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Metal–organic frameworks were synthesized to prepare Pickering emulsions that showed excellent catalytic activity in the deacetalization-Knoevenagel tandem reaction.

Porous organic polymer (POP) coated on a metal-organic framework (MOF) has the functions and advantages of MOF and POP at the same time and has excellent catalytic ability. In this study, an efficient dual-functional core-shell composite MOF@POP with Lewis acid and Brønsted base sites was synthesized using the impregnation method in which MIL-101(Cr) was the core component and polymelamine formaldehyde (PMF) was the shell component. Most importantly, the obtained MIL-101(Cr)@PMF showed perfect catalytic activity in the deacetalization-Knoevenagel tandem reaction. In addition, it could still maintain ultrahigh physical and chemical stability.

A new rhombic dodecahedron Cu–MOP with high absorption of CO2 has been successfully synthesized, and it exhibits excellent performance in chemical fixation of CO2 into cyclic carbonates under ambient conditions.

Core–shell spiny globe shaped Co2P@Ni2P/NiCo2O4@CoO–NF (CNNCC–NF) was constructed. The CNNCC–NF shows ultrahigh areal capacitance (10.11 F cm−2 at 2 mA cm−2). The CNNCC–NF//AC–NF device exhibits a high energy density and excellent stability.

Herein, we reported a facile strategy for the preparation of trifunctional ionic metal-organic frameworks (MOFs) incorporating imidazolium cation functionalities. This strategy exploits the Debus-Radziszewski reaction to create the cationic imidazole ring by postsynthetic modification, meanwhile introducing exchangeable counteranions. On the basis of this strategy, MIL-101-IMOH-Br- has been synthesized, which combines Lewis acidic sites, Bronsted acidic sites, and nucleophilic centers to achieve catalysis for the carbon dioxide-epoxide cycloaddition into cyclocarbonate without any cocatalyst and solvent.

A new metal-organic polyhedron with a high surface area of 407 m

A cationic covalent organic polymer with bifunctional active site was synthesized, which was treated by N, N'-bis(5-bromomethylsalicylaldehyde)ethylenediamine (salen ligand) and tris(1H-imidazol-1-yl) triazine (TIT) in the presence of aluminum ethoxide. The bifunctional cationic covalent organic polymer was investigated by various characterization technologies including PXRD, FT-IR, XPS, TG, SEM, EDS, N2-adsorption and CO2-adsorption. In this polymer, aluminum acts as lewis acid site and bromine ion acts as nucleophile, cooperatively catalyzing the cycloaddition reaction of CO2 and epoxides. Due to its cooperative effect, a higher catalytic activity was found to exhibit 98.1% conversion of epichlorohydrin under optimized conditions (Initial pressure 1.0 MPa, 0.57 mol% catalyst of COP-Al, 90 °C, reaction time 18 h, in the absence of a co-catalyst). Notably, the heterogeneous catalyst still showed good activity and stability after five cycles. A salen-based cationic covalent organic polymers (COP-Al) was used as a bifunctional catalyst for the cycloaddition reaction of CO2 and epoxides with high activity under solvent-free and co-catalyst-free conditions.

The use of transition metal oxides (TMOs) as electrode materials remains challenging because TMOs undergo volume expansion during energy storage. In this work, a core–shell heterostructured nanowire array-assembled hexagonal petal-like CoO encapsulated by MOF-derived Co/N co-doped carbon composite (NF@CoO@Co/N–C) was synthesized on a conductive substrate (Ni foam, NF) using a zeolitic imidazolate skeleton (ZIF-67) as the template via “anchor-etch-calcine” processes. The synergetic function of the heteroatom co-doping, the in-site encapsulation of the carbon matrix, and the unique structural characteristics largely enhance the electrochemical performance. As expected, the NF@CoO@Co/N–C electrode material exhibits an ultrahigh areal capacitance, which is at least two-fold that of its corresponding transition metal oxide. Finally, an asymmetrical-solid-state supercapacitor (ASC) fabricated by NF@CoO@Co/N–C and activated carbon with high volumetric capacity (11.06 F cm−3), high energy density (5.05 mW h cm−3) and a long-term cyclability is demonstrated (94.5% capacitance retention after 10 000 cycles at 10 mA cm−2). This study provides rational guidance toward the design of TMOs electrode materials with extended-life energy storage performance.

