active tetrathiafulvalene (TTF) ligands, nickel bis(dithiolene-dibenzoic acid), [Ni(C2S2(C6H4COOH)2)2], has been designed and developed as an inorganic analogue of the corresponding TTF-type donors (such as tetrathiafulvalene-tetrabenzoate, TTFTB), where a metal site (Ni) replaces the central C═C bond. In this work, [Ni(C2S2(C6H4COOH)2)2] and In3+ have been successfully assembled into a three-dimensional MOF, (Me2NH2+){InIII-[Ni(C2S2(C6H4COO)2)2]}·3DMF·1.5H2O (1, DMF = N,N-dimethylformamide), with satisfying chemical and thermal stabilities. With the combination of reversible redox activity and unsaturated metal sites originated from [Ni(C2S2(C6H4COOH)2)2], 1 showed a significantly enhanced performance in electrocatalytic CO2 reduction compared with the isomorphic MOF, (Me2NH2+)[InIII-(TTFTB)]·0.7C2H5OH·DMF (2, with TTFTB ligand). More importantly, by mimicking the active [NiS4] sites of formate dehydrogenase and CO-dehydrogenase, a prominently higher conversion rate and Faradaic efficiency (FE), with FEHCOO- increasing from 54.7% to 89.6% (at -1.3 V vs RHE, jHCOO- = 36.0 mA cm-2), were achieved in 1. Mechanistic investigations further confirm that [NiS4] can serve as a CO2 binding site and efficient catalytic center. This unprecedented effect of redox-active nickel dithiolene-based MOF catalysts on the performance of electroreduction of CO2 provides an important strategy for designing stable and efficient crystalline enzyme-mimicking catalysts for the conversion of CO2 into high-value chemical stocks.

Shear viscosity prediction of alcohols, hydrocarbons, halogenated, carbonyl, nitrogen-containing, and sulfur compounds using the variable force fields.

Viscosity of organic liquids is an important physical property in applications of printing, pharmaceuticals, oil extracting, engineering, and chemical processes. Experimental measurement is a direct but time-consuming process. Accurately predicting the viscosity with a broad range of chemical diversity is still a great challenge. In this work, a protocol named Variable Force Field (VaFF) was implemented to efficiently vary the force field parameters, especially λvdW, for the van der Waals term for the shear viscosity prediction of 75 organic liquid molecules with viscosity ranging from -9 to 0 in their nature logarithm and containing diverse chemical functional groups, such as alcoholic hydroxyl, carbonyl, and halogenated groups. Feature learning was applied for the viscosity prediction, and the selected features indicated that the hydrogen bonding interactions and the number of atoms and rings play important roles in the property of viscosity. The shear viscosity prediction of alcohols is very difficult owing to the existence of relative strong intermolecular hydrogen bonding interaction as reflected by density functional theory binding energies. From radial and spatial distribution functions of methanol, we found that the van der Waals related parameters λvdW are more crucial to the viscosity prediction than the rotation related parameters, λtor. With the variable λvdW-based all-atom optimized potentials for liquid simulations force field, a great improvement was observed in the viscosity prediction for alcohols. The simplicity and uniformity of VaFF make it an efficient tool for the prediction of viscosity and other related properties in the rational design of materials with the specific properties.

Successive Storage of Cations and Anions by Ligands of π-d-Conjugated Coordination Polymers Enabling Robust Sodium-Ion Batteries.

