Multiphase Porous Electrochemical Catalysts Derived from Iron-Based Metal-Organic Framework Compounds.

Herbicide use has attracted attention recently due to potential damage to human health and lethality to the honey bees and other pollinators. Fenton reagent treatment processes can be applied for the degradation of herbicidal contaminants from water. However, the need to carry out the normal Fenton reactions under acidic conditions often hinders their practical application for pollution control. Herein, we report on the synthesis and application of multiphasic porous electro-Fenton catalysts prepared from calcinated metal-organic framework compounds, CMOF@PCM, and their application for the mineralization of herbicides in aqueous solution at circum-neutral pH. CMOF nanoparticles (NPs) are anchored on porous carbon monolithic (PCM) substrates, which allow for binder-free application. H2O2 is electrochemically generated on the PCM substrate which serves as a cathode, while ·OH is generated by the CMOF NPs at low applied potentials (-0.14 V). Results show that the structure and reactivity of the CMOF@PCM electro-Fenton catalysts are dependent on the specific MOF precursor used during synthesis. For example, CMIL-88-NH2, which is prepared from MIL-88(Fe)-NH2, is a porous core-shell structured NP comprised of a cementite (Fe3C) intermediate layer that is sandwiched between a graphitic shell and a magnetite (Fe3O4) core. The electro-Fenton production of hydroxyl radical on the CMOF@PCM composite material is shown to effectively degrade an array of herbicides.

Sustainable Radical Cascades to Synthesize Difluoroalkylated Pyrrolo[1,2-a]indoles.

We disclose herein a photocatalytic difluoroalkylation and cyclization cascade reaction of N-(but-2-enoyl)indoles with broad substrate scopes in up to 90% isolated yield. This method provides sustainable and efficient access to synthesize difluoroalkylated pyrrolo[1,2-a]indoles with a quaternary carbon center under mild conditions.

Prognostic impact of the Controlling Nutritional Status Score in patients with biliary tract cancer: a systematic review and meta-analysis.

Background: Biliary tract cancer (BTC) is a malignancy associated with unfavorable outcomes. Advanced BTC patients have a propensity to experience compromised immune and nutritional status as a result of obstructive jaundice and biliary inflammation. Currently, there is a lack of consensus on the impact of the Controlling Nutritional Status (CONUT) score in the context of BTC prognosis. The purpose of this study is to conduct a meta-analysis on the association between CONUT and the prognosis of patients suffering from BTC. Methods: A defined search strategy was implemented to search the PubMed, Embase, and Web of Science databases for eligible studies published until March 2023, with a focus on overall survival (OS), relapse-free survival/recurrence-free survival(RFS), and relevant clinical characteristics. The prognostic potential of the CONUT score was evaluated using hazard ratios (HRs) or odds ratios (ORs) with 95% confidence intervals (CIs). Results: In this meta-analysis, a total of 1409 patients from China and Japan were involved in 9 studies. The results indicated that the CONUT score was significantly correlated with worse OS (HR=2.13, 95% CI 1.61-2.82, P<0.0001) and RFS (HR=1.83, 95% CI 1.44-2.31, P<0.0001) in patients with BTC. And, the analysis showed that a high CONUT score was significantly associated with clinical characteristics such as jaundice (OR=1.60, 95% CI=1.14-2.25, P=0.006), poorly differentiated tumor (OR=1.43, 95% CI=1.03-1.99, P=0.03), pT3 and 4 stage of the tumor (OR=1.87, 95% CI=1.30-2.68, P=0.0007), and complications of Clavien-Dindo classification grade IIIa or higher (OR=1.79, 95% CI=1.03-3.12, P=0.04). Conclusion: This meta-analysis indicates that a high CONUT score can serve as a significant prognostic indicator for survival outcomes among patients diagnosed with BTC.

Topology Optimization Via Spatially-Varying TPMS.

Structural design with multi-family triply periodic minimal surfaces (TPMS) is a meaningful work that can combine the advantages of different types of TPMS. However, very few methods consider the influence of the blending of different TPMS on structural performance, and the manufacturability of final structure. Therefore, this work proposes a method to design manufacturable microstructures with topology optimization (TO) based on spatially-varying TPMS. In our method, different types of TPMS are simultaneously considered in the optimization to maximize the performance of designed microstructure. The geometric and mechanical properties of the unit cells generated with TPMS, that is minimal surface lattice cell (MSLC), are analyzed to obtain the performance of different types of TPMS. In the designed microstructure, MSLCs of different types are smoothly blended with an interpolation method. To analyze the influence of deformed MSLCs on the performance of the final structure, the blending blocks are introduced to describe the connection cases between different types of MSLCs. The mechanical properties of deformed MSLCs are analyzed and applied in TO process to reduce the influence of deformed MSLCs on the performance of final structure. The infill resolution of MSLC within a given design domain is determined according to the minimal printable wall thickness of MSLC and structural stiffness. Both numerical and physical experimental results demonstrate the effectiveness of the proposed method.

