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[Display omitted] • A novel collector BHBA is developed based on benzohydroxamic acid (BHA) structure. • 4-butoxy- N -hydroxybenzamide (BHBA) has a good selectivity in cassiterite flotation. • BHBA has a longer carbon chain and enhanced reactivity of the N -hydroxyamide group. • These two factors enhance BHBA's ability to collect cassiterite more effectively. In cassiterite flotation, the superior selectivity of benzohydroxamic acid (BHA) leads to its common use as a collector. However, its weak collecting ability necessitates the synthesis of 4-butoxy- N -hydroxybenzamide (BHBA) by introducing a butoxy group at the para -position of the N -hydroxyamide group in BHA molecular structure. BHBA, when functioning as a collector in the flotation separation of cassiterite and calcite, retains BHA selectivity while enhancing its collecting ability. Zeta potential experiments show that under same reagent dosage and slurry pH conditions, BHBA is adsorbed in larger amounts on cassiterite surface than on calcite, conferring its stronger collecting ability in cassiterite flotation. X-ray photoelectron spectroscopy reveals that BHBA donates more electrons to Sn4+ ions on cassiterite surface versus Ca2+ ions on calcite surface, resulting in the intensified adsorption affinity of BHBA on cassiterite. First-principles calculations indicate that BHBA achieves higher recoveries of cassiterite relative to BHA, attributed to its longer hydrophobic carbon chain and the electron-donating nature of the butoxy group, which enhances the reactivity of the N -hydroxy amide group in BHBA. [ABSTRACT FROM AUTHOR]

• DDAIP is synthesized through incorporating a 2-hydroxy propyl group into DDA. • DDAIP has better selectivity in flotation separation of apatite/quartz than DDA. • DDAIP has a stronger affinity on quartz surface with a similar affinity on apatite. • The OH group enhances the interaction of DDAIP with Si atoms on quartz surface. • Steric hindrance hinders N and O of DDAIP from simultaneous reactions with apatite. This study synthesized a novel amine collector, 1-(dodecylamino)-2-propanol (DDAIP), by incorporating a 2-hydroxy propyl group into the molecular structure of dodecylamine (DDA). Flotation experiments showed that utilizing DDAIP collector resulted in a substantial difference of ∼80% in flotation recoveries between apatite and quartz. Employing DDA as the collector yielded a difference of ∼30% in flotation recoveries between the two minerals. DDAIP demonstrated a superior selectivity in the reverse flotation separation of apatite and quartz in comparison to DDA. Zeta potential experiments indicated that, under identical dosages, DDAIP demonstrated increased adsorption capacities on quartz surface in contrast to DDA, whereas the adsorption amounts on apatite surface remained similar for both the collectors. By combining XPS analysis and first-principles calculations, DDAIP demonstrated enhanced chemical interactions with the Si atoms on quartz surface and a greater number of hydrogen bonds with quartz surface compared to DDA. The presence of an isopropyl group between the hydroxyl and secondary amine groups in DDAIP molecular structure leads to steric hindrance, hindering the simultaneous chemical interactions of the O and N atoms in DDAIP with the Ca2+ ions on apatite surface. Thus, the incorporation of the 2-hydroxy propyl group into DDAIP molecular structure does not enhance its adsorption strength on apatite surface when compared to DDA. [ABSTRACT FROM AUTHOR]

A novel photothermal agent based on PEGylated SnS nanosheets is developed via a simple solvothermal route and the subsequent exfoliation is carried out using an ultrasonication method. The PEGylated SnS nanosheets exhibit much higher extinction coefficient and photothermal conversion efficiency than bulk SnS. With the irradiation of the NIR light, cancer cells in vitro can be efficiently killed by the photothermal effects of the SnS nanosheets. The findings reported here show promising potential for further exploration of 2D nanomaterials as a nanoplatform for cancer therapy. [ABSTRACT FROM AUTHOR]

We report a facile and low-cost approach to design a difunctional nanoplatform (CuS@mSiO2-PEG) as a near-infrared (NIR) light responsive drug delivery system for efficient chemo-photothermal therapy. The nanoplatform demonstrated good biocompatibility and colloidal stability, as well as high loading capacity for the anticancer drug (26.5 wt% for doxorubicin (DOX)). The CuS nanocrystals (core) within these CuS@mSiO2-PEG core–shell nanoparticles can effectively absorb and convert NIR light to fatal heat under NIR light irradiation for photothermal therapy, and the release of DOX from the mesoporous silica (shell) can be triggered by pH and NIR light for chemotherapy. When the CuS@mSiO2-PEG/DOX nanocomposites were irradiated by 980 nm light, both chemotherapy and photothermal therapy were simultaneously driven, resulting in a synergistic effect for killing cancer cells. Importantly, compared with chemotherapy or photothermal treatment alone, the combined therapy significantly improved the therapeutic efficacy. [ABSTRACT FROM AUTHOR]

Highlights: [•] Highly CO2-soluble ethylene oxide diphosphates were designed and synthesized. [•] Solubility were determined and correlated by Bartle and Chrastil model. [•] Partial molar volumes of these compounds in scCO2 were estimated. [•] Branched side chain played an important role in the enhancement of solubility. [ABSTRACT FROM AUTHOR]

Fluoxetine hydrochloride enantiomers were separated by chromatography on Tris‐(3,5‐dimethylphenyl carbamate) cellulose as a chiral stationary phase (CSP). The effects of mobile phase composition, flow rate, and column temperature on capacity factor, separation factor, and resolution were studied systematically. Best separation was obtained with a mobile phase composition of hexane/isopropyl alcohol/diethylamine of 98/2/0.2 (v/v/v) at 15°C. The optimal flow rate was 0.24 mL/min from the Van Deemter equation. However, baseline resolution (R S >1.5) was achieved under a flow rate of 0.8 mL/min. Thermodynamic parameters Δ H 0 , Δ S,R Δ H 0 , and Δ S,R Δ S 0 were calculated. In the temperature range examined, the enthalpic contribution to the enantiomer transfer energy was found to be more significant than the entropic one. [ABSTRACT FROM AUTHOR]

To develop a process for separation of natural α-tocopherol from γ- and δ-tocopherols by supercritical fluid chromatography, the effects of pressure, temperature and the ethanol concentration in the mobile phase on the retention factor and resolution of tocopherols were studied comprehensively. The ranges of the studied pressure, temperature and ethanol concentration were 12 to 20 MPa, 30 to 90 °C and 0 to 6.54 wt% respectively. It was found that the retention factors of the tocopherols decrease as the ethanol concentration in the mobile phase increases. The resolution of tocopherols increases as the temperature increases and as the pressure decreases, and there is a maximum of the ethanol concentration curve at a definite temperature and pressure. A simplified model of the retention factor ln k′=A+SHAPE = "SOL" ALIGN="C" STYLE="S">BT+Cρ−D(SHAPE = "SOL" ALIGN="C" STYLE="S">ρT)+E(SHAPE = "SOL" ALIGN="C" STYLE="S">ρ2T) based on the unified molecular theory was proposed. The experimental data were correlated by the model with the AARD% less than 14.70%. [Copyright &y& Elsevier]

