Ionic Liquids Functionalized MOFs for Adsorption.

Metal-organic frameworks (MOFs) and ionic liquids (ILs) represent promising materials for adsorption separation. ILs incorporated into MOF materials (denoted as IL/MOF composites) have been developed, and IL/MOF composites combine the advantages of MOFs and ILs to achieve enhanced performance in the adsorption-based separation of fluid mixtures. The designed different ILs are introduced into the various MOFs to tailor their functional properties, which affect the optimal adsorptive separation performance. In this Perspective, the rational fabrication of IL/MOF composites is presented, and their functional properties are demonstrated. This paper provides a critical overview of an emergent class of materials termed IL/MOF composites as well as the recent advances in the applications of IL/MOF composites as adsorbents or membranes in fluid separation. Furthermore, the applications of IL/MOF in adsorptive gas separations (CO2 capture from flue gas, natural gas purification, separation of acetylene and ethylene, indoor pollutants removal) and liquid separations (separation of bioactive components, organic-contaminant removal, adsorptive desulfurization, radionuclide removal) are discussed. Finally, the existing challenges of IL/MOF are highlighted, and an appropriate design strategy direction for the effective exploration of new IL/MOF adsorptive materials is proposed.

Se-(Fluoromethyl) Benzenesulfonoselenoates: Shelf-Stable, Easily Available Reagents for Monofluoromethylselenolation.

A new class of electrophilic monofluoromethylselenolation reagents, Se-(fluoromethyl) benzenesulfonoselenoates, has been developed. They can be readily prepared from sodium benzenesulfinates, Se powder and ClCFH2 in one step under mild reaction conditions. Se-(fluoromethyl) benzenesulfonoselenoates are efficient electrophilic monofluoromethylselenolation reagents for a wide range of nucleophiles including indole, 6-azaindole, pyrrole, thiophene, electron-rich arene, aryl boronic acid and alkyne. The monofluoromethylselenolation approach features mild and environmentally friendly reaction conditions, good tolerance of various functional groups, and broad substrate scope.

Switchable, Reagent-Controlled C(sp3)-H Selective Iodination and Acetoxylation of 8-Methylquinolines.

An efficient Pd-catalyzed C(sp3)-H selective iodination of 8-methylquinolines is reported herein for the first time. Because of the versatility of organic iodides, the method offers a facile access to various C8-substituted quinolines. By slightly switching the reaction conditions, an efficient C(sp3)-H acetoxylation of 8-methylquinolines has also been enabled. Both approaches feature mild reaction conditions, good tolerance of functional groups, and a broad substrate scope.

Synthesis of Acyl Hydrazides via a Radical Chemistry of Azocarboxylic tert-Butyl Esters.

A new chemistry of azo compounds, that is, addition of free radicals generated in situ to access various acyl hydrazides, has been developed. The protocol provides a novel strategy for the synthesis of valuable acyl hydrazides. The transformation features mild reaction conditions, good tolerance of functional groups, and a broad substrate scope. In view of the importance of acyl hydrazides in functional materials and medicinal chemistry, this approach would find broad applications.

A well-defined hierarchically porous metal-organic framework and its application in separation and purification of steviol glycosides.

The separation and removal of stevioside from natural product steviol glycosides to obtain high-purity rebaudioside A is of great significance for the application of steviol glycosides in food, medicine, and other fields. Here, in order to explore the adsorbent pore structure suitable for the separation of stevioside and rebaudioside A, a hierarchically porous amino-functionalized metal-organic framework (HP-NH2 -MIL-53) with an appropriate and narrow pore size distribution was prepared using a modulator-induced defect-formation strategy. The results showed that the hierarchically porous structure with micropores and mesopores increased the specific surface area and exposed amino groups compared with original metal organic framework (NH2 -MIL-53), and the maximum adsorption capacity of HP-NH2 -MIL-53 for stevioside and rebaudioside A was 233.89 mg/g. The narrow pore size distribution close to 3.80 nm promoted the screening effect, resulting in a maximum adsorption selectivity of 4.13. This work proves that when the pore size of the adsorbent is between 1.41 and 3.80 nm, it has a certain pore size screening effect on stevioside and rebaudioside A, and the hierarchically porous metal-organic frameworks provide a pre-design idea of adsorbent structure for the separation of natural products with molecular weight of 800-1000 Da.

Synthesis of Aporphine Analogues via Palladium-Catalyzed Intramolecular Aryl-Aryl Dehydrogenative Coupling.

