High-Pressure Molecular Sieving of High-Humidity C2H4/C2H6 Mixture by a Hydrophobic Flexible Metal-Organic Framework.

Molecular sieving is an ideal separation mechanism, but controlling pore size, restricting framework flexibility, and avoiding strong adsorption are all very challenging. Here, we report a flexible adsorbent showing molecular sieving at ambient temperature and high pressure, even under high humidity. While typical guest-induced transformations are observed, a high transition pressure of 16.6 atm is observed for C2H4 at 298 K because of very weak C2H4 adsorption (~16 kJ mol-1). Also, C2H6 is completely excluded below the pore-opening pressure of 7.7 atm, giving single-component selectivity of ca. 300. Quantitative high-pressure column breakthrough experiments using 1:1 C2H4/C2H6 mixture at 10 atm as input confirms molecular sieving with C2H4 adsorption of 0.73 mmol g-1 or 32 cm3(STP) cm-3 and negligible C2H6 adsorption of 0.001(2) mmol g-1, and the adsorbent can be completely regenerated by inert gas purging. Furthermore, it is highly hydrophobic with negligible water adsorption, and the C2H4/C2H6 separation performance is unaffected at high humidity.

Enrooted-Type Metal-Support Interaction Boosting Oxygen Evolution Reaction in Acidic Media.

Supported metal catalysts with appropriate metal-support interactions (MSIs) hold a great promise for heterogeneous catalysis. However, ensuring tight immobilization of metal clusters/nanoparticles on the support while maximizing the exposure of surface active sites remains a huge challenge. Herein, we report an Ir/WO3 catalyst with a new enrooted-type MSI in which Ir clusters are, unprecedentedly, atomically enrooted into the WO3 lattice. The enrooted Ir atoms decrease the electron density of the constructed interface compared to the adhered (root-free) type, thereby achieving appropriate adsorption toward oxygen intermediates, ultimately leading to high activity and stability for oxygen evolution in acidic media. Importantly, this work provides a new enrooted-type supported metal catalyst, which endows suitable MSI and maximizes the exposure of surface active sites in contrast to the conventional adhered, embedded, and encapsulated types.

Universal Synthesis of Single-Atom Catalysts by Direct Thermal Decomposition of Molten Salts for Boosting Acidic Water Splitting.

Single-atom catalysts (SACs) are considered prominent materials in the field of catalysis due to their high metal atom utilization and selectivity. However, the wide-ranging applications of SACs remain a significant challenge due to their complex preparation processes. Here, a universal strategy is reported to prepare a series of noble metal single atoms on different non-noble metal oxides through a facile one-step thermal decomposition of molten salts. By using a mixture of non-noble metal nitrate and a small-amount noble metal chloride as the precursor, noble metal single atoms can be easily introduced into the non-noble metal oxide lattice owing to the cation exchange in the in situ formed molten salt, followed by the thermal decomposition of nitrate anions during the heating process. Analyses using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure spectroscopy confirm the formation of the finely dispersed single atoms. Specially, the as-synthesized Ir single atoms (10.97 wt%) and Pt single atoms (4.60 wt%) on the Co3O4 support demonstrate outstanding electrocatalytic activities for oxygen evolution reaction and hydrogen evolution reaction, respectively.

Crystal Engineering of MOF-Derived Bimetallic Oxide Solid Solution Anchored with Au Nanoparticles for Photocatalytic CO2 Reduction to Syngas and C2 Hydrocarbons.

Considering that CO2 reduction is mostly a multielectron reaction, it is necessary for the photocatalysts to integrate multiple catalytic sites and cooperate synergistically to achieve efficient photocatalytic CO2 reduction to various products, such as C2 hydrocarbons. Herein, through crystal engineering, we designed and constructed a metal-organic framework-derived Zr/Ti bimetallic oxide solid solution support, which was confirmed by X-ray diffraction, electron microscopy and X-ray absorption spectroscopy. After anchoring Au nanoparticles, the composite photocatalyst exhibited excellent performances toward photocatalytic CO2 reduction to syngas (H2 and CO production rates of 271.6 and 260.6 µmol g-1 h-1) and even C2 hydrocarbons (C2H4 and C2H6 production rates of 6.80 and 4.05 µmol g-1 h-1). According to the control experiments and theoretical calculations, the strong interaction between bimetallic oxide solid solution support and Au nanoparticles was found to be beneficial for binding intermediates and reducing CO2 reduction, highlighting the synergy effect of the catalytic system with multiple active sites.