[Display omitted] • A novel collector LDEA is synthesized on dodecylamine (DDA) molecular structure. • LDEA has a better selectivity in flotation separation of apatite/quartz/K-feldspar. • LDEA and DDA exhibit comparable adsorption levels on apatite surfaces. • The adsorption configurations of LDEA and DDA on apatite surfaces markedly differ. • LDEA adsorption structure on apatite surface dictates its weak collecting ability. In the reverse flotation separation of apatite and its associated siliceous gangue minerals, the common collector dodecylamine (DDA) exhibits a poor selectivity. To remedy this issue, this study implements a change to DDA molecular structure by integrating two 2-hydroxyethyl groups at the N atom position, ultimately producing a freshly developed collector, lauryldiethanolamine (LDEA). Micro-flotation experiments reveal that, relative to DDA, LDEA showcases an enhanced selectivity in separating apatite from its associated siliceous gangue minerals quartz and K-feldspar through reverse flotation. This difference primarily stems from the weaker collecting ability of LDEA for apatite particles relative to DDA. Nevertheless, zeta potential measurements and X-ray photoelectron spectroscopic tests consistently show that, under identical dosage conditions, LDEA and DDA exhibit similar adsorption quantities on apatite surfaces. This observation implies that factors beyond its adsorption quantities inevitably influence the collecting ability of LDEA for apatite particles. First-principles calculations unveil markedly different adsorption configurations of LDEA and DDA on apatite surfaces, suggesting that the difference in the adsorption configurations of LDEA and DDA accounts for the significant variance in their collecting abilities for apatite particles. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel collector DDALA is developed based on dodecylamine (DDA) structure. • The reagent system composed of DDALA and xanthan gum has better flotation selectivity for apatite/quartz. • DDALA/oleic acid combined collector exhibits different competitive adsorption configurations on apatite and dolomite surfaces. • DDALA/oleic acid molecular aggregates on apatite surface dictate its weakened capturing ability. This paper introduces a novel amphoteric collector, N -dodecyl-β-alanine (DDALA), derived from the molecular structure of dodecylamine, with the incorporation of a propionic acid group. In the study, flotation experiments are undertaken to examine the selectivity of DDALA in apatite flotation. Results demonstrate that DDALA, in combination with xanthan gum (XG) depressant and oleic acid collector successfully accomplishes the reverse flotation separation of apatite from quartz and dolomite. In addition, the synergistic application of zeta potential experiments, X-ray photoelectron spectroscopic tests, and first-principles calculations has been employed to delve into the action mechanisms of DDALA collector and XG depressant. By combining the results with existing research, the paper proposes that the selective adsorption of XG between apatite and quartz surfaces facilitates the selective separation of these two minerals by DDALA collector. Moreover, the intermediate collecting ability of DDALA/oleic acid combined collector for dolomite results from the competitive adsorption of DDALA neutral molecules and oleic acid anions on dolomite surface. Furthermore, the formation of hydrophilic molecular aggregates between DDALA neutral molecules and oleic acid anions on apatite surface diminishes the collecting ability of DDALA/oleic acid combined collector for apatite compared to the individual use of each collector. [ABSTRACT FROM AUTHOR]

Pioglitazone has been developed as an effective insulin-sensitizing agent for the treatment of type II diabetes mellitus. Selective hydrogenation of the benzylidenethiazolidinedione exocyclic alkene is a committed step in the industrial manufacturing of pioglitazone. However, the strong coordination between metallic sites of commercial hydrogenation catalysts and benzylidenethiazolidinedione might cause catalyst poisoning and lead to poor activity and selectivity. In this context, an effective and anti-poisoning catalyst with highly dispersed palladium nanoparticles supported on biomass-derived nitrogen-doped carbon with mesoporous structures has been established. A systematic investigation of the structure–activity relationship was performed with a series of Pd/CNx by regulating the ratio of precursors D-glucosamine hydrochloride (GAH) and melamine, and it demonstrated that large specific surface area, rich pore structure and strong Pd–N interaction were essential for the high catalytic performance. The optimal Pd/CN1.2 catalyst exhibited nearly 100% conversion and 95.5% selectivity under optimized reaction conditions. Remarkably, compared with commercial Pd/C catalyst, Pd/CN1.2 displayed almost twice the catalytic productivity and provided better poisoning resistance and leaching resistance. Moreover, its stability was also acceptable and good activity could be maintained after exposed in the air for 4 months. [ABSTRACT FROM AUTHOR]

In China, the rapid development greatly promotes the national economic power and living standard but also inevitably brings a series of environmental problems. In order to resolve these problems fundamentally, Chinese scientists have been undertaking research in the area of green chemical engineering (GCE) for many years and achieved great progresses. In this paper, we reviewed the research progresses related to GCE in China and screened four typical topics related to the Chinese resources characteristics and environmental requirements, i.e. ionic liquids and their applications, biomass utilization and bio-based materials/products, green solvent-mediated extraction technologies, and cold plasmas for coal conversion. Afterwards, the perspectives and development tendencies of GCE were proposed, and the challenges which will be faced while developing available industrial technologies in China were mentioned. [ABSTRACT FROM AUTHOR]

[Display omitted] • A new cationic collector BHCPDA is developed based on dodecylamine (DDA) structure. • BHCPDA has superior selectivity over DDA in flotation separation of apatite/quartz. • BHCPDA has a higher adsorption amount on quartz, leading to its better selectivity. • Varied adsorption arrangements of BHCPDA and DDA impacts their apatite collections. Dodecylamine (DDA) is a commonly used cationic collector in the reverse flotation of apatite and quartz but has poor selectivity. To improve the selectivity of DDA, two 2-hydroxy-3-chloropropyl groups are introduced to the structure of DDA to create a novel cationic collector N,N -bis(2-hydroxy-3-chloropropyl) dodecylamine (BHCPDA). Flotation experiments demonstrate that BHCPDA has better selectivity than DDA. The findings from zeta potential experiments and X-ray photoelectron spectroscopy analysis consistently indicate that BHCPDA exhibits a greater adsorption amount on quartz surface compared to apatite. This observation explains its heightened ability for collecting quartz in the flotation relative to apatite. However, both the methods also reveal that BHCPDA displays a higher adsorption amount on apatite surface than DDA, whereas DDA demonstrates a greater efficiency in collecting apatite. This implies that the efficacies of flotation collectors in collecting minerals are not solely dependent on their adsorption amounts on the mineral surfaces. First-principles calculations indicate that BHCPDA and DDA adopt distinct adsorption configurations on quartz surface, leading to a reduced collecting ability of BHCPDA for quartz. The integration of the flotation experiments with the various test methods leads to the conclusion that the adsorption configurations of collectors on mineral surfaces significantly influence their abilities to collect the minerals. [ABSTRACT FROM AUTHOR]