Reported herein is an intramolecular dehydrogenative coupling of two inert aryl C-H bonds for the synthesis of aporphine analogues. The process represents a novel tool for the preparation of aporphines via palladiun-catalyzed C-H bond activation. The present reaction is compatible with various functional groups, and the coupling products have been further applied for the synthesis of natural products aporphine and zenkerine.

Synthesis of trifluoromethylthioesters from aldehydes via a visible light-promoted radical process.

We report herein an efficient, economical, and scalable trifluoromethylthiolation of aldehydes to generate trifluoromethylthioesters via a visible light-promoted radical process. The transformation features cheap reagents, simple operation, a broad substrate scope, and especially no metal involved in the reaction. Trifluoromethylthiolations of several complex aldehyde-containing bioactive compounds have been realized; thus the approach has the potential to be an important tool for the late-stage functionalization of advanced synthetic intermediates and bioactive molecules, and should have many applications in medicinal chemistry.

Mixed matrix membranes with fast and selective transport pathways for efficient CO2 separation.

To improve CO2 separation performance, porous carbon nanosheets (PCNs) were used as a filler into a Pebax MH 1657 (Pebax) matrix, fabricating mixed matrix membranes (MMMs). The PCNs exhibited a preferential horizontal orientation within the Pebax matrix because of the extremely large 2D plane and nanoscale thickness of the matrix. Therefore, the micropores of the PCNs provided fast CO2 transport pathways, which led to increased CO2 permeability. The reduced pore size of the PCNs was a consequence of the overlapping of PCNs and the polymer chains penetrating into the pores of the PCNs. The reduction in the pore size of the PCNs improved the CO2/gas selectivity. As a result, the CO2 permeability and CO2/CH4 selectivity of the Pebax membrane with 10 wt% PCNs-loading (Pebax-PCNs-10) were 520 barrer and 51, respectively, for CO2/CH4 mixed-gas. The CO2 permeability and CO2/N2 selectivity of the Pebax-PCNs-10 membrane were 614 barrer and 61, respectively, for CO2/N2 mixed-gas.

Hot Deformation Behavior of a Hot-Isostatically Pressed Ti-6Al-4V Alloy from Recycled Powder.

In this work, a new use of mixed Ti-6Al-4V powder, consisting of the retained powder after screening for additive manufacturing and the recycled powder after multiple printing, has been exploited. The powder mixture has been hot-isostatically-pressed (HIPed) at 930 °C/120 MPa for 3 h to reach full density. The hot deformation behavior of the as-HIPed powder compacts were investigated through isothermal compression tests, kinetic analyses, and hot processing maps. Finally, the optimized hot working parameters were validated using upsetting tests. The results show that the as-HIPed Ti-6Al-4V alloy has a fine and homogeneous microstructure. The activation energies were calculated to be 359 kJ/mol in the α + ß phase regime and 463 kJ/mol in the ß phase regime, respectively. The optimal hot working parameters are a deformation temperature above 950 °C and strain rate higher than 0.1 s-1. The hot workability of as-HIPed powder compacts is better than the as-cast billets. The deformed microstructure can be finer than that of as-HIPed state, and the mechanical performance can be further improved by the optimal thermo-mechanical processing treatment.

Palladium-Catalyzed Three-Component Regioselective Dehydrogenative Coupling of Indoles, 2-Methylbut-2-ene, and Carboxylic Acids.

Five-carbon (C5) structural units are the fundamental building blocks of many natural products. An unprecedented palladium-catalyzed three-component dehydrogenative cascade coupling of indoles, 2-methylbut-2-ene, and carboxylic acids has been developed. The approach enables the straightforward introduction of a C3'-bonded five-carbon structural unit with a tertiary alcohol quaternary carbon center into indoles. The protocol employs 2-methylbut-2-ene as the C5 source and is featured by a broad substrate scope, atom and step economies, and high chemo- and regioselectivies.

Palladium-Catalyzed Dehydrogenative Fluoroalkoxylation of Benzaldehydes.

A direct and efficient palladium-catalyzed oxidative dehydrogenative fluoroalkoxylation of benzaldehydes is reported here for the first time. The method features mild reaction conditions, good tolerance of functional groups, and a broad substrate scope. The protocol employs the transient directing group strategy, thereby avoiding the additional installation and removal of directing groups, endowing the method with great advantages of atom and step economy. The approach should find broad applications in drug synthesis and discovery processes.

Aerobic Oxidative Dehydrogenation of Ketones to 1,4-Enediones.