The oxidation of π-d-conjugated coordination polymers (CCPs) accompanied with anion insertion has the merits of increasing the capacity and elevating the discharge voltages. However, previous reports on this mechanism either required more investigations or showed low capacity and poor cyclablity. Herein, triphenylene-catecholate-based two-dimensional CCPs are constructed by employing inactive transition-metal ions (Zn2+ ) as nodes, forming Zn-HHTP. Substantial characterizations and theoretical calculations indicate the successive storage of cations and anions by redox reactions of only ligands, leading to a high reversible capacity of ≈150 mAh g-1 at 100 mA g-1 and a remarkable capacity retention of 90 % after 1000 cycles. On the contrary, as a control experiment, the analogous CCPs (Cu-HHTP) with Cu2+ nodes, where both ligands and metal ions undergo redox reactions, accompanied by the storage of only Na+ cations, show a much poorer cyclability. These results highlight the importance of redox reactions of only ligands for long-term cycle life and the insight into the storage mechanisms deepens our understanding on CCPs for the further design of CCPs with high performance.

Hydrogen Bonding Promoted Tautomerism between Azo and Hydrazone Forms in Calcon with Multistimuli Responsiveness and Biocompatibility.

Realization of multistimuli responsiveness in one molecule remains a challenge due to the difficulty in understanding and control of comprehensive interplay between the external stimuli and the subtle conformation changes. The coexistence of dynamic bonding interactions, hydroxyl group, and the azo chromophore in calcon causes the multistimuli responsiveness to external stimuli including temperature, pH variation, and light irradiation. Density functional theory (DFT), time-dependent DFT (TDDFT), and various molecular dynamics (MD) simulations are employed to systematically investigate the azo-hydrazone tautomerism and E-to- Z isomerization. The inter/intramolecular hydrogen bonding interactions promote the azo-hydrazone tautomerism at different pH conditions. The strong n → π* absorption in the visible light region gives an advantage of calcon without the harm to living cells from UV light. The facial tautomerism renders the calcon temperature sensitivity, which could be triggered at body temperature (311 K) with distinct color change from red to blue. It is also found that in pH = 6.8 both azo and hydrazone isomers have no cytotoxicity on the human lung cells (A549 and H1299) and hepatic epithelial cell of rat (FL83B). The visible-light absorption, pH, and temperature sensitiveness and biocompatibility render calcon potential candidates for biomedical applications.

Charge-Storage Aromatic Amino Compounds for Nonvolatile Organic Transistor Memory Devices.

Here, charge-storage nonvolatile organic field-effect transistor (OFET) memory devices based on interfacial self-assembled molecules are proposed. The functional molecules contain various aromatic amino moieties (N-phenyl-N-pyridyl amino- (PyPN), N-phenyl amino- (PN), and N,N-diphenyl amino- (DPN)) which are linked by a propyl chain to a triethoxysilyl anchor group and act as the interface modifiers and the charge-storage elements. The PyPN-containing pentacene-based memory device (denoted as PyPN device) presents the memory window of 48.43 V, while PN and DPN devices show the memory windows of 24.88 and 8.34 V, respectively. The memory characteristic of the PyPN device can remain stable along with 150 continuous write-read-erase-read cycles. The morphology analysis confirms that three interfacial layers show aggregation due to the N atomic self-catalysis and hydrogen bonding effects. The large aggregate-covered PyPN layer has the full contact area with the pentacene molecules, leading to the high memory performance. In addition, the energy level matching between PyPN molecules and pentacene creates the smallest tunneling barrier and facilitates the injection of the hole carriers from pentacene to the PyPN layer. The experimental memory characteristics are well in agreement with the computational calculation.

[Application of suprarenal inferior vena cava filter placement in patients with venous thromboembolism].

OBJECTIVE: To evaluate the safety and efficacy of suprarenal inferior vena cava (IVC) filter implantation in patients with venous thromboembolism (VTE). METHODS: Between May 2006 and December 2014, 28 patients with VTE underwent suprarenal IVC filter implantation, anticoagulant treatment and/or catheter-directed thrombolysis at the affiliated hospital of Xuzhou medical college. Follow up examination with color Doppler ultrasound was taken after treatment to eassess the patency of IVC. RESULTS: One filter was successfully implanted in suprarenal IVC in each patient intraoperatively. The filter was retrieved in 26 patients after indwelling of 5 to 17 (mean 11 ± 3) days. The filter was permanently indwelled in 2 patients. There were no complications of filter tilt and migration in all cases. Twenty eight patients were followed up for 2 to 104 (mean 34 ± 34) months. None of the 2 patients whose filters were permanently indwelled presented complications of recurrent pulmonary embolism and IVC occlusion due to the filter. Among 26 patients whose filters were retrieved, the IVC was patent. CONCLUSION: Suprarenal IVC filter placement is a safe and effective method in the treatment of VTE.