Cage‐like metal–organic frameworks (MOFs) are promising for hexane isomer separation, but their aperture sizes are difficult to control precisely. Herein, a molecular valve strategy is proposed to fine‐tune the aperture of cage‐like MOFs, thereby enhancing their separation performance for hexane isomers. Three novel isostructural cage‐like MOFs, namely Cu‐MO4‐TPA, are synthesized using different oxometallate anions (MO42−, M = Cr, Mo, and W) and the ligand tri(pyridin‐4‐yl)amine (TPA). The different oxometallate anions induce varying degrees of twisting in the TPA ligand, leading to sub‐angstrom tuning in the aperture size of the MOFs. The materials can separate hexane isomers based on their degree of branching, with the smallest aperture material (Cu‐MoO4‐TPA) showing molecular sieving of di‐branched isomers. Adsorption isotherms, kinetic, and breakthrough measurements, Monte Carlo, and density functional theory calculations confirm the aperture size differences result in superior separation of hexane isomers by molecular sieving on Cu‐MoO4‐TPA. The results demonstrate the effectiveness of molecular valve strategy for fine‐tuning MOF aperture size for selective separation applications. [ABSTRACT FROM AUTHOR]

The separation of structurally similar compounds, such as cholic acid (CA) and deoxycholic acid (DCA), is challenging due to their nearly identical physicochemical properties. This study demonstrates a synergistic 'push and pull' strategy with an ionic liquid (IL) biphasic system for significantly enhanced CA/DCA separation efficiency. Ethyl acetate was selected as the feed solvent to 'push' CA into the IL-rich extractant phase, while the IL 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl) was chosen to 'pull' CA due to their strong hydrogen bonding interaction. This 'push and pull' system yielded a remarkable CA/DCA selectivity up to 47.8, much higher than the case using n-butanol which pulls both CA and DCA. The underlying separation mechanism was elucidated through computational screening with COSMO-RS, NMR analysis, and solvatochromic measurements. Results revealed the critical roles of specific hydrogen bonding between the chloride anion of [EMIM]Cl and the hydroxyl/carboxyl groups of CA/DCA, along with nonspecific interactions between the feed solvent and CA/DCA. Thermodynamic analysis of the phase transfer process confirmed the 'push and pull' synergy is energetically favorable for preferentially transferring CA from the ethyl acetate feed solution into the IL-rich extractant phase. Multi-stage simulation indicated that 99% purity and recovery of both CA and DCA can be obtained through this biphasic system under optimized conditions. Overall, strategically tuning both the feed solvent and IL extractant could significantly enhance the separation efficiency of structurally similar compounds while minimizing solvent and energy consumption. This 'push and pull' approach may shed light on improving separation processes for other structural analogues. [ABSTRACT FROM AUTHOR]

The one‐step purification of ethylene (C2H4) from mixtures containing ethane (C2H6) and acetylene (C2H2) is an industrially important yet challenging process. In this work, we present a site‐engineering strategy aimed at manipulating the spatial distribution of binding sites within a confined pore space. We realized successfully by incorporating nitrogen‐containing heterocycles, such as indole‐5‐carboxylic acid (Ind), benzimidazole‐5‐carboxylic acid (Bzz), and indazole‐5‐carboxylic acid (Izo), into the robust MOF‐808 platform via post‐synthetic modification. The resulting functionalized materials, namely MOF‐808‐Ind, MOF‐808‐Bzz, and MOF‐808‐Izo, demonstrated significantly improved selectivity for C2H2 and C2H6 over C2H4. MOF‐808‐Bzz with two uniformly distributed nitrogen binding sites gave the optimal geometry for selective ethane trapping through multiple strong C−H⋅⋅⋅N hydrogen bonds, leading to the highest C2H2/C2H4 and C2H6/C2H4 combined selectivities among known MOFs. Column breakthrough experiments validated its ability to purify C2H4 from ternary C2H2/C2H4/C2H6 mixtures in a single step. [ABSTRACT FROM AUTHOR]

The one‐step purification of ethylene (C2H4) from mixtures containing ethane (C2H6) and acetylene (C2H2) is an industrially important yet challenging process. In this work, we present a site‐engineering strategy aimed at manipulating the spatial distribution of binding sites within a confined pore space. We realized successfully by incorporating nitrogen‐containing heterocycles, such as indole‐5‐carboxylic acid (Ind), benzimidazole‐5‐carboxylic acid (Bzz), and indazole‐5‐carboxylic acid (Izo), into the robust MOF‐808 platform via post‐synthetic modification. The resulting functionalized materials, namely MOF‐808‐Ind, MOF‐808‐Bzz, and MOF‐808‐Izo, demonstrated significantly improved selectivity for C2H2 and C2H6 over C2H4. MOF‐808‐Bzz with two uniformly distributed nitrogen binding sites gave the optimal geometry for selective ethane trapping through multiple strong C−H⋅⋅⋅N hydrogen bonds, leading to the highest C2H2/C2H4 and C2H6/C2H4 combined selectivities among known MOFs. Column breakthrough experiments validated its ability to purify C2H4 from ternary C2H2/C2H4/C2H6 mixtures in a single step. [ABSTRACT FROM AUTHOR]

Efficient separation of acetylene (C2H2)/ethylene (C2H4) and acetylene/carbon dioxide (CO2) by adsorption is an industrially promising process, but adsorbents capable of simultaneously capturing trace acetylene from ethylene and carbon dioxide are scarce. Herein, a gate‐opening effect on three isomorphous flexible metal–organic frameworks (MOFs) named Co(4‐DPDS)2MO4 (M = Cr, Mo, W; 4‐DPDS = 4,4‐dipyridyldisulfide) is modulated by anion pillars substitution. The shortest CrO42− strengthens intraframework hydrogen bonding and thus blocks structural transformation after activation, striking a good balance among working capacity, separation selectivity, and trace impurity removal of flexible MOFs out of nearly C2H2/C2H4 and C2H2/CO2 molecular sieving. The exceptional separation performance of Co(4‐DPDS)2CrO4 is confirmed by dynamic breakthrough experiments. It reveals the specific threshold pressures control in anion‐pillared flexible materials enabled elimination of the impurity leakage to realize high purity products through precise control of the intraframework interaction. The adsorption mechanism and multimode structural transformation property are revealed by both calculations and crystallography studies. This work demonstrates the feasibility of modulating flexibility for controlling gate‐opening effect, especially for some cases of significant aperture shrinkage after activation. [ABSTRACT FROM AUTHOR]

As a new class of porous crystalline materials, hydrogen‐bonded organic frameworks (HOFs) assembled from building blocks by hydrogen bonds have gained increasing attention. HOFs benefit from advantages including mild synthesis, easy purification, and good recyclability. However, some HOFs transform into unstable frameworks after desolvation, which hinders their further applications. Nowadays, the main challenges of developing HOFs lie in stability improvement, porosity establishment, and functionalization. Recently, more and more stable and permanently porous HOFs have been reported. Of all these design strategies, stronger charge‐assisted hydrogen bonds and coordination bonds have been proven to be effective for developing stable, porous, and functional solids called hybrid HOFs, including ionic and metallized HOFs. This Review discusses the rational design synthesis principles of hybrid HOFs and their cutting‐edge applications in selective inclusion, proton conduction, gas separation, catalysis and so forth. [ABSTRACT FROM AUTHOR]