Reticular framework materials for photocatalytic organic reactions.

Photocatalytic organic reactions, harvesting solar energy to produce high value-added organic chemicals, have attracted increasing attention as a sustainable approach to address the global energy crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), are widely considered as promising candidates for photocatalysis owing to their high crystallinity, tailorable pore environment and extensive structural diversity. Although the design and synthesis of MOFs and COFs have been intensively developed in the last 20 years, their applications in photocatalytic organic transformations are still in the preliminary stage, making their systematic summary necessary. Thus, this review aims to provide a comprehensive understanding and useful guidelines for the exploration of suitable MOF and COF photocatalysts towards appropriate photocatalytic organic reactions. The commonly used reactions are categorized to facilitate the identification of suitable reaction types. From a practical viewpoint, the fundamentals of experimental design, including active species, performance evaluation and external reaction conditions, are discussed in detail for easy experimentation. Furthermore, the latest advances in photocatalytic organic reactions of MOFs and COFs, including their composites, are comprehensively summarized according to the actual active sites, together with the discussion of their structure-property relationship. We believe that this study will be helpful for researchers to design novel reticular framework photocatalysts for various organic synthetic applications.

Proteomic and metabolomic approaches elucidate the molecular mechanism of emodin against neuropathic pain through modulating the gamma-aminobutyric acid (GABA)-ergic pathway and PI3K/AKT/NF-κB pathway.

Neuropathic pain (NeP) is a major health concern. Due to the complex pathological mechanisms, management of NeP is challenging. Emodin, a natural anthraquinone derivative, exerts excellent analgesic effects. However, its mechanisms of action are still poorly understood. In this study, we investigated the mechanisms underlying pain-relief effects of emodin in the cerebral cortex using proteomic and metabolomic approaches. After 15 days of emodin administration, the mechanical withdrawal threshold (MWT) and thermal withdrawal latency (TWL) values in the emodin groups were significantly higher than those in the chronic constriction injury (CCI) group (p < .05), suggesting emodin treatment could reverse CCI-induced hyperalgesia. Emodin treatment evoked the expression alteration of 402 proteins (153 up-regulated and 249 down-regulated) in the CCI models, which were primarily involved in PI3K/AKT signaling pathway, gamma-aminobutyric acid (GABA) receptor signaling, complement and coagulation cascades, cGMP/PKG signaling pathway, MAPK signaling pathway, and calcium signaling pathway. In parallel, emodin intervention regulated the abundance alteration of 27 brain metabolites (20 up-regulated and 7 down-regulated) in the CCI rats, which were primarily implicated in carbon metabolism, biosynthesis of amino acids, pentose phosphate pathway, and glucagon signaling pathway. After a comprehensive analysis and western blot validation, we demonstrated that emodin alleviated NeP mainly through regulating GABAergic pathway and PI3K/AKT/NF-κB pathway.

Coupling Ruthenium Bipyridyl and Cobalt Imidazolate Units in a Metal-Organic Framework for an Efficient Photosynthetic Overall Reaction in Diluted CO2.

Artificial photocatalytic CO2 reduction, using water as the reductant, is challenging mainly because it is difficult for multiple functional units to cooperate efficiently. Here, we show that the classic photosensitive and H2O-oxidizing ruthenium bipyridyl units and CO2-reducing cobalt imidazolate units can be incorporated into a metal-organic framework using a classic organic ligand, imidazo[4,5-f][1,10]phenanthroline. Under visible light without additional sacrificial agents and photosensitizers, the overall conversion of CO2 and H2O to CO and O2 was achieved by the multifunctional photocatalyst in the CH3CN/H2O mixed solvent with a high CO production rate of 11.2 µmol g-1 h-1 and CO selectivity of ca. 100%. Thanks to its ultramicroporous structure with moderately strong CO2 adsorption ability, the photocatalyst also exhibited high performances with CO/CH4 production rates of 5.15/0.62 and 4.26/0.20 µmol g-1 h-1 in the gas phase with pure and even diluted CO2, respectively. Photoluminescence emission spectroscopy and photoelectrochemical tests confirmed that the photosensitive and catalytic units cooperated well to give suitable photocatalytic redox potentials and fast electron-hole separation.