[MRV comparison of the angle between the right hepatic vein and the inferior vena cava for patients with membranous obstruction of the inferior vena cava].

OBJECTIVE: To determine whether there are differences in both the right hepatic vein (RHV) morphology and the size of the angle between the inferior vena cava and the RHV in patients with membranous obstruction of the inferior vena cava (MOVC),in healthy individuals and in patients with cinhosis (HLC), in order to help guide development of an effective interventional treatment program. METHODS: Consecutive patients (n=248) were divided into the following three groups: group A (control; n=94), group B (MOVC patients; n=68), group C (HLC patients; n=86). The angle between the hepatic vein and inferior vena cava was measured and defined as the T value. The morphology of the RHV was classified as N, U, or I. The difference of the constituent ratio was compared among the three groups for the T value and the angle type.Measurement data was calculated as x ± s,and groups were compared using one-way ANOVA; count data was calculated as relative number, and groups were compared using the chi-square test. RESULTS: The average T value of group B was significantly higher than that of group A (56.1 ± 13.7 vs. 49.3 ± 7.8, P=0.010) and of group C (vs. 51.5 ± 10.0, P < 0.001); the difference was statistically significant (F=8.750, P < 0.001), but there was no significant difference between the groups A and C.N-type proportion of B group was 48.5% (33/68), greater than that of group A(16.0%,15/94) and C (16.3%, 14/86), x² = 20.1, x² =18.6.U-type proportion of B group was 11.8% (8/68), smaller than that of groups A (28.7%,27/94) and C (37.2%, 32/86), 2 2 = 6.70, x² =12.8, and the differences were statistically significant (P < 0.01). For groups A and C, the N and U types were not significantly different. CONCLUSION: The angle between the RHV and the inferior vena cava in MOVC patients is morphologically different from that in healthy humans, with the angle value in MOVC patients being slightly larger. However, this difference is irrelevant to cirrhosis.

Clinical outcomes of warfarin anticoagulation after balloon dilation alone for the treatment of Budd-Chiari syndrome complicated by old inferior vena cava thrombosis.

BACKGROUND: To evaluate the safety and clinical efficacy of warfarin anticoagulation after balloon dilation alone for the treatment of Budd-Chiari syndrome (BCS) complicated by old inferior vena cava (IVC) thrombosis. METHODS: From January 2008 to November 2013, 19 BCS patients complicated with old IVC thrombosis were treated with balloon dilation followed by oral administration of anticoagulant warfarin. Follow-up was performed at 1 week, then 1, 2, 3, 6, and 12 months after balloon dilation, and then annually thereafter. IVC patency and morphologic changes of the old thrombus were examined by ultrasound, and clinical symptoms and signs were determined by clinical examinations during follow-up. RESULTS: Successful IVC balloon dilation was achieved in the 19 patients (100%). Inferior vena cavography demonstrated the patency of IVC lumen, and the size of the old thrombus was not altered. The mean pressure gradient between IVC and the right atrium was reduced from 27.5 ± 3.0 cm H2O (range, 22-35) before treatment to 5.4 ± 1.3 cm H2O (range: 2-7) after treatment (t = 41.6, P < 0.05; 1 cm H2O = 0.098 kPa). Patients were followed up as outpatients for an average of 15.9 ± 14.4 months (range, 3-66). Anticoagulation with warfarin was well tolerated in all patients after balloon dilation alone. Of the 19 patients, complete resolution of the old thrombus was achieved in 12 patients and partial resolution was achieved in 7 patients. Color Doppler ultrasound showed that 17 patients had IVC lumen patency, and 2 patients had IVC reocclusion. None of the patients had recurrence of thrombosis, symptomatic pulmonary embolism, and bleeding complications throughout the follow-up period. CONCLUSIONS: Our results indicate that warfarin anticoagulation after balloon dilation alone is a safe and effective therapy for BCS patients with old IVC thrombosis.