Heterogeneous Brønsted acidic catalysts such as phosphoric acids are the conventional activators for organic transformations. However, the photocatalytic performance of these catalysts is still rarely explored. Herein, a novel Zr-based metal−organic framework Zr-MOF-P with phosphoric acids as a heterogeneous photocatalyst has been fabricated, which shows high selectivity and reactivity towards the photo-oxidation of sulfides under white light illumination. A mechanism study indicates that the selective oxygenation of sulfides occurs with triplet oxygen rather than common reactive oxygen species (ROS). When Zr-MOF-P is irradiated, the hydroxyl group of phosphoric acid is converted into oxygen radical, which takes an electron from the sulfides, and then the activated substrates react with the triplet oxygen to form sulfoxides, avoiding the destruction of the catalysts and endowing the reaction with high substrate compatibility and fine recyclability. [ABSTRACT FROM AUTHOR]

Adsorptive separation of xenon (Xe) and krypton (Kr) is a promising technique but remains a daunting challenge since they are atomic gases without dipole or quadruple moments. Herein we report a strategy for fabricating angular anion‐pillared materials featuring shell‐like Xe nano‐traps, which provide a cooperative effect conferred by the pore confinement and multiple specific interactions. The perfect permanent pore channel (4–5 Å) of Ni(4‐DPDS)2MO4 (M=Cr, Mo, W) can host Xe atoms efficiently even at ultra‐low concentration (400 ppm Xe), showing the second‐highest selectivity of 30.2 in Ni(4‐DPDS)2WO4 and excellent Xe adsorption capacity in Ni(4‐DPDS)2CrO4 (15.0 mmol kg−1). Crystallography studies and DFT‐D calculations revealed the energy favorable binding sites and angular anions enable the synergism between optimal pore size and polar porosity for boosting Xe affinity. Dynamic breakthrough experiments demonstrated three MOFs as efficient adsorbents for Xe/Kr separation. [ABSTRACT FROM AUTHOR]

Adsorptive separation of xenon (Xe) and krypton (Kr) is a promising technique but remains a daunting challenge since they are atomic gases without dipole or quadruple moments. Herein we report a strategy for fabricating angular anion‐pillared materials featuring shell‐like Xe nano‐traps, which provide a cooperative effect conferred by the pore confinement and multiple specific interactions. The perfect permanent pore channel (4–5 Å) of Ni(4‐DPDS)2MO4 (M=Cr, Mo, W) can host Xe atoms efficiently even at ultra‐low concentration (400 ppm Xe), showing the second‐highest selectivity of 30.2 in Ni(4‐DPDS)2WO4 and excellent Xe adsorption capacity in Ni(4‐DPDS)2CrO4 (15.0 mmol kg−1). Crystallography studies and DFT‐D calculations revealed the energy favorable binding sites and angular anions enable the synergism between optimal pore size and polar porosity for boosting Xe affinity. Dynamic breakthrough experiments demonstrated three MOFs as efficient adsorbents for Xe/Kr separation. [ABSTRACT FROM AUTHOR]

• A new strategy to realize efficient kinetic separation of hexane isomers. • A benchmark for the hexane isomers separation via kinetic mechanism. • Record capacity, record kinetic selectivities and record productivity. The separation of mono- and di-branched hexane isomers remains an important and challenging industrial process for the production of high-octane gasoline. Suitable adsorbents with high adsorption selectivity and capacity are urgently required. Herein, we demonstrate a strategy to realize highly efficient kinetically controlled hexane isomers adsorption separation that utilizes the tunability of the pore limiting diameter in M 2 TTFTB (M=Zn, Mn, Cd) by metal substitution. The appropriate refinement of the partially contracted pore not only improved the kinetic selectivities, but also enhanced the host–guest interaction and increased the adsorption capacity of 3MP and nHEX. The resulting Mn 2 TTFTB brought about both the record capacity of 3MP and the record kinetic selectivities of 3MP/22DMB and nHEX/22DMB, exhibiting the largest productivity of high-purity 22DMB in the breakthrough experiments, which sets a new benchmark for the hexane isomers separation via a rarely reported kinetically controlled mechanism. [ABSTRACT FROM AUTHOR]

Xe/Kr separation is an industrially important but challenging process owing to their inert properties and low concentrations in the air. Energy‐effective adsorption‐based separation is a promising technology. Herein, two isostructural hydrogen‐bonded metal–nucleobase frameworks (HOF‐ZJU‐201 and HOF‐ZJU‐202) are capable of separating Xe/Kr under ambient conditions and strike an excellent balance between capacity and selectivity. The Xe capacity of HOF‐ZJU‐201a reaches 3.01 mmol g−1 at 298 K and 1.0 bar, while IAST selectivity and Henry's selectivity are 21.0 and 21.6, respectively. Direct breakthrough experiments confirmed the excellent separation performance, affording a Xe capacity of 25.8 mmol kg−1 from a Xe/Kr mixed‐gas at dilute concentrations. Density functional theory calculations revealed that the selective binding arises from the enhanced polarization in the confined electric field produced by the electron‐rich anions and the electron‐deficient purine heterocyclic rings. [ABSTRACT FROM AUTHOR]

Xe/Kr separation is an industrially important but challenging process owing to their inert properties and low concentrations in the air. Energy‐effective adsorption‐based separation is a promising technology. Herein, two isostructural hydrogen‐bonded metal–nucleobase frameworks (HOF‐ZJU‐201 and HOF‐ZJU‐202) are capable of separating Xe/Kr under ambient conditions and strike an excellent balance between capacity and selectivity. The Xe capacity of HOF‐ZJU‐201a reaches 3.01 mmol g−1 at 298 K and 1.0 bar, while IAST selectivity and Henry's selectivity are 21.0 and 21.6, respectively. Direct breakthrough experiments confirmed the excellent separation performance, affording a Xe capacity of 25.8 mmol kg−1 from a Xe/Kr mixed‐gas at dilute concentrations. Density functional theory calculations revealed that the selective binding arises from the enhanced polarization in the confined electric field produced by the electron‐rich anions and the electron‐deficient purine heterocyclic rings. [ABSTRACT FROM AUTHOR]

