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Surgery has been considered the main treatment for submucosal tumors (SMTs); however, endoscopic resection is currently accepted for gastric SMTs smaller than 3cm. Endoscopic submucosal dissection (ESD) is considered the technique of choice and submucosal tunneling endoscopic resection shows successful results with low complication rate in the recent meta-analysis by Cao et al. The major limitation of these methods is the technical difficulty to be applied in certain anatomic locations.Three different manganese(II) porphyrins have been exploited to react with 4-methylimidazolate (4-MeIm-), and the five-coordinate products are characterized by ultraviolet-visible, single-crystal X-ray, and electronic paramagnetic resonance spectroscopies. Interestingly, 4-MeIm- is found to bond to the metal center through either of the two N atoms (N1 or N3), which yielded two linkage isomers with either an unhindered or a hindered ligand conformation, respectively. Investigations revealed it is the large metal out-of-plane displacements (Δ24 and Δ4 ≥ 0.59 Å) that have rendered the equivalence of two isomers with a small energy difference (5.2-8.3 kJ/mol). The nonbonded intra- and intermolecular interactions thus become crucial factors in the balance of linkage isomerization. All of the products in both solution and solid states show the same characteristic resonances of high-spin Mn(II) (S = 5/2) with g⊥ ≈ 5.9 and g∥ ≈ 2.0 at 4 K, consistent with the weak effects of the axial ligand on core conformation and metal electronic configurations. Zero-field splitting parameters obtained through simulations are also reported.Porous solids in the form of adsorbents and catalysts play a crucial role in various industrially important chemical, energy, and environmental processes. Formulating them into structured configurations is a key step toward their scale up and successful implementation at the industrial level. Additive manufacturing, also known as 3D printing, has emerged as an invaluable platform for shape engineering porous solids and fabricating scalable configurations for use in a wide variety of separation and reaction applications. However, formulating porous materials into self-standing configurations can dramatically affect their performance and consequently the efficiency of the process wherein they operate. Toward this end, various research groups around the world have investigated the formulation of porous adsorbents and catalysts into structured scaffolds with complex geometries that not only exhibit comparable or improved performance to that of their powder parents but also address the pressure drop and attrition issues of traditional configurations. In this comprehensive review, we summarize the recent advances and current challenges in the field of adsorption and catalysis to better guide the future directions in shape engineering solid materials with a better control on composition, structure, and properties of 3D-printed adsorbents and catalysts.Carbon-based perovskite solar cells without a hole transport layer (HTL) are considered to be highly stable and of low cost. CDK inhibitor review However, the deficient interface contact and inferior hole extraction capability restrict the further improvement of the device efficiency. Introducing a hole transporting layer, such as cuprous thiocyanate (CuSCN), can enhance the hole extraction ability and improve the interface contact. However, our further studies indicated that-at a certain temperature-for carbon-based solar cells, in the CuSCN layer, the diffusion of SCN- into the perovskite film would produce more interfacial defects and aggravate nonradiative recombination, thus hindering the carrier transport. We further disclosed the reasons for performance attenuation during the thermal treatment of carbon electrodes, proposed a vacuum-assisted drying process for carbon electrodes to suppress the destructive effect, and finally, achieved an enhanced efficiency for perovskite solar cells with a CuSCN inorganic HTL and screen-printable carbon electrode. Also, the unencapsulated perovskite solar cell demonstrated over 80% efficiency retention after being stored in an ambient atmosphere (45-70% relative humidity (RH)) for over 1000 h and maintained over 85% efficiency retention for 309 h of 1-sun irradiation under a continuous nitrogen flow under open-circuit conditions.62 chlorinated polyfluorooctane ether sulfonate (62 Cl-PFESA) was previously shown to undergo limited dechlorination in rainbow trout to yield 62 hydrogen-substituted polyfluorooctane ether sulfonate (62 H-PFESA) as the sole metabolite. However, the biotransformation susceptibility of 62 Cl-PFESA has not been investigated in mammals and the biological behavior of 62 H-PFESA has not been defined in any species. We investigated the respective transformation products of 62 Cl-PFESA and 62 H-PFESA and their toxicokinetic properties in male Sprague-Dawley rats as a mammalian model. 62 H-PFESA was the sole detectable metabolite of 62 Cl-PFESA, with a transformation percentage of 13.6% in rat liver, but it resisted further degradation. 62 Cl-PFESA also transformed to 62 H-PFESA in reductive rat liver S9 incubations but remained stable under oxidative conditions, suggesting a reductive enzyme-dependent transformation pathway. 