An efficient and unprecedented strategy for the synthesis of 1,4-enediones from saturated ketones has been developed via palladium-catalyzed oxidative dehydrogenation. The protocol employs molecular oxygen as the sole oxidant and represents an atom- and step-economic process. The approach showed broad substrate scope, good functional group tolerance, and complete E-stereoselectivity. The reaction mechanism has been investigated through deuterium-labeling experiments and intermediate experiments.

rhFGF20 promotes angiogenesis and vascular repair following traumatic brain injury by regulating Wnt/ß-catenin pathway.

The pathology of cerebrovascular disorders takes an important role in traumatic brain injury (TBI) by increasing intracranial pressure. Fibroblast growth factor 20 (FGF20) is a brain-derived neurotrophic factor, that has been shown to play an important role in the survival of dopaminergic neurons and the treatment of Parkinson's disease (PD). However, little is known about the role of FGF20 in the treatment of TBI and its underlying mechanism. The purpose of this study was to evaluate the protective effect of recombinant human FGF20 (rhFGF20) on protecting cerebral blood vessels after TBI. In this study, we indicated that rhFGF20 could reduce brain edema, Evans blue penetration and upregulated the expression of blood-brain barrier (BBB)-related tight junction (TJ) proteins, exerting a protective effect on the BBB in vivo after TBI. In the TBI repair phase, rhFGF20 promoted angiogenesis, neurological and cognitive function recovery. In tumor necrosis factor-α (TNF-α)-induced human brain microvascular endothelial cells (hCMEC/D3), an in vitro BBB disruption model, rhFGF20 reversed the impairment in cell migration and tube formation induced by TNF-α. Moreover, in both the TBI mouse model and the in vitro model, rhFGF20 increased the expression of ß-catenin and GSK3ß, which are the two key regulators in the Wnt/ß-catenin signaling pathway. In addition, the Wnt/ß-catenin inhibitor IWR-1-endo significantly reversed the effects of rhFGF20. These results indicate that rhFGF20 may prevent vascular repair and angiogenesis through the Wnt/ß-catenin pathway.

Synthesis of difluoromethylselenoesters from aldehydes via a radical process.

Difluoromethylselenoester compounds, another important kind of organoselenium compounds, are reported herein for the first time. They can be efficiently synthesized from aldehydes and BnSeCF2H. The synthetic method features mild reaction conditions, broad substrate scope, good tolerance of functional groups, and importantly, no metal is involved in the reaction.

[Microbial Diversity and Influencing Factors in a Small Watershed in Winter].

The water quality of a small watershed will directly affect the water quality safety of the entire watershed. The Lidu small watershed of the Fulin District in Chongqing was selected for this study. The characteristics of runoff and the microbial community in the receiving water body were analyzed by high-throughput sequencing technology. The effects of the physical and chemical factors of the water body on the microbial diversity in the water body were also investigated. The results showed that the small watershed of Lidu was an important source of nitrite and dissolved organic carbon for the receiving water. There was no significant difference in the microbial richness and diversity of the water flowing through different pollution sources in the small watershed, and the microbial diversity index was negatively correlated with the total phosphorus (r -0.79--0.84, P ≤ 0.01) and phosphate (r -0.71--0.80, P ≤ 0.01) of the water. At the phylum level, Actinobacteria (37.33% ±14.69%) accounted for the largest proportion of runoff flowing through the agricultural area, followed by Proteobacteria (32.53% ±7.18%), Cyanobacteria (14.65% ±22.64%), Bacteroidetes (8.50% ±3.67%), and others. Proteobacteria (43.67% ±10.80%) accounted for the largest proportion of runoff flowing through the industrial area, followed by Bacteroidetes (25.33% ±11.97%), Actinobacteria (24.17% ±14.66%), Firmicutes (2.53% ±0.72%), and others. At the genus level, hgcI_clade (19.08% ±13.46%) accounted for the largest proportion of runoff flowing through the agricultural area, followed by CL 500-29 _marine_group (7.40% ±4.44%), Limnohabitans (7.05% ±3.14%), and others. Flavobacterium (20.40% ±12.37%) accounted for the largest proportion of runoff flowing through the industrial area, followed by hgcI_clade (15.30% ±11.11%), Acinetobacter (9.33% ±11.50%), and others. The Flavobacterium in the runoff water may be related to the input of industrial sources in the watershed. Nitrous nitrogen, total phosphorus, phosphate, pH, and Zn2+ were the main environmental factors that affected the microbial community in the small watershed. They can explain the variance of microbial community 0.26, 0.21, 0.20, 0.15, and 0.14, respectively. DOC, nitrate nitrogen, and heavy metal ions such as Cu2+, Zn2+, Mn2+, and As3+ were also related to the proportion of some microorganisms in the water.

