Converting CO into fuels via photochemical reactions relies on highly efficient and selective catalysts. We demonstrate that the catalytic active metal center can cooperate with neighboring hydroxide ligands to boost the photocatalytic CO reduction. Six cobalt-based metal-organic frameworks (MOFs) with different coordination environments are studied at the same reaction condition (photosensitizer, electron donor, water/organic mixed solvent, and visible light). In pure CO at 1.0 atm, the MOFs bearing μ-OH ligands neighboring the open Co centers showed CO selectivities and turnover frequencies (TOFs) up to 98.2% and 0.059 s, respectively. More importantly, their TOFs reduced only ca. 20% when the CO partial pressure was reduced to 0.1 atm, while other MOFs reduced by at least 90%. Periodic density functional theory calculations and isotope tracing experiments showed that the μ-OH ligands serve not only as strong hydrogen-bonding donors to stabilize the initial Co-CO adduct but also local proton sources to facilitate the C-O bond breaking.
Efficient adsorptive separation of propylene/propane (C 3 H 6 /C 3 H 8 )i sh ighly desired and challenging.K nown strategies focus on either the thermodynamic or the kinetic mechanism. Here,w er eport an interesting reactivity of am etal-organic framework that improves thermodynamic and kinetic adsorption selectivity simultaneously.W hen the metal-organic framework is heated under oxygen flow, half of the soft methylene bridges of the organic ligands are selectively oxidized to form the more polar and rigid carbonyl bridges. Mixture breakthrough experiments showed drastic increase of C 3 H 6 /C 3 H 8 selectivity from 1.5 to 15. Forc omparison, the C 3 H 6 /C 3 H 8 selectivities of the best-performing metal-organic frameworks Co-MOF-74 and KAUST-7 were experimentally determined to be 6.5 and 12, respectively.G as adsorption isotherms/kinetics,s ingle-crystal X-ray diffraction, and computational simulations revealed that the oxidation gives additional guest recognition sites,w hich improve thermodynamic selectivity,a nd reduces the framework flexibility,w hich generate kinetic selectivity.
The results of this study suggest that salvage liver resection after downstaging of unresectable hepatocellular carcinoma in patients with a complete response to transarterial chemoembolization (TACE) has a comparable long-term outcome in this good-prognosis group. Salvage liver resection may provide a better long-term outcome compared with TACE alone, but only in patients with macroscopic vascular invasion or those with a partial response to TACE.
Aim: In this study, we aimed to explore the toxic mechanisms of cardiovascular injuries induced by ambient fine particulate matter (PM2.5) in atherosclerotic-susceptible ApoE−/− mice. An acute toxicological animal experiment was designed with PM2.5 exposure once a day, every other day, for three days. Methods: ApoE−/− and C57BL/6 mice were randomly categorized into four groups, respectively (n = 6): one control group, three groups exposed to PM2.5 alone at low-, mid-, and high-dose (3, 10, or 30 mg/kg b.w.). Heart rate (HR) and electrocardiogram (ECG) were monitored before instillation of PM2.5 and 24 h after the last instillation, respectively. Cardiac function was monitored by echocardiography (Echo) after the last instillation. Biomarkers of systemic oxidative injuries (MDA, SOD), heart oxidative stress (MDA, SOD), and NAD(P)H oxidase subunits (p22phox, p47phox) mRNA and protein expression were analyzed in mice. The results showed that PM2.5 exposure could trigger the significant increase of MDA, and induce the decrease of heart rate variability (HRV), a marker of cardiac autonomic nervous system (ANS) function with a dose–response manner. Meanwhile, abnormal ECG types were monitored in mice after exposure to PM2.5. The expression of cytokines related with oxidative injuries, and mRNA and protein expression of NADPH, increased significantly in ApoE−/− mice in the high-dose group when compared with the dose-matched C57BL6 mice, but no significant difference was observed at Echo. In conclusion, PM2.5 exposure could cause oxidative and ANS injuries, and ApoE−/− mice displayed more severe oxidative effects induced by PM2.5.
Pancreatic neuroendocrine neoplasms (p-NENs) are slowly growing tumors with frequent liver metastasis. There is a variety of approaches to treat non-functional p-NENs with synchronous liver metastasis (LM) which complicates the determination of optimal treatment. Based on updated literature review, we discussed the treatment strategy determinants for p-NEN with LM. According to the resectability of primary tumor, the WHO 2010 grade classification and the radiological type of liver metastasis, the CSNET group reached agreements on a number of issues, including the following. Prior to treatment, biopsy is required to confirm pathology. Liver biopsy is important for more accurate grading of tumor and percutaneous core needle biopsy is more available than EUS-FNA. In patients with unresectable primary, surgical resection for liver-metastatic lesions should be avoided. Curative surgery is recommended for G1/G2 p-NET with type I LM and R1 resection also seems to improve overall survival rate. Cytoreductive surgery is recommended for G1/G2 p-NET with type II LM in select patients, and should meet stated requirements. Surgical resection for G1/G2 p-NET with type III LM and p-NEC with LM should be avoided, and insufficient evidence exists to guide the surgical treatment of G3 p-NET with LM. Liver transplantation may be an option in highly select patients. In addition, the optimal time for surgical approach is still required for more evidence.
The source and degree of elemental fractionation is one of the remaining challenges in LA-ICP-MS. In this study, the ICP-induced fractionation behavior of 63 elements was studied using a local aerosol extraction strategy while using a 193 nm excimer laser ablation system for sampling. We found that the sampling distance between the ablation site and the gas outlet nozzle tip positively correlated with the size of the laser ablation produced aerosol particles or agglomerates in the local aerosol extraction strategy.Therefore, the local aerosol extraction strategy allowed detailed studies of the ICP-induced fractionation behaviors for different elements. At a low makeup gas flow rate of 0.6 L min À1 (hot plasma conditions), the increase in the size of aerosol agglomerates or particles because of the increased sampling distance from 1 mm to 10 mm does not affect the ionization efficiency of the sample aerosol in ICP. In contrast, at a high makeup gas flow rate of 0.9 L min À1 , the normalized signal intensities of the elements significantly differ when the sampling distance increases from 1 mm to 10 mm. These experimental results suggest that the changes in the size of aerosol particles or agglomerates under our given conditions do not affect the transport efficiency of aerosol particles but affect the vaporization of aerosol particles in ICP. The mass load effect is more significant in the presence of large amounts of large aerosol particles and agglomerates, which deteriorates the vaporization of aerosol particles. Our experimental results also show that the sample position in the normal ablation cell affects the size of laser ablation produced aerosol particles or agglomerates. The high velocity of the carrier gas flow rate on the ablation site facilitates the production of small aerosol agglomerates or particles. To reduce the ICP-induced fractionation behaviors in LA-ICP-MS, hot plasma conditions and high velocity of the carrier gas flow rate on the ablation site are required.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.