Trimetallic carbon-based catalysts derived from metal-organic frameworks for electro-Fenton removal of aqueous pesticides.

Pesticide overuse has posed a threat to agricultural community as well as aquatic animals. Heterogeneous electro-Fenton (HEF) processes have received considerable attention for aqueous contaminants removal, and metal-organic frameworks (MOFs) serve as promising templates for fabrication of carbon-based HEF catalysts with low Fe leaching and enhanced stability. Herein, multimetallic MOF-derived HEF catalysts CMOFs@PCM have been demonstrated as efficient and stable HEF catalysts for aqueous pesticide degradation and mineralization. The porous carbon monolith (PCM) substrate effectively catalyzed 2-electron oxygen reduction reaction (ORR) over the pH range of 4-10 to in situ generate H2O2, which was then activated by the anchored Fe3O4, Fe3C and NiO into OH for pesticide degradation. Fe8Al7Ni5-CMOF@PCM achieved over 90% napropamide degradation within 60 min in the pH range of 4-10, and 96% degradation at neutral condition, 39% higher than monometallic CMIL-88(Fe)@PCM. Meanwhile, the embedded NiO and γ-Al2O3 showed synergistic effect in promoting the catalytic activity of Fe sites, resulting in substantially enhanced performance of trimetallic FexAlyNiz-CMOF@PCM compared to the monometallic counterparts. On the other hand, the unique core-shell structure and Fe3C interlayer formed by co-pyrolyzing Fe-containing MOFs-NH2 with PCM greatly minimized the metal leaching and enhanced the stability of the electrocatalysts.

A Support-Free Infill Structure Based on Layer Construction for 3D Printing.

The design of the light-weight infill structure is a hot research topic in additive manufacturing. In recent years, various infill structures have been proposed to reduce the amount of printing material. However, 3D models filled with them may have very different structural performances under different loading conditions. In addition, most of them are not self-supporting. To mitigate these issues, a novel light-weight infill structure based on the layer construction is proposed in this article. The layers of the proposed infill structure continuously and periodically transform between triangles and hexagons. The geometries of two adjacent layers are controlled to be self-supporting for different 3D printing technologies. The machine code (Gcode) of the filled 3D model is generated in the construction of the infill structure for 3D printers. That means 3D models filled with the proposed infill structure do not need an extra slicing process before printing, which is time consuming in some cases. Structural simulations and physical experiments demonstrate that our infill structure has comparable structural performance under different loading conditions. Furthermore, the relationship between the structural stiffness and the parameters of the infill structure is investigated, which will be helpful for non-professional users.

Oolong Tea Consumption and the Risk of Oral Squamous Cell Carcinoma: A Propensity Score-Based Analysis in Southeast China.

Oolong tea is one of the world's most popular non-alcoholic beverages, particularly in coastal Southeast China. Hitherto, epidemiological studies on the association between oolong tea consumption and the risk of patients with oral squamous cell carcinoma (OSCC) are very limited. This study aimed to evaluate the potential effect of oolong tea consumption on OSCC risk in Southeast China. From January 2010 to October 2020, face-to-face interviews were conducted for 744 newly diagnosed OSCC patients and 1,029 healthy controls to collect information on demographics, oolong tea consumption behaviors, and other lifestyle factors. Propensity score matching (PSM), inverse probability of treatment weight (IPTW), and stabilized inverse probability of treatment weight (SIPTW) were utilized to minimize confounding effects. Multivariate, conditional, and weighted logistic regression was used to evaluate the associations of oolong tea consumption behaviors with OSCC risk. Participants who drank oolong tea showed a lower risk of OSCC when compared to their non-drink counterparts [PSM population, OR (95%CI): 0.69 (0.49-0.97); SIPTW population, OR (95%CI): 0.74 (0.58-0.94)]. Moreover, the reduced risk was found to be significantly associated with certain tea-drinking habits (consumed amount over 500 mL per day, a duration of <20 years, age at initiation older than 30 years, and warm and moderately concentrated tea). Similar results were yielded in the sensitivity analyses (Multivariate adjustment and the IPTW analysis). Furthermore, subgroup analysis revealed that the negative association of oolong tea drinking with OSCC risk was more evident among those with poor oral hygiene. This study provides supportive evidence that oolong tea consumption may have a potentially beneficial effect in preventing OSCC, especially for those with poor oral hygiene.

