RESUMO
A strategy of tuning azole-based ionic liquids for reversible CO2 capture from ambient air was reported. Through tuning the basicity of anion as well as the type of cation, an ideal azole-based ionic liquid with both high CO2 capacity and excellent stability was synthesized, which exhibited a highest single-component isotherm uptake of 2.17â mmol/g at the atmospheric CO2 concentration of 0.4â mbar at 30 °C, even in the presence of water. The bound CO2 can be released by relatively mild heating of the IL-CO2 at 80 °C, which makes it promising for energy-efficient CO2 desorption and sorbent regeneration, leading to excellent reversibility. To the best of our knowledge, these azole-based ionic liquids are superior to other adsorbent materials for direct air capture due to their dual-tunable properties and high CO2 capture efficiency, offering a new prospect for efficient and reversible direct air capture technologies.
RESUMO
MOFs are considered as efficient NH3 adsorbents for their high capacity but are accompanied by the collapse of MOFs. In this work, macromolecule-metal complexes (MMCs), which could provide metal sites like MOFs, were developed for reversible NH3 uptake with high capacity with the assistance of the polymeric ligands. Based on the tunable structure of MMCs, the role of the polymeric ligands and metallic center was investigated. Thereinto, MMCs-3 with dual polymeric ligands presented higher NH3 adsorption capacity and reversibility of adsorbents compared with MMCs containing a single polymeric ligand (MMCs-1 and MMCs-2). Combined with the NH3 adsorption test, characterization of FT-IR, UV-vis, EPR spectroscopy, NH3-TPD measurement, and the DFT calculations, it was found that the neutral polymeric ligands PVIm contributed to improve the stability of MMCs-3 under a NH3 atmosphere for the tough networks of PVIm-M(II), while the polymeric ligands with a carboxylate anion together with M(II) enhanced the NH3 capacity for the feasible coordination of a carboxylate anion with M(II). The mechanism of NH3 uptake by PVIm-Co-PVBA was proposed that the NH3 was fixed through the coordination with Co(II) along with the departure of PVBA and the following hydrogen bonding interaction with PVBA, while the coordination between PVIm and Co(II) was not destroyed. Thus, MMCs-3 with dual polymeric ligands presented a higher NH3 uptake capacity and stability. Optimally, PVIm-M-PVBA with the metal center of Co(II), Cu(II), and Ni(II) were obtained with a high capacity of 20.8-23.7 NH3 mmol/g at 25 °C and 1 bar and a high selectivity of NH3 over CO2 (54.9-99.9) and N2 (73.0-187.6) through the breakthrough measurement with a gas mixture of 0.2% NH3, 2% CO2, and 99.6% N2 at 25 °C.
RESUMO
Due to the active unstable nature of carbon anions, it is challenging to develop carbanion-functionalized ionic liquids (ILs) for efficient and reversible carbon dioxide (CO2) capture. Here, a series of carbanion-based ILs with large conjugated structures were designed and a promising system was achieved through tuning the nucleophilicity of carbanions and screening the cation. The ideal carbanion-functionalized IL trihexyl(tetradecyl)phosphonium N,N-diethycyanoacetoamide ([P66614][DECA]) showed equimolar chemisorption of CO2 (up to 0.98 mol CO2 /mol IL) under ambient pressure and excellent absorption rate. What's more, the combined CO2 can be released easily, leading to excellent reversibility due to high stability of anion conjugated structures. More importantly, the presence of water had negligible effect on the absorption capacity, which makes it potential to be applied to the CO2 capture in industrial flue gas. The chemisorption mechanism of the carbanion and CO2 was confirmed by spectroscopic investigations and DFT calculations, where carboxylic acid product was formed through proton transfer after the carbanions reacted with CO2. Considering that high capacity, quick rate as well as excellent reversibility, these carbanion-functionalized IL should certainly represent competitive candidates for further scale up and practical application in CO2 capture.
RESUMO
As a dietary strategy, methionine restriction has been reported to promote longevity and regulate metabolic disorders. However, the role and possible regulatory mechanisms underlying methionine in neurodegenerative diseases such as Alzheimer's disease (AD), remain unexplored. This study utilized the data from BXD recombinant inbred (RI) mice to establish a correlation between the AD phenotype in mice and methionine level. Gene enrichment analysis indicated that the genes associated with the concentration of methionine in the midbrain are involved in the dopaminergic synaptic signaling pathway. Protein interaction network analysis revealed that glycogen synthase kinase 3 beta (GSK-3ß) was a key regulator of the dopaminergic synaptic pathway and its expression level was significantly correlated with the AD phenotype. Finally, in vitro experiments demonstrated that methionine deprivation could reduce the expression of Aß and phosphorylated Tau, suggesting that lowering methionine levels in humans may be a preventive or therapeutic strategy for AD. In conclusion, our findings support that methionine is a high risk factor for AD. These findings predict potential regulatory network, theoretically supporting methionine restriction to prevent AD.