Abstract: A magnesium-based metal organic framework (MOF), also known as Mg-MOF-74, was successfully synthesized, characterized, and evaluated for adsorption equilibria and kinetics of CO2 and CH4. The Mg-MOF-74 crystals were characterized with scanning electron microscopy for crystal structure, powder X-ray diffraction for phase structure, and nitrogen adsorption for pore textural properties. Adsorption equilibrium and kinetics of CO2 and CH4 on the Mg-MOF-74 adsorbent were measured in a volumetric adsorption unit at 278, 298, and 318K and pressures up to 1bar. It was found that the Mg-MOF-74 adsorbent prepared in this work has a median pore width of 10.2Å, a BET specific surface area of 1174m2/g, CO2 and CH4 adsorption capacities of 8.61mmolg−1 (37.8wt.%) and 1.05mmolg−1 (1.7wt.%), respectively, at 298K and 1bar. Both CO2 and CH4 adsorption capacities are significantly higher than those of zeolite 13X under similar conditions. The pressure-dependent equilibrium selectivity of CO2 over CH4 (q CO2/q CH4) in the Mg-MOF-74 adsorbent showed a trend similar to that of zeolite 13X and the intrinsic selectivity of Mg-MOF-74 at zero adsorption loading is 283 at 298K. The initial heats of adsorption of CO2 and CH4 on the Mg-MOF-74 adsorbent were found to be 73.0 and 18.5kJmol−1, respectively. The adsorption kinetic measurements suggest that the diffusivities of CO2 and CH4 on Mg-MOF-74 were comparable to those on zeolite 13X. CH4 showed relatively faster adsorption kinetics than CO2 in both adsorbents. The diffusion time constants of CO2 and CH4 in the Mg-MOF-74 adsorbent at 298K were estimated to be 8.11×10−3 and 4.05×10−2 s−1, respectively, showing a modest kinetic selectivity of about 5 for the separation CH4 from CO2. [Copyright &y& Elsevier]

Abstract: Adsorption isotherms of artemisinin from supercritical CO2 on silica gel were measured at temperatures from 308.1 to 328.1K and at pressures from 14.1 to 18.1MPa with a frontal analysis method. The adsorption amount of artemisinin from CO2 on silica gel decreased with the increase of pressure. The adsorption amount decreased with increasing temperature at a constant CO2 density of 0.79gcm−3; however it increased with increasing temperature at constant pressure within the range of 14.1 to 18.1MPa. The adsorption amount of artemisinin from CO2 on silica gel was greatly affected by the solvating power of CO2. CO2 probably could not be regard as a non-adsorbed substance and it competed with artemisinin for adsorption sites on silica gel. The competitive adsorption of CO2 on silica gel enhanced as pressure increased. The isotherms of artemisinin were corrected with Freundlich model and a thermodynamic model based on the real adsorption solution theory. [Copyright &y& Elsevier]

Abstract: The equilibrium and kinetics of levulinic acid (LA) adsorption on two basic polymeric adsorbents, 335 (highly porous gel) and D315 (macroreticular), were investigated. Experimental adsorption rates in batch stirred vessels under a variety of operating conditions were described successfully by the parallel pore and surface diffusion model taking into account external mass transfer and nonlinear Toth isotherm. The film-pore diffusion model was matched with the rate data and the resulting apparent pore diffusivities were strongly concentration-dependent and approached to a constant value for 335 adsorbent. Thus, the constant value was taken as the accurate pore diffusivity, while the pore diffusivity in D315 was estimated from the particle porosity. The surface diffusivities decreased with increasing initial bulk concentration for both adsorbents. The inverse concentration dependence was correlated reasonably well to the change of isosteric heat of adsorption as amount adsorbed. [Copyright &y& Elsevier]

A high-performance liquid chromatographic method coupled with evaporative light-scattering detector was used for the accurate quantification of soybean phospholipids. This method is based on normal-phase chromatography with silica gel as stationary phase and a ternary gradient with n-hexane, isopropanol, and water as mobile phase. Major soybean phospholipid classes were separated by optimizing the solvent systems. The ternary solvent of n-hexane:isopropanol:water (53:42:5, by volume) was suitable for the separation of neutral lipids (NL), glycolipids (GL), and phosphatidylethanolamine (PE). By using hexane:isopropanol:water (17:66:17, by volume), phosphatidylcholine (PC), sphingomyelin (SM), and lysophosphatidylcholine (LPC) were separated. PE and phosphatidylinositol (PI), phosphatidic acid (PA), and PC were base line resolved by carefully adjusting the flow rate and switch time of intermediate gradients. The analysis was completed in 32 min, and repeated injections of the samples were possible. The method has good repeatability and accuracy from the view point of high recovery, and low coefficients of variance in retention time and peak area for each phospholipid. Comparison was made between three detectors, i.e., ELSD, UV, and RI. The results show that ELSD is the best in phospholipids analysis. [ABSTRACT FROM AUTHOR]

Hydrogen‐bonded organic frameworks (HOFs) have emerged as rapidly growing porous materials while established permanent porosities are very fragile and difficult to stabilize due to weak hydrogen‐bonding interactions among building units. Herein, we report a stable hydrogen‐bonded metallotecton framework (termed as HOF‐ZJU‐102) that was constructed through hydrogen‐bonding networks between cationic metal‐organic complexes [Cu2(Hade)4(H2O)2]4+ (Hade=adenine) and GeF62− anions. The framework not only shows permanent porosity, but also exhibits efficient separation performance of C2H2/C2H4 at room temperature. More interestingly, its crystal structure could be irreversibly transformed into isostructural counterpart HOF‐ZJU‐101 by ion exchange in the SiF62− containing solution, evidenced by multiple characterization techniques including gas sorption measurements, 19F NMR spectra, FTIR and EDS. Utilizing such an ion exchange mechanism, the collapsed HOF‐ZJU‐102 could be restored into HOF‐ZJU‐101 by simply soaking in the salt solution. [ABSTRACT FROM AUTHOR]

Using a multilayer helical separation column coaxially mounted on a horizontal rotary shaft, retention of the stationary phase and partition efficiency were studied at various rotation speeds ranging from 20 to 800 rpm. A binary two-phase solvent system composed of chloroform/water was used to elute the lower organic phase through the head of the rotating column. The results indicated that best retention of the stationary phase was obtained at a low rotation speed of 75 rpm yielding the highest peak resolution between caffeine and theophylline. Because of its simplicity and low rotation speed, the system has a potential to be scaled-up for an industrial-scale separation simply by increasing the capacity of the helical column. [ABSTRACT FROM AUTHOR]

There is growing interest in developing triplet photosensitizers in terms of implementing photochemical strategies in synthetic chemistry. However, synthesis of stable triplet organic photosensitizers is nontrivial and often requires the use of heavy atoms. Herein, an alternative strategy is demonstrated to enhance the triplet generation efficiency by implanting lone‐pair donor–acceptor bonds in the conjugated covalent organic frameworks (COFs). This powerful method is validated using COFs that host triazine, a moiety that has been extensively investigated in photocatalysis. Spectroscopic analysis and theoretical calculations reveal substantial improvements in the photoabsorptivity and triple‐state photogeneration efficiency, consistent with catalytic tests concerning industrially relevant sulfide oxidation. These systems represent a promising addition to the rapidly increasing arsenal of synthetic photocatalytic systems. [ABSTRACT FROM AUTHOR]