62 Cl-PFESA was more enriched in lipid-rich tissues, while 62 H-PFESA was more prone to cumulative urinary excretion. From this perspective, it may suggest a detoxification mechanism for organisms to form the less hydrophobic 62 H-PFESA to alleviate total burdens. To date, 62 Cl-PFESA was the second perfluoroalkyl acid reported to undergo biotransformation in mammals. The toxicokinetic properties determined for 62 Cl-PFESA and 62 H-PFESA in blood and urine were found to be structure and dose dependent.Oxidopyridinium ions bearing an ester group at the 5-position undergo (4 + 3) cycloaddition reaction to afford congeners of 7-azabicyclo[4.3.1]decane. The reaction generally proceeds in high yield, although an excess of diene is often required to achieve such yields. The reaction is highly regioselective, but not endo/exo selective. It appears the cycloaddition process can be either kinetically or thermodynamically controlled, depending on the nature of the diene used and the reaction time. An intramolecular Heck reaction was used to demonstrate that some chemistry is possible with the cycloadducts.The drying behavior of two different polymers [polyvinyl pyrrolidone (PVP) and polyisobutylene (PIB)] with different glass transition temperatures are investigated and compared as a function of film thickness from micrometer (∼3 μm) to nanometer scale (∼10 nm). The focus of this study is to distinguish between solvent diffusion, polymer relaxation, and substrate confinement of polymer chain mobility toward the interface as the dominating mechanism of drying kinetics. Relaxation kinetics becomes more dominant when the film thickness is reduced, which is shown experimentally for the first time for nanometer-scale film thicknesses. Identical drying curves regardless of the film thickness of PVP/methanol indicate the limitation of solvent transport by relaxation kinetics. The viscoelastic relaxation behavior of the polymer/solvent film is modeled by a Maxwell element. The results are in accordance with the experimental drying curves and allow for the determination of the characteristic relaxation time. Relaxation limitation becomes relevant at high diffusion Deborah numbers when the relaxation time-which is a function of the deployed material and the polymer/solvent composition-is higher than the characteristic diffusion time in the film. The latter is a function of the polymer/solvent composition and the thickness of the film. Drying curves of PIB/toluene films show additional effect in a substrate-near region of about 5 nm in which polymer chain mobility is confined, resulting in decelerated solvent diffusion. Although this effect near the substrate interface is expected to be present regardless of the film thickness, it becomes more dominant when the substrate-near region represents a significant fraction of the total film thickness. The key to the derived methodology for characterization of the polymer/solvent drying process is to vary dry film thickness from micrometers to a few nanometers which allows us to determine the dominating mechanism of drying kinetics.The Helmholtz free energy, energy, and entropy of mixing of N,N-dimethylformamide (DMF) and water are calculated in the entire composition range by means of Monte Carlo computer simulations and thermodynamic integration using all possible combinations of five DMF and three widely used water models. Our results reveal that the mixing of DMF and water is highly non-ideal. Thus, in their dilute solutions, both molecules induce structural ordering of the major component, as evidenced by the concomitant decrease in the entropy. Among the 15 model combinations considered, only 4 reproduce the well-known full miscibility of DMF and water, 3 of which strongly exaggerate the thermodynamic driving force of the miscibility. Thus, the combination of the CS2 model of DMF and the TIP4P/2005 water model reproduces the properties of the DMF-water mixtures far better than the other combinations tested. Our results also reveal that moving a fractional negative charge from the N atom to the O atom of the DMF molecule, leading to the increase in its dipole moment, improves the miscibility of the model with water. Starting from the CS2 model and optimizing the charge to be moved, we propose a new model of DMF that reproduces very accurately both the Helmholtz free energy of mixing of aqueous DMF solutions in the entire composition range (when used in combination with the TIP4P/2005 water model) and also the internal energy of neat DMF.Nanofibrous aerogels constructed by ceramic fiber components (CNFAs) feature lightweight, compressibility, and high-temperature resistance, which are superior to brittle ceramic aerogels assembled from nanoparticles. Up to now, in order to obtain CNFAs with stable framework and multifunctionality such as hydrophobicity and gas absorption, it is necessary to perform binding and surface modification processes, respectively. However, the microstructure as well as properties of CNFAs are deteriorated by the direct addition of binders and modifiers. To tackle these problems, we introduced a unique low-temperature (100 °C) chemical vapor deposition method (LTCVD) to achieve the cross-linking and hydrophobization of Si3N4 CNFA in only one step. More importantly, during the LTCVD process, SiOx coatings and nanowire arrays were in situ formed via vapor-solid (VS) and vapor-liquid-solid (VLS) mechanisms on the surface and intersection of Si3N4 nanofibers, which cemented the aerogel framework, endowed it with hydrophobicity, and improved its oxidation resistance at high temperature. Compared to most of its counterparts, the Si3N4/SiOx CNFA exhibited better mechanical properties, higher capability of oil/water separation (33-76 g·g-1), lower thermal conductivity (0.0157 W/m·K-1), and superior structural stability in a wide temperature range of -196-1200 °C. This work not only presents an excellent Si3N4/SiOx CNFA for the first time but also provides fresh insights for the exquisite preparation strategy of CNFAs.