Prognostic value of preoperative combined with postoperative systemic immune-inflammation index for disease-free survival after radical rectal cancer surgery: a retrospective cohort study.

Background: Colorectal cancer (CRC) ranks highly in malignant tumor incidence and mortality rates, severely affecting human health. The predictive value of the systemic immune-inflammation index (SII) in CRC prognosis is gaining attention, but there is limited research on the combined preoperative and postoperative SII. This study aims to explore the prognostic value of combined SII on disease-free survival (DFS) in patients undergoing radical surgery for rectal cancer. Methods: We enrolled 292 patients with rectal cancer who underwent radical resection at the Affiliated Hospital of Xuzhou Medical University from May 2018 to September 2020, along with regular follow-ups to document the DFS. Patients' complete blood cell counts were assessed before surgery and between 21-56 days postoperatively. Calculating preoperative and postoperative SII, patients were categorized into four groups based on the optimal cutoff values: (I) low-low group (preoperative SII <449.325 and postoperative SII <568.13); (II) high-low group (preoperative SII ≥449.325 and postoperative SII <568.13); (III) low-high group (preoperative SII <449.325 and postoperative SII ≥568.13); and (IV) high-high group (preoperative SII ≥449.325 and postoperative SII ≥568.13). The receiver operating characteristic (ROC) curve analysis evaluated the prediction efficacy of preoperative, postoperative, and combined SII. Kaplan-Meier analysis generated DFS curves, and Cox regression analysis determined prognostic factors. Results: With a median follow-up of 41 months, 65.4% (191/292) patients reached DFS. The clinical pathological features between the four groups are balanced and comparable (P>0.05). The area under the ROC curve for preoperative, postoperative, and combined SII was 0.668 [95% confidence interval (CI): 0.6-0.737], 0.696 (95%CI: 0.63-0.763), and 0.741 (95% CI: 0.681-0.802), respectively. After adjusting for confounding factors such as adjuvant therapy, differentiation, vascular invasion, neural invasion, tumor-node-metastasis (TNM) stage, carcinoembryonic antigen (CEA), and carbohydrate antigen 19-9 (CA19-9), significant differences were observed between the high-low group [hazard ratio (HR) =2.403; 95% CI: 1.255-4.602; P=0.008], low-high group (HR =5.058; 95% CI: 2.389-10.71; P<0.001), and high-high group (HR =6.214; 95% CI: 3.474-11.115; P<0.001) compared to the low-low group, with higher risks of adverse outcomes. Conclusions: Combined SII has better predictive efficacy than monitoring preoperative or postoperative SII alone in rectal cancer patients undergoing radical surgery.

The Synergistic Effect between Metal and Sulfur Vacancy to Boost CO2 Reduction Efficiency: A Study on Descriptor Transferability and Activity Prediction.

Both metal center active sites and vacancies can influence the catalytic activity of a catalyst. A quantitative model to describe the synergistic effect between the metal centers and vacancies is highly desired. Herein, we proposed a machine learning model to evaluate the synergistic index, PSyn, which is learned from the possible pathways for CH4 production from CO2 reduction reaction (CO2RR) on 26 metal-anchored MoS2 with and without sulfur vacancy. The data set consists of 1556 intermediate structures on metal-anchored MoS2, which are used for training. The 2028 structures from the literature, comprising both single active site and dual active sites, are used for external test. The XGBoost model with 3 features, including electronegativity, d-shell valence electrons of metal, and the distance between metal and vacancy, exhibited satisfactory prediction accuracy on limiting potential. Fe@Sv-MoS2 and Os@MoS2 are predicted to be promising CO2RR catalysts with high stability, low limiting potential, and high selectivity against hydrogen evolution reactions (HER). Based on some easily accessible descriptors, transferability can be achieved for both porous materials and 2D materials in predicting the energy change in the CO2RR and nitrogen reduction reaction (NRR). Such a predictive model can also be applied to predict the synergistic effect of the CO2RR in other oxygen and tungsten vacancy systems.