An emerging organic structure with excellent 2e- oxygen-reduction activity in the photosynthesis of H 2 O 2 has been developed, of which the photocatalytic performance was significantly improved after anchoring the active moiety into extending conjugated covalent organic frameworks. The resulting materials rendered high H 2 O 2 productivity in pure water. [Display omitted] • An emerging organic photocatalytic structure for the photosynthesis of H 2 O 2 from oxygen and water has been developed. • Extending conjugated COFs promotes H 2 O 2 productivity in pure water. • The suitable distance of active moiety generates the highest efficiency. • An alternative strategy for constructing 2e- oxygen reduction photocatalyst. Direct synthesis of hydrogen peroxide (H 2 O 2) using oxygen and water through the photocatalytic route is a prospective approach for the on-site production of H 2 O 2. However, the limited varieties of photocatalytic sites and ambiguous structure-active relationship impede the development of environmentally friendly technology. Herein, we report a active compound (benzotrithiophene, BTT) for the photosynthesis of H 2 O 2 using oxygen and water, and design four benzotrithiophene-based 2D covalent organic frameworks (BTT-COFs) linked with aromatic amines linkers. Significant enhancement in photocatalytic activity has been observed via the introduction of BTT struct into 2D COFs. The high crystallinity of COFs increases the visible light absorption ability and photostability of BTT. The suitable distance of BTT struct in COFs and the construction of donor–acceptor (D-A) structure further promote the carrier generation and transfer. The COF-BTT-TAPT exhibited the highest H 2 O 2 production rate of 620 μmol g−1 h−1. Mechanism investigation experiments have given the validation that BTT-COFs efficiently reduce oxygen in pure water to form H 2 O 2 under visible-light irradiation. This work paves a revolutionary way for designing and fabricating high-performance metal-free photocatalysts for visible-light-driven H 2 O 2 production. [ABSTRACT FROM AUTHOR]

Demonstration of DEMO relevant fusion power (Pfus) level and tritium self-sufficiency are two important goals of the China fusion engineering testing reactor (CFETR). In this work the integrated modeling including self-consistent core–pedestal coupling are used to design the hybrid scenario plasmas at flat-top phase for these goals. Such plasmas have been taken as the reference plasma for studying the compatibility of the hybrid scenario with CFETR engineering design in the past two years. The physics justification for the selection of plasma density, Zeff, safety factor profile, and in particular the choice of auxiliary heating and current drive is presented. According to a scan of plasma density and Zeff, the target of Pfus ≈ 1 GW and finite ohmic flux consumption ∆Φohm (4 h) ⩽ 250 Vs can be met with Zeff = 1.9–2.2 and the density at the pedestal top set at 90% of the Greenwald limit. Turbulent transport analysis using the gyro-Landau-fluid model TGLF shows that the electromagnetic effects can enhance the energy confinement but reduce the particle confinement and thus Pfus. A baseline hybrid scenario case matching the target in the concept design is built using a combination of neutral beams (NB) and electron cyclotron (EC) waves to flatten the safety factor profile in the deep core region (with the normalized plasma radius ρ ⩽ 0.4). Such profile can yield better particle and energy confinement than that with either higher magnetic shear in the deep core region or higher q value in outer core region (e.g., due to the addition of lower hybrid current drive). Switching a part of auxiliary heating from electron to ions, e.g., replacing a part of EC waves by waves in the ion cyclotron range of frequencies, reduces the particle confinement and thus Pfus. Since high harmonic fast waves (HHFW) can drive current at the same location as ECCD with higher current drive efficiency than ECCD and yield more electron heating than NB, the case using HHFW to replace a part of EC waves and NB can yield higher Pfus and lower ∆Φohm than the baseline case. A discussion is given on future simulations to explore the improvement in plasma performance and the broadening of the feasible design space. [ABSTRACT FROM AUTHOR]

Separation of Xe and Kr is one of the greatest challenges in the gas industries owing to their close molecular structure and similar properties. Energy‐effective adsorption‐based separation using chemically stable carbon adsorbents is a promising technology. We propose a strategy for Xe/Kr separation using MOF‐derived metallic carbon adsorbents. M‐Gallate (M=Ni, Co) were used as precursors to fabricate CoNi alloy nanoparticles embedded carbon adsorbents by one‐step auto‐reduction pyrolysis. The optimal NiCo@C‐700 exhibits record‐high IAST selectivity (24.1) and Henry's selectivity (20.1) of Xe/Kr among reported carbon adsorbents. DFT calculations, local density of states calculation, charge density difference, and Bader charge analysis reveal the great affinity with Xe benefits from the presence of Ni or CoNi nanoparticles as a result of more charge transfer from Xe than Kr to metal, thus providing higher binding energy. Breakthrough experiments further verify NiCo@C‐700 a promising candidate for Xe/Kr separation. [ABSTRACT FROM AUTHOR]

Separation of Xe and Kr is one of the greatest challenges in the gas industries owing to their close molecular structure and similar properties. Energy‐effective adsorption‐based separation using chemically stable carbon adsorbents is a promising technology. We propose a strategy for Xe/Kr separation using MOF‐derived metallic carbon adsorbents. M‐Gallate (M=Ni, Co) were used as precursors to fabricate CoNi alloy nanoparticles embedded carbon adsorbents by one‐step auto‐reduction pyrolysis. The optimal NiCo@C‐700 exhibits record‐high IAST selectivity (24.1) and Henry's selectivity (20.1) of Xe/Kr among reported carbon adsorbents. DFT calculations, local density of states calculation, charge density difference, and Bader charge analysis reveal the great affinity with Xe benefits from the presence of Ni or CoNi nanoparticles as a result of more charge transfer from Xe than Kr to metal, thus providing higher binding energy. Breakthrough experiments further verify NiCo@C‐700 a promising candidate for Xe/Kr separation. [ABSTRACT FROM AUTHOR]

Shaping metal-organic frameworks (MOFs) powders into formed bodies plays a crucial role in opening up the excellent properties of MOFs to a broad range of applications. Gallate-based MOFs, termed as M-gallate (M = Co, Mg, Ni), have shown excellent performance for adsorption separation of C 2 hydrocarbons. However, the industrial applications of MOF powders will inevitably confront problems of high pressure drop, pipe blockage, and dust pollution. Herein, we use hydroxypropyl cellulose (HPC) as a binder to produce gallate-based MOFs pellets. The crystal structure of the well-shaped materials after molding remained intact, and the surface area of the materials hardly decreases after shaping. Adsorption isotherms of C 2 hydrocarbons including ethylene, ethane and acetylene on the activated powders and pellets of M-gallate were recorded and compared with the outperformers. The shaped pellets were also examined by breakthrough experiments on the fixed-bed separation of C 2 H 2 /C 2 H 4 (1:99, v/v) and C 2 H 4 /C 2 H 6 (50:50, v/v) gas mixtures. These results proved that M-gallate pellets was promising candidates for the practical industrial realization of C 2 hydrocarbons separation. [ABSTRACT FROM AUTHOR]