FGF20 Protected Against BBB Disruption After Traumatic Brain Injury by Upregulating Junction Protein Expression and Inhibiting the Inflammatory Response.

Disruption of the blood-brain barrier (BBB) and the cerebral inflammatory response occurring after traumatic brain injury (TBI) facilitate further brain damage, which leads to long-term complications of TBI. Fibroblast growth factor 20 (FGF20), a neurotrophic factor, plays important roles in brain development and neuronal homeostasis. The aim of the current study was to assess the protective effects of FGF20 on TBI via BBB maintenance. In the present study, recombinant human FGF20 (rhFGF20) reduced neurofunctional deficits, brain edema, Evans blue extravasation and neuroinflammation in a TBI mouse model. In an in vitro TNF-α-induced human brain microvascular endothelial cell (HBMEC) model of BBB disruption, rhFGF20 reduced paracellular permeability and increased trans-endothelial electrical resistance (TEER). Both in the TBI mouse model and in vitro, rhFGF20 increased the expression of proteins composing in BBB-associated tight junctions (TJs) and adherens junctions (AJs), and decreased the inflammatory response, which protected the BBB integrity. Notably, rhFGF20 preserved BBB function by activating the AKT/GSK3ß pathway and inhibited the inflammatory response by regulating the JNK/NFκB pathway. Thus, FGF20 is a potential candidate treatment for TBI that protects the BBB by upregulating junction protein expression and inhibiting the inflammatory response.

Non-Mitogenic Fibroblast Growth Factor 1 Enhanced Angiogenesis Following Ischemic Stroke by Regulating the Sphingosine-1-Phosphate 1 Pathway.

Ischemic strokes account for about 80% of all strokes and are associated with a high risk of mortality. Angiogenesis of brain microvascular endothelial cells may contribute to functional restoration following ischemia. Fibroblast growth factor 1 (FGF1), a member of FGF superfamily, involved in embryonic development, angiogenesis, wound healing, and neuron survival. However, the mitogenic activity of FGF1 is known to contribute to several human pathologies, thereby questioning the safety of its clinical applications. Here, we explored the effects and mechanism of action of non-mitogenic FGF1 (nmFGF1) on angiogenesis in mice after ischemia stroke and an oxygen-glucose deprivation (OGD)-induced human brain microvascular endothelial cells (HBMECs) injury model. We found that intranasal administration nmFGF1 significantly promoted angiogenesis in mice after stroke, and significantly increased the formation of matrigel tube and promoted scratch migration in a dose-dependent manner in OGD-induced HBMECs in vitro. However, the co-administration of an FGF receptor 1 (FGFR1)-specific inhibitor PD173074 significantly reversed the effects of nmFGF1 in vitro, suggesting that nmFGF1 functions via FGFR1 activation. Moreover, nmFGF1 activated sphingosine-1-phosphate receptor 1 (S1PR1, S1P1) in mice after stroke in vivo. S1P1 protein antagonist VPC23019 and agonist FTY720 were used to confirm that nmFGF1 promotes angiogenesis in vitro partially through the S1P1 pathway. OGD induced downregulation of S1P1 expression. The S1P1 antagonist VPC23019 blocked the stimulatory effects of nmFGF1, whereas the S1P1 agonist FTY720 exerted effects comparable with those of nmFGF1. Furthermore, PD173074 reversed the effect of nmFGF1 on upregulating S1P1 signaling. In conclusion, nmFGF1 enhanced angiogenesis in mice following stroke and OGD-induced HBMECs through S1P1 pathway regulation mediated via FGFR1 activation. This new discovery suggests the potential therapeutic role of nmFGF1 for the treatment of ischemic strokes.

FGF21 Attenuated LPS-Induced Depressive-Like Behavior via Inhibiting the Inflammatory Pathway.