Efficacy and Safety of Snap Needles in the Treatment of Postoperative Hemorrhoidal Pain: A Systematic Review and Meta-Analysis.

Purpose: The aim of this study is to evaluate the efficacy and safety of Snap Needles (SN) in the management of Postoperative Hemorrhoidal Pain (POHP). Patients and Methods: A systematic search was conducted in various databases, including EMBASE, Web of Science, PubMed, WanFang database, China National Knowledge Infrastructure (CNKI), China Biomedical Literature Database (CBM), and China Science and Technology Journal Database (VIP), spanning from their inception to August 2023, to identify relevant randomized controlled trials (RCTs) on SN for POHP. The primary outcome measure was the Visual Analog Scale (VAS), while secondary outcomes encompassed the Total Effective Rate (TER), Wound Healing Time (WHT), Pain Relief Time (PRT), Pain Disappearance Time (PDT), and Adverse Events (AEs). The Cochrane Risk of Bias Tool was employed to assess the quality of individual studies. A meta-analysis was conducted using RevMan 5.4.1 software. Results: The meta-analysis included 11 RCTs involving 1188 POHP patients, with an overall assessment of study quality ranging from very low to moderate. The findings revealed that the SN group exhibited significant improvements in treatment outcomes when compared to the control group (CG). These improvements were reflected in reduced VAS scores (mean difference [MD] = -1.10, 95% confidence interval [CI]: -1.31, -0.89, P < 0.05), shorter WHT (MD = -2.55, 95% CI: -3.02, -2.09, P < 0.05), quicker PRT (MD = -7.99, 95% CI: -8.48, -7.49, P < 0.05), fewer AEs (risk ratio [RR] = 0.38, 95% CI: 0.22, 0.67, P < 0.05), improved TER (RR = 1.18, 95% CI: 1.09, 1.27, P < 0.05), and faster PDT (MD = 19.24, 95% CI: 14.17, 24.31, P < 0.05). Conclusion: The use of SN appears to yield favorable outcomes in the treatment of POHP, and is potentially an alternative therapy to western drug therapy.

Ultrastable Anion Radicals in Ligand-Dimerized Frameworks for Self-Accumulated Electrochemiluminescence.

Electrochemiluminescence (ECL) is a light-emitting process that occurs via an annihilation reaction among energetic radical intermediates, whose stabilities determine the ECL efficiency. In this study, a ligand-dimerized metal-organic framework (MOF) with ultrastable anion radical is designed as an efficient nanoemitter for self-accumulated ECL. Due to the nonplanar structure of perylene diimide (PDI) derivate, two PDI ligands in the framework form a J-dimer unit with a vertical distance of ∼5.74 Å. In cathodic scanning, the ligand-dimerized MOF demonstrates three-step ECL emissions with a gradual increase in ECL intensity. Unlike the decrease in the PDI ligand, the self-accumulated ECL of the MOF was observed with 16.8-fold enhancement due to the excellent stability of radical intermediates in frameworks. Electron paramagnetic resonance demonstrated the ultrastability of free radicals in the designed frameworks, with 82.2% remaining even after one month of storage. Density functional theory calculations supported that PDI dimerization was energetically favorable upon successive electron injection. Moreover, the ECL wavelength is 610 nm, corresponding to the emission of excited dimers. The radical-stabilized reticular nanoemitters open up a new platform for decoding the fundamentals of self-accumulated ECL systems.