The pathogenesis and treatment mechanism of Parkinson's disease from the perspective of traditional Chinese medicine.

BACKGROUND: Parkinson's disease (PD) is the second most common neurodegenerative disease with no treatment currently available to modify its progression. Traditional Chinese medicine (TCM) has gained attention for its unique theoretical basis and clinical effects. Many studies have reported on the clinical effects and pharmacological mechanisms of Chinese herbs in PD. However, few studies have focused on the treatment mechanisms of anti-PD TCM drugs from the perspective of TCM itself. PURPOSE: To elaborate the treatment mechanisms of anti-PD TCM drugs in the perspective of TCM. METHODS: We performed a literature survey using traditional books of Chinese medicine and online scientific databases including PubMed, Web of Science, Google Scholar, China National Knowledge Infrastructure (CNKI), and others up to July 2021. RESULTS: TCM theory states that PD is caused by a dysfunction of the zang-fu organs (liver, spleen, kidney, and lung) and subsequent pathogenic factors (wind, fire, phlegm, and blood stasis). Based on the pathogenesis, removing pathogenic factors and restoring visceral function are two primary treatment principles for PD in TCM. The former includes dispelling wind, clearing heat, resolving phlegm, and promoting blood circulation, while the latter involves nourishing the liver and kidney and strengthening the spleen. The anti-PD mechanisms of the active ingredients of TCM compounds and herbs at different levels include anti-apoptosis, anti-inflammation, and anti-oxidative stress, as well as the restoration of mitochondrial function and the regulation of autophagy and neurotransmitters. CONCLUSION: Chinese herbs and prescriptions can be used to treat PD by targeting multiple pharmacological mechanisms.

A Cu(111)@metal-organic framework as a tandem catalyst for highly selective CO2 electroreduction to C2H4.

Here, we report an improved tandem catalytic mechanism for electroreduction of CO2 to C2H4. Cu(111) nanoparticles with an average size of 5.5 ± 0.9 nm were anchored on a conductive Cu-based metal-organic framework (Cu-THQ) by in situ electrochemical synthesis. Compared to Cu(111) nanoparticles, the C2H4 faradaic efficiency of the tandem catalyst Cu(111)@Cu-THQ was increased doubly.

Electrostatic Attraction-Driven Assembly of a Metal-Organic Framework with a Photosensitizer Boosts Photocatalytic CO2 Reduction to CO.

Reducing CO2 into fuels via photochemical reactions relies on highly efficient photocatalytic systems. Herein, we report a new and efficient photocatalytic system for CO2 reduction. Driven by electrostatic attraction, an anionic metal-organic framework Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) as host and a cationic photosensitizer [Ru(phen)3]2+ (phen = 1,10-phenanthroline) as guest were self-assembled into a photocatalytic system Ru@Cu-HHTP, which showed high activity for photocatalytic CO2 reduction under laboratory light source (CO production rate of 130(5) mmol g-1 h-1, selectivity of 92.9%) or natural sunlight (CO production rate of 69.5 mmol g-1 h-1, selectivity of 91.3%), representing the remarkable photocatalytic CO2 reduction performance. More importantly, the photosensitizer [Ru(phen)3]2+ in Ru@Cu-HHTP is only about 1/500 in quantity reported in the literature. Theoretical calculations and control experiments suggested that the assembly of the catalysts and photosensitizers via electrostatic attraction interactions can provide a better charge transfer efficiency, resulting in high performance for photocatalytic CO2 reduction.

Mutations in DNAH8 contribute to multiple morphological abnormalities of sperm flagella and male infertility.

Asthenoteratospermia is an important cause of male infertility. Here, we report two infertile patients with severe asthenoteratospermia accompanied by new genetic abnormality. Whole-exome sequencing and bioinformatics analysis suggested that compound heterozygous mutations in DNAH8 (MIM:603337) may be responsible for multiple morphological abnormalities of the sperm flagella (MMAF). Immunofluorescence assay showed that DNAH8 protein expression was significantly decreased in the sperm tail of the patients, and electron microscopy exhibited an abnormal flagellum ultrastructure, while clinical pregnancy could be achieved by intracytoplasmic sperm injection. Therefore, the compound heterozygous mutations in the DNAH8 gene may be responsible for MMAF.