Various toxic metal ions were successfully removed from solid matrix into supercritical CO2 (scCO2) by open-chain crown ether bridged diphosphates at 313.15 K and 20 MPa, these diphosphates with different ester side chains and different length of ethylene oxide bridge group are highly soluble in supercritical CO2. The extraction efficiency (E%) of heavy metals is between 55 and 89%. Mulliken charge distribution of ligand's P=O coordination group was calculated to indicate the stability of metal complex. The ligand structure effects and the rationale for different selectivity were discussed. In addition, binding property of these diphosphates towards the alkaline earth metals was further studied following the same extraction procedures. Alkaline earth metal ions Ca2+, Sr2+ and Ba2+ were extracted with E% at 49–74%, 50–73% and 16–64%, respectively. DFT calculations were performed to investigate the interaction energy of the complexes and the correlation with the E% was discussed. [ABSTRACT FROM AUTHOR]

C2‐C3 alkyne/alkene separation is of great importance; however, designing materials for an efficient molecular sieving of alkenes from alkynes remains challenging. Now, two hydrolytically stable layered MOFs, [Cu(dps)2(GeF6)] (GeFSIX‐dps‐Cu, dps=4,4′‐dipyridylsulfide) and [Zn(dps)2(GeF6)] (GeFSIX‐dps‐Zn), can achieve almost complete exclusion of both C3H6 and C2H4 from their alkyne analogues. GeFSIX‐dps‐Cu displays a notable advanced threshold pressure for alkynes adsorption and thus substantial uptakes at lower pressures, providing record C3H4/C3H6 uptake ratios and capacity‐enhanced C2H2/C2H4 sieving for a wide composition range. Metal substitution (Zn to Cu) affords fine tuning of linker rotation and layer stacking, creating slightly expanded pore aperture and interlayer space coupled with multiple hydrogen‐bonding sites, allowing easier entrance of alkyne while excluding alkene. Breakthrough experiments confirmed tunable sieving by these MOFs for C3H4/C3H6 and C2H2/C2H4 mixtures. [ABSTRACT FROM AUTHOR]

A series of cyclodextrin‐derived room temperature macromolecular ionic liquids carrying rather low glass transition temperatures of −20 to −40 °C are synthesized via sequential esterification, quaternization, and anion metathesis reactions. In addition to being ionic in nature, they are viscous liquids at room temperature with more fluidic behavior at elevated temperatures. They serve as a solvent for organic dyes or iodine separation via a liquid–liquid extraction approach. This strategy is useful for the development of various sugar (macro)molecule‐based functional ionic liquids as well as macromolecular ionic liquids. [ABSTRACT FROM AUTHOR]

The separation of xenon/krypton (Xe/Kr) mixture is of great importance to industry, but the available porous materials allow the adsorption of both, Xe and Kr only with limited selectivity. Herein we report an anion‐pillared ultramicroporous material NbOFFIVE‐2‐Cu‐i (ZU‐62) with finely tuned pore aperture size and structure flexibility, which for the first time enables an inverse size‐sieving effect in separation along with record Xe/Kr selectivity and ultrahigh Xe capacity. Evidenced by single‐crystal X‐ray diffraction, the rotation of anions and pyridine rings upon contact of larger‐size Xe atoms adapts cavities to the shape/size of Xe and allows strong host‐Xe interaction, while the smaller‐size Kr is excluded. Breakthrough experiments confirmed that ZU‐62 has a real practical potential for producing high‐purity Kr and Xe from air‐separation byproducts, showing record Kr productivity (206 mL g−1) and Xe productivity (42 mL g−1, in desorption) as well as good recyclability. [ABSTRACT FROM AUTHOR]

The separation of xenon/krypton (Xe/Kr) mixture is of great importance to industry, but the available porous materials allow the adsorption of both, Xe and Kr only with limited selectivity. Herein we report an anion‐pillared ultramicroporous material NbOFFIVE‐2‐Cu‐i (ZU‐62) with finely tuned pore aperture size and structure flexibility, which for the first time enables an inverse size‐sieving effect in separation along with record Xe/Kr selectivity and ultrahigh Xe capacity. Evidenced by single‐crystal X‐ray diffraction, the rotation of anions and pyridine rings upon contact of larger‐size Xe atoms adapts cavities to the shape/size of Xe and allows strong host‐Xe interaction, while the smaller‐size Kr is excluded. Breakthrough experiments confirmed that ZU‐62 has a real practical potential for producing high‐purity Kr and Xe from air‐separation byproducts, showing record Kr productivity (206 mL g−1) and Xe productivity (42 mL g−1, in desorption) as well as good recyclability. [ABSTRACT FROM AUTHOR]

The separation of acetylene from ethylene is of paramount importance in the purification of chemical feedstocks for industrial manufacturing. Herein, an isostructural series of gallate‐based metal–organic frameworks (MOFs), M‐gallate (M=Ni, Mg, Co), featuring three‐dimensionally interconnected zigzag channels, the aperture size of which can be finely tuned within 0.3 Å by metal replacement. Controlling the aperture size of M‐gallate materials slightly from 3.69 down to 3.47 Å could result in a dramatic enhancement of C2H2/C2H4 separation performance. As the smallest radius among the studied metal ions, Ni‐gallate exhibits the best C2H2/C2H4 adsorption separation performance owing to the strongest confinement effect, ranking after the state‐of‐the‐art UTSA‐200a with a C2H4 productivity of 85.6 mol L−1 from 1:99 C2H2/C2H4 mixture. The isostructural gallate‐based MOFs, readily synthesized from inexpensive gallic acid, are demonstrated to be a new top‐performing porous material for highly efficient adsorption of C2H2 from C2H4. [ABSTRACT FROM AUTHOR]

• A three-wavelength quadrature phase compensation method for recovering dynamic signals in extrinsic Fabry–Perot interferometers (EFPIs) is proposed and experimentally demonstrated. • The influence of the direct current component is eliminated by using three symmetrical interferometric signals, and two orthogonal signals are obtained by the phase compensation algorithm to extract the phase change. • This technique is suitable for measuring EFPI sensor cavity length changes under dynamic signals. A three-wavelength quadrature phase compensation method for recovering dynamic signals in extrinsic Fabry–Perot interferometers (EFPIs) is proposed and experimentally demonstrated. The influence of the direct current component is eliminated by using three symmetrical interferometric signals, and two orthogonal signals are obtained by the phase compensation algorithm to extract the phase change. A sinewave with a frequency of 1000 Hz was applied on an EFPI sensor. The cavity length of the EFPI sensor is 643.0299 μm. The demodulated signal is a sinewave with a frequency of 1000 Hz. The demodulated frequency shows good agreement with the frequency of the applied signal. This technique is suitable for measuring EFPI sensor cavity length changes under dynamic signals. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Hierarchical CuCo 2 O 4 nanowire arrays wrapped with metal oxides nanosheets have been successfully fabricated. • The CuCo 2 O 4 @NiO electrode exhibits high areal capacitance of 2.3 F/cm2 at 2 mA/cm2 and excellent cycling stability. • The asymmetric supercapacitor shows a high energy density of 38.9 Wh/kg at 750 W/kg. Abstract Herein, we report the rational design and fabrication of multicomponent, hierarchical CuCo 2 O 4 nanowire arrays wrapped with metal oxides (NiO, Co 3 O 4 and MnO 2) nanosheets for use in high-performance supercapacitors. Among all the composite electrodes prepared, the CuCo 2 O 4 @NiO electrode exhibits the best electrochemical behavior with a high areal capacitance of 2.3 F/cm2 at 2 mA/cm2 and excellent cycling stability. The asymmetric supercapacitor with CuCo 2 O 4 @NiO as the positive electrode shows a superior specific capacitance of 124.6 F/g at 1 A/g, exceptional energy density of 38.9 Wh/kg at 750 W/kg, and long cycle life with ∼81.3% capacitance retention after 6000 cycles. The results indicate that the CuCo 2 O 4 @NiO electrode shows great potential for high-performance electrochemical energy storage. [ABSTRACT FROM AUTHOR]