Major depressive disorder is a serious neuropsychiatric disorder with high rates of recurrence and mortality. Many studies have supported that inflammatory processes play a central role in the etiology of depression. Fibroblast growth factor 21 (FGF21), a member of the fibroblast growth factors (FGFs) family, regulates a variety of pharmacological activities, including energy metabolism, glucose and lipid metabolism, and insulin sensitivity. In addition, recent studies showed that the administration of FGF21, a regulator of metabolic function, had therapeutic effects on mood stabilizers, indicating that FGF21 could be a common regulator of the mood response. However, few studies have highlighted the antidepressant effects of FGF21 on lipopolysaccharide (LPS)-induced mice, and the anti-inflammatory mechanism of FGF21 in depression has not yet been elucidated. The purpose of the current study was to determine the antidepressant effects of recombinant human FGF21 (rhFGF21). The effects of rhFGF21 on depression-like behaviors and the inflammatory signaling pathway were investigated in both an LPS-induced mouse model and primary microglia in vitro. The current study demonstrated that LPS induced depressive-like behaviors, upregulated proinflammatory cytokines, and activated microglia in the mouse hippocampus and activated the inflammatory response in primary microglia, while pretreatment with rhFGF21 markedly improved depression-like behavior deficits, as shown by an increase in the total distance traveled and number of standing numbers in the open field test (OFT) and a decrease in the duration of immobility in the tail suspension test (TST) and forced swimming test (FST). Furthermore, rhFGF21 obviously suppressed expression levels of the proinflammatory cytokines interleukin-1ß (IL-1ß), tumor necrosis factor-α (TNF-α), and interleukin-6 (IL-6) and inhibited microglial activation and the nuclear factor-κB (NF-κB) signing pathway. Moreover, coadministration of rhFGF21 with the fibroblast growth factor receptor 1 (FGFR1) inhibitor PD173074 significantly reversed these protective effects, indicating that the antidepressant effects of rhFGF21 occur through FGFR1 activation. Taken together, the results of the current study demonstrated for the first time that exogenous rhFGF21 ameliorated LPS-induced depressive-like behavior by inhibiting microglial expression of proinflammatory cytokines through NF-κB suppression. This new discovery suggests rhFGF21 as a new therapeutic candidate for depression treatment.

Introducing hydrophilic ultra-thin ZIF-L into mixed matrix membranes for CO2/CH4 separation.

Mixed matrix membranes (MMMs) were developed by mixing hydrophilically modified two-dimensional (2D) imidazole framework (named as hZIF-L) flakes into a Pebax MH 1657 (Pebax) matrix, and designed to separate carbon dioxide/methane (CO2/CH4) mixtures. The hZIF-L flakes were important for increasing the effectiveness of the MMMs. First, the tannic acid (TA) etched hZIF-L flakes have a large number of microporous (1.8 nm) and two-dimensional anisotropic transport channels, which offered convenient gas transport channels and improved the permeability of CO2. Second, the TA molecules provide the surface of the ZIF-L flakes with more hydrophilic functional groups such as carbonyl groups (C[double bond, length as m-dash]O) and hydroxyl groups (-OH), which could effectively prevent non-selective interfacial voids and filler agglomeration in the Pebax matrix, and also presented strong binding ability to water and CO2 molecules. The satisfactory interface compatibility and affinity with the CO2 molecule promoted its permeability, solubility, and selectivity. As a result, the MMMs exhibited the highest performance of gas separation with the hZIF-L flake weight content of 5%, at which the CO2 permeability and CO2/CH4 selectivity were 502.44 barrer and 33.82 at 0.2 MPa and 25 °C, respectively.

Selective Adsorption and Purification of the Acteoside in Cistanche tubulosa by Molecularly Imprinted Polymers.

Acteoside (ACT) is the main component of phenylethanoid glycosides in Cistanche tubulosa, and it is extremely desirable for obtaining high purification of ACT by molecularly imprinted polymers (MIPs) from their extracts. In this study, MIPs were designed and synthetized to adsorb selectively the ACT in C. tubulosa. The effects of different functional monomers, cross-linkers, and solvents of MIPs were investigated. MIPs were studied in terms of static adsorption experiments, dynamic adsorption experiments, and selectivity experiments. The optimal functional monomer, cross-linking agent, and solvent are 4-vinylpyridine, ethylene glycol dimethylacrylate, and the mixed solvent (acetonitrile and N,N-dimethylformamide, 1:1.5, v/v), respectively. Under the optimal conditions, the synthesized MIP1 has a high adsorption performance for ACT. The adsorption capacity of MIP1 to ACT reached 112.60 mg/g, and the separation factor of ACT/echinacoside was 4.68. Because the molecularly imprinted cavities of MIP1 resulted from template molecules of ACT, it enables MIP1 to recognize selectively ACT. Moreover, the N-H groups on MIP1 can form hydrogen bonds with the hydroxyl groups on the ACT; this improves the separation factor of MIP1. The dynamic adsorption of ACT accorded with the quasi-second-order kinetics; it indicated that the adsorption process of MIP1 is the process of chemical adsorption to ACT. MIPs can be applied as a potential adsorption material to purify the active ingredients of herbal medicines.