A Hydrogen-Bonded yet Hydrophobic Porous Molecular Crystal for Molecular-Sieving-like Separation of Butane and Isobutane.

Porous molecular crystals sustained by hydrogen bonds and/or weaker connections are an intriguing type of adsorbents, but they rarely demonstrate efficient adsorptive separation because of poor structural robustness and tailorability. Herein, we report a porous molecular crystal based on hydrogen-bonded cyclic dinuclear AgI complex, which exhibits exceptional hydrophobicity with a water contact angle of 134°, and high chemical stability in water at pH 2-13. The seemingly rigid adsorbent shows a pore-opening or nonporous-to-porous type butane adsorption isotherm and complete exclusion of isobutane, indicating potential molecular sieving. Quantitative column breakthrough experiments show slight co-adsorption of isobutane with an experimental butane/isobutane selectivity of 23, and isobutane can be purified more efficiently than for butane. In situ powder/single-crystal X-ray diffraction and computational simulations reveal that a trivial guest-induced structural transformation plays a critical role.

Pathway optimization of China's carbon emission reduction and its provincial allocation under temperature control threshold.

As the largest carbon emitter in the world, China faces great pressure to fulfill the temperature control targets, i.e., 2 °C and 1.5 °C, proposed in the Paris Agreement. Thus, selecting a development path that could both meet the temperature targets and economic growth is essential and worth investigating. We propose an optimization model to analyze China's carbon dioxide emission paths from 2010 to 2050 in three scenarios, namely baseline, and 1.5 °C and 2 °C target scenarios. The marginal cost of carbon abatement in China's 30 provinces (excluding Hong Kong, Macao, Taiwan, and Tibet) were also calculated using the quadratic directional distance function model, and the quotas of carbon dioxide emission among provinces were allocated. Carbon dioxide emission peak will occur in 2040 under the 2 °C target scenario and in 2030 under the 1.5 °C target scenario. The marginal cost of carbon abatement to achieve the 1.5 °C goal is approximately 1.6 times more expensive than the 2 °C goal. We suggest to implement emission reduction policies in the Eastern coastal areas of China and to allocate greater carbon dioxide emission quotas in under-developed areas in the Central and Western regions. Provincial quota allocation may also help to balance regional development and achieve the mutually beneficial goal of economic growth and carbon emission reduction in China. Our findings provide practical guidance on achieving carbon dioxide emission reduction and critical enlightenments on policymaking.

A metal-organic framework with in situ generated low-coordinate binuclear Cu(i) units as a highly effective catalyst for photodriven hydrogen production.

Herein, we report a metal-organic framework featuring a binuclear copper unit, showing extraordinarily high catalytic activity (102.8 mmol g-1 h-1) for photodriven hydrogen generation, which is attributed to the synergistic catalytic effect between the two copper ions.

A local hydrophobic environment in a metal-organic framework for boosting photocatalytic CO2 reduction in the presence of water.

The methylene groups surrounding the metal center in a metal-organic framework provide hydrophobic repulsive forces to H2O, resulting in a high catalytic activity (TOF = 73.8 h-1, selectivity of 96%) for photodriven CO2 reduction into CO.

Intermediate-sized molecular sieving of styrene from larger and smaller analogues.

Molecular sieving can lead to ultrahigh selectivity and low regeneration energy because it completely excludes all larger molecules via a size restriction mechanism. However, it allows adsorption of all molecules smaller than the pore aperture and so separations of complicated mixtures can be hindered. Here, we report an intermediate-sized molecular sieving (iSMS) effect in a metal-organic framework (MAF-41) designed with restricted flexibility, which also exhibits superhydrophobicity and ultrahigh thermal/chemical stabilities. Single-component isotherms and computational simulations show adsorption of styrene but complete exclusion of the larger analogue ethylbenzene (because it exceeds the maximal aperture size) and smaller toluene/benzene molecules that have insufficient adsorption energy to open the cavity. Mixture adsorption experiments show a high styrene selectivity of 1,250 for an ethylbenzene/styrene mixture and 3,300 for an ethylbenzene/styrene/toluene/benzene mixture (orders of magnitude higher than previous reports). This produces styrene with a purity of 99.9%+ in a single adsorption-desorption cycle. Controlling/restricting flexibility is the key for iSMS and can be a promising strategy for discovering other exceptional properties.

Selective Aerobic Oxidation of a Metal-Organic Framework Boosts Thermodynamic and Kinetic Propylene/Propane Selectivity.