Ternary metal oxide embedded carbon derived from metal organic frameworks for adsorption of methylene blue and acid red 73.

Organic dyes can enter water bodies through industrial wastes and may pose a threat to the health of aquatic organisms and human. Metal organic framework derived carbon materials (CMOFs) have shown excellent performance for aqueous dye adsorption. However, few have studied multimetallic CMOFs for dye removal. Herein, a ternary metal oxide embedded carbon derived from amino-modified metal organic framework (CMOF(Fe/Al/Ni 8/7/5)-NH2) has been developed as an efficient adsorbent to remove aqueous methylene blue (MB) and acid red 73 (AR-73). CMOF(Fe/Al/Ni 8/7/5)-NH2 reached adsorption equilibrium for both MB and AR-73 within 30 min at neutral pH condition. It also achieved 18 and 24 times higher adsorption than commercial activated carbon (AC) in 10 min for MB and AR-73, respectively. Compared to other CMOFs-NH2, CMOF(Fe/Al/Ni 8/7/5)-NH2 had the highest adsorption capacity for both cationic MB and anionic AR-73. In addition, CMOF(Fe/Al/Ni 8/7/5)-NH2 had < 0.15% metal leaching in 90 min in the pH range of 4-10, and it also maintained 89% and 95% adsorption capacity for MB and AR-73 in five consecutive adsorption batches, respectively. Electrostatic interaction was identified as the primary interaction between CMOFs-NH2 and the dyes, and the embedded crystalline metal oxides with different points of zero charge (PZCs) were identified to be the key adsorption sites. A uniformly distributed surface charge model was proposed to explain the exceptional adsorption capacity of CMOF(Fe/Al/Ni 8/7/5)-NH2. With fast kinetics, high adsorption capacity, wide applicability and good stability, CMOF(Fe/Al/Ni 8/7/5)-NH2 may be an effective adsorbent for many other ionic organic pollutants.

Porous carbon monoliths for electrochemical removal of aqueous herbicides by "one-stop" catalysis of oxygen reduction and H2O2 activation.

The overuse of herbicides has posed a threat to human health and the aquatic environment via DNA mutations and antibiotic gene resistance. Carbon-based cathodic electrochemical advanced oxidation has evolved as a promising technology for herbicide degradation by generating hydroxyl radicals (•OH). However, conventional electro-Fenton process relies on interaction of multiple species that adds to the system complexity and cost and narrows the working pH range. Herein, a series of porous carbon monoliths (PCMs) were developed as a "one-stop" platform for catalysis of the 2-electron ORR coupled with further catalytic reductive cleavage of H2O2 to produce •OH. A PCM prepared using 1,6-hexamethylene diamine (denoted as PCM-HDA) produced H2O2 at a level that was 374% higher than that obtained using commercially available carbon black at circum-neutral pH. Meanwhile, the generated H2O2 was catalytically decomposed to produce •OH. Based on these results, the PCM-HDA electrode achieved an 80 ± 2% degradation of napropamide in 60 min over the pH range of 4-10 at a mildly reducing potential, with a 69 ± 2% TOC reduction at circum-neutral condition in 2 h. This simplified system overcomes the system complexity and pH limitation of the conventional electron-Fenton processes.

Cylindrical Fused Silica Resonators Driven by PZT Thin Film Electrodes with Q Factor Achieving 2.89 Million after Coating.

Cylindrical shell fused silica resonators coated with 8 axisymmetric Pb(Zr0.53Ti0.47)O3 (PZT) thin film electrodes (thickness ~2 µm) were reported. The resonators were firstly designed and fabricated, then annealed and processed by chemical etching to increase mechanical quality factor (Q factor) of resonators, which achieved as high as 2.89 million for n = 2 wineglass modes after being coated with PZT thin film electrodes. The n = 2 wineglass modes of the resonators were driven by PZT thin film electrodes in experiment and simulation with fine vibratory shape, which demonstrated the feasibility of the cylindrical fused silica resonator driven by PZT thin film electrodes. The application of PZT thin film electrodes to drive and detect cylindrical shell fused silica resonator can significantly improve Q factor of resonators and improve the sensitivity of Coriolis Vibratory Gyroscope (CVG).

Alkyl radical triggered in situ SO2-capture cascades.

An unprecedented in situ SO2-capture cascade triggered by alkyl radicals has been documented herein. Mechanistic investigations suggest that, triggered by alkyl radicals, SO2 was released in situ and subsequently fixed into polycyclic small molecules. A wide range of alkylsulfonyl substituted polycyclic compounds were easily prepared with high yields and good functional group tolerability.