Selective oxidation of olefins to α,β-unsaturated ketones under mild reaction conditions has attracted considerable interest, since α,β-unsaturated ketones can serve as synthetic precursors for various downstream chemical products. The major inherent challenges with this chemical oxidation are chemo- and regio-selectivity as well as environmental concerns, i.e. catalyst recycle, safety and cost. Using atmospheric oxygen as an environmentally friendly oxidant, we found that a metal–organic framework (MOF) constructed with Mn and a tetrazolate ligand (CPF-5) showed good activity and selectivity for the allylic oxidation of olefins to α,β-unsaturated ketones. Under the optimized conditions, we could achieve 98% conversion of cyclohexene and 87% selectivity toward cyclohexanone. The combination of a substoichiometric amount of TBHP (tert-butylhydroperoxide) and oxygen not only provides a cost effective oxidation system but significantly enhances the selectivity to α,β-unsaturated ketones, outperforming most reported oxidation methods. This catalytic system is heterogeneous in nature, and CPF-5 could be reused at least five times without a significant decrease in its catalytic activity and selectivity. [ABSTRACT FROM AUTHOR]

• Treated the textile dyeing sludge by CO 2 thermal plasma gasification for the first time. • The carbon conversion efficiency was up to 99.9%. • Syngas-rich produced gas with a higher lower heating value was obtained. • The solid product was harmless. Textile dyeing sludge is complex hazardous material with increasing amount year by year, and the conventional treatment techniques are limited by many drawbacks such as water/soil contamination, incomplete degradation of hazardous organics or inefficient fixation of toxic heavy metals. This work reported the first example of thermal plasma gasification treatment of textile dyeing sludge in a homemade rotating arc plasma reactor, which not only significantly reduced the volume and eliminated the safety risk of textile dyeing sludge, but also produced valuable syngas that can be used for chemical industry. At a feed rate of 36 g/min and a CO 2 flow rate of 0.43 Nm3/h (14.08 g/min), the carbon conversion efficiency of gasification was 99.9%; and the energy conversion efficiency could reach 71.8%; and the lower heating value of syngas-rich produced gas was 8.91 MJ/Nm3. At the same time, the volume reduction ratio of sludge was 41.19% and the fixing efficiency of the heavy metals in solid products reached above 99%. Toxicity characteristic leaching procedure confirmed the solid products were harmless in a wide environmental pH range. The proposed method exhibits its great potential of simultaneously realizing harmless, minimization and reclamation of textile dyeing sludge and even other hazardous solid waste. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • CO 2 -soluble polyethylene glycol diphosphates designed and synthesized elaborately. • Solubility of ligands determined and steric structure affected behavior in scCO 2. • Lanthanides extractions investigated and ligands showed good extraction capability. • Effect of ligand's solubility and steric effect on metal extraction were discussed. Abstract A series of highly CO 2 -soluble open-chain crown ether bridged diphosphates were designed and prepared as chelating ligands which were used to extract lanthanide ions from cellulose paper into supercritical CO 2 (ScCO 2). These ligands were designed by introducing different ester side chains and joining the two phosphorus groups with different length of ethylene oxide group which could provide enhanced solubility and complexation ability. The solubility data of these synthesized diphosophates in ScCO 2 were measured at 313.15 K and 10.65 MPa–13.69 MPa. Lanthanides metal ions including La3+, Ce3+, Pr3+, Nd3+, Sm3+, Gd3+, Er3+, and Yb3+ were successfully removed from the solid matrix by supercritical fluid extractions using these chelating ligands at 313.15 K and 20 MPa. The extraction efficiency of metal ion was affected by chelating ligands' side chain, which increased from 68% to 94% mainly driven by the increased solubility capability. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Single crystal of Ca(squarate) MOF was synthesized by hydrothermal method. • Ca(squarate) has excellent selectivities for C 2 H 2 /C 2 H 4 (8.1) and C 2 H 4 /C 2 H 6 (5.9) at 298 K and 100 kPa. • Ca(squarate) is structurally stable when exposed to air for 2 weeks or soaked in water for 5 days. • The π-π interaction was the mainly factor governing the selective adsorption separation of C 2 light hydrocarbons. Abstract Ideal metal-organic frameworks (MOFs) are those have not only significant adsorption separation performances but also excellent vapor and/or thermal stability. In this work, a calcium-based metal-organic framework with high vapor-stability and thermostability, Ca(squarate), was prepared using readily available precursor (CaCO 3) and squaric acid as starting materials by hydrothermal method. Characterization techniques including PXRD, TGA and BET surface area analysis reveal that this MOF remains stable no matter whether it was soaked in water or exposed to air for as long as 2 weeks. Moreover, the studied MOF material is capable of discriminating C 2 hydrocarbon molecules as it has an appropriate pore diameter around 3.4 Å. Excellent efficient separation for C 2 H 2 /C 2 H 4 mixture (50:50, v/v) with an adsorption selectivity of 8.1 was realized at room temperature and ambient pressure, on the other hand, it also displayed a good separation performance for C 2 H 4 /C 4 H 6 mixture (50:50, v/v) with an adsorption selectivity of 5.9. Furthermore, adsorption mechanism of C 2 hydrocarbons in this framework was investigated by the DFT-D calculation. The results revealed that this framework discriminated light hydrocarbons as a result of different interaction strength between hydrocarbons and framework that mainly arise from π-π interactions. [ABSTRACT FROM AUTHOR]

Abstract: Tetrabutyl ammonium iodide catalyzed cross-dehydrogenative coupling reaction between α-C(sp3)-H of isochromans and N-hydroxyphathalimide has been achieved using tert-butylhydroxyperoxide as the terminal oxidant. This method offers rapid access to prevalent α-aminoxyl isochroman architectures. A diverse of synthetic isochromans was tolerated with this protocol, giving the corresponding product in moderate to good yields.Graphical Abstract: [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Thiourea itself was used as an organocatalyst for C(sp3) H bond activation. • α-Aminonitriles were obtained in good to excellent yields. • Thiourea acts as a radical initiator instead of non-covalent H-bond donor. Abstract Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N -aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experimental investigations demonstrated that thiourea acts as a radical initiator by abstracting hydroxyl radical (OH) from tert -butyl hydroperoxide (TBHP) directly instead of non-covalent hydrogen bondings (H-bondings) activation. The use of thiourea as a radical initiator offers a new avenue for innovative chemical transformations in organocatalyzed radical chemistry. [ABSTRACT FROM AUTHOR]