Efficient adsorptive separation of propylene/propane (C3 H6 /C3 H8 ) is highly desired and challenging. Known strategies focus on either the thermodynamic or the kinetic mechanism. Here, we report an interesting reactivity of a metal-organic framework that improves thermodynamic and kinetic adsorption selectivity simultaneously. When 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 C3 H6 /C3 H8 selectivity from 1.5 to 15. For comparison, the C3 H6 /C3 H8 selectivities of the best-performing metal-organic frameworks Co-MOF-74 and KAUST-7 were experimentally determined to be 6.5 and 12, respectively. Gas adsorption isotherms/kinetics, single-crystal X-ray diffraction, and computational simulations revealed that the oxidation gives additional guest recognition sites, which improve thermodynamic selectivity, and reduces the framework flexibility, which generate kinetic selectivity.

An exceptionally stable octacobalt-cluster-based metal-organic framework for enhanced water oxidation catalysis.

Extensive efforts have been devoted to developing efficient and durable catalysts for water oxidation. Herein, we report a highly stable metal-organic framework that shows high catalytic activity and durability for electrically driven (an overpotential of 430 mV at 10 mA cm-2 in neutral aqueous solution) and photodriven (a turnover frequency of 16 s-1 and 12 000 cycles) water oxidation, representing the best catalyst for water oxidation reported to date. Computational simulation and isotope tracing experiments showed that the µ4-OH group of the {Co8(µ4-OH)6} unit participates in the water oxidation reaction to offer an oxygen vacancy site with near-optimal OH- adsorption energy.

DNA methylation of a non-CpG island promoter represses NQO1 expression in rat arsenic-transformed lung epithelial cells.

NAD(P)H:quinone oxidoreductase 1 (NQO1), a phase II flavoenzyme that catalyzes reduction reactions to protect cells against electrophiles and oxidants, is involved in tumorigenesis. Altered methylation of the NQO1 gene has been observed and is speculated to result in aberrant NQO1 expression in rat cells undergoing chemical carcinogenesis, although this has not been proven experimentally. In this study, we first investigated the potential epigenetic mechanisms underlying the phenomenon of NQO1 differential expression in individual subclones of rat arsenic-transformed lung epithelial cells (TLECs). NQO1 expression of TLEC subclones with or without 5-aza-2'-deoxycytidine (5-Aza-CdR) treatment was assessed by reverse transcriptase-polymerase chain reaction (RT-PCR), western blot analysis, and real-time PCR. Methylation status of the NQO1 promoter in TLEC subclones was analyzed by bisulfite sequencing. Transcriptional activity of NQO1 promoter in vitro methylated was determined by luciferase assay using a CpG-free luciferase reporter driven by the NQO1 promoter region (-435 to +229). We found that non-CpG island (non-CpGI) within the NQO1 promoter was hyper- or hypo-methylated in TLEC subclones and corresponded to low and high gene expressions, respectively. Following the treatment with 5-Aza-CdR, transcription of the NQO1 gene in the hypermethylated subclones was restored, accompanied by demethylation of the NQO1 promoter. In vitro promoter methylation almost completely silenced reporter activity in TLECs. These results indicate that DNA methylation of the non-CpGI promoter contributes to epigenetic silencing of NQO1 in rat TLECs.

STK24 expression is modulated by DNA copy number/methylation in lung adenocarcinoma and predicts poor survival.

AIM: To explore the independent prognostic value of STK24 expression in terms of overall survival and recurrence-free survival and the potential mechanisms of its dysregulation in non-small-cell lung adenocarcinoma. PATIENTS & METHODS: Data were from the Cancer Genome Atlas-lung adenocarcinoma. RESULTS: Increased STK24 expression was an independent prognostic indicator of unfavorable overall survival (Hazard ratio: 1.478; 95% CI: 1.149-1.901; p < 0.002) and recurrence-free survival (Hazard ratio: 1.855; 95% CI: 1.399-2.458; p < 0.001). DNA amplification was associated with significantly upregulated STK24 expression. There was a weak negative correlation between STK24 expression and its DNA methylation (Pearson's r = -0.32). CONCLUSION: Aberrant STK24 expression was an independent prognostic indicator in lung adenocarcinoma patients. Its dysregulation was associated with its DNA copy number alteration and methylation.