Metal–organic framework (MOF)-derived transition metal oxides and transition metal phosphides have great application potential as electrode materials for supercapacitors, owing to their excellent redox activity and high conductivity. However, their electrochemical performances are limited by the stability of the nanostructures. Herein, hierarchical porous honeycomb nanosheets (NiCo2O4@Co2P/Ni2P-CC), for the first time, were prepared on carbon cloth by using ZIF-67 as a sacrificial template via in situ growth-etching and an ion exchange-carbonization-phosphorization method. Benefiting from its unique structure with hierarchical pores, a large specific surface area, transition metal oxide and transition metal phosphide, when employed as an electrode material in an asymmetric supercapacitor, the NiCo2O4@Co2P/Ni2P-CC nanosheets deliver an outstanding areal capacitance of 2881.88 mF cm−a at 2 mA cm−t, which is far superior to NiCo2O4-CC (1458.45 mF cm−C at 2 mA cm−t). An asymmetric supercapacitor was successfully assembled using NiCo2O4@Co2P/Ni2P-CC as a positive electrode and activated carbon/carbon cloth (AC/CC) as a negative electrode, exhibiting a maximum volumetric energy density of 2.53 mW h cm− at a volumetric power density of 22.77 mW cm−c, and excellent cycling stability (87.6% after 10 000 cycles). In this work, MOF-derived NiCo2O4@Co2P/Ni2P-CC nanosheets are used as an ideal electrode material, providing a reference for the rational design and preparation of electrode materials for asymmetric supercapacitors.

Metal–organic frameworks (MOFs) are a novel category of crystalline porous materials, which have become preferred heterogeneous catalysts for many reactions. MOFs are widely used in catalysis because of a combination of many advantages, such as large pore dimensions and surface area, abundant active sites, and possibility to be designed and modified after synthesis. As an important branch of the MOF family, lanthanide metal–organic frameworks (Ln-MOFs)—comprising a variety of multitopic organic ligands and Ln3+ ions/clusters—are a very fascinating MOF materials with complex and diverse topologies. As the functional metal center of MOFs, lanthanide metal ions have a higher coordination number and abundant coordination geometries compared with transition metal ions, which establishes the potential application of Ln-MOFs in the field of catalysis. In addition, Ln-MOFs have the same characteristics as MOFs, including structural diversity and tailorability, high surface area, and high thermal and chemical stability; therefore, Ln-MOFs and their derivatives are suitable for heterogeneous catalysis under various conditions. In this review, an overview of the recent developments achieved in Ln-MOF catalysis, including heterogeneous organic catalysis and photocatalysis over Ln-MOFs and their derivative materials, is provided.

Metal–organic frameworks (MOFs) are promising electrode materials for supercapacitors; however, their electrochemical performances are limited by their low electrical conductivities. To address this problem, “conductive ink” poly(3,4-ethylenedioxythiophene) (PEDOT) was used to enhance the conductivity, while “electron sponge” polyoxometalate [PMo12O40]3− (PMo12) with large electronic transfer capability was used as the capacitance contributor. Finally, MOFs (PCN-224) acted as the host of this composite that provided the electrical double-layer capacitor and a PCN-224@PEDOT/PMo12–CC-II hierarchical hollow micro-vesicle nanostructure was obtained via a simple one-step electro-codeposition. The microvesicle nanocomposite was interspersed in MOF hosts. Benefiting from the novel structure and the synergistic effect of three components, the optimal areal capacitance of the PCN-224@PEDOT/PMo12–CC-II electrode was 4077.8 mF cm−2 at 5 mA cm−2 (the concentration ratio of EDOT : PMo12 is 1 : 0.75), which is 32.9 times more than that of pristine PCN-224 (123.6 mF cm−2). Furthermore, a symmetric supercapacitor device was constructed by the PCN-224@PEDOT/PMo12–CC-II nanocomposite, which possessed an excellent energy density of 0.297–0.0192 mW h cm−2 (at a power density of 0.324–5.128 W cm−2) and a good long-term cycle ability (84.59% for 10 000 cycles at 5 mA cm−2). This study presented a one-step electro-deposition synthetic strategy for the design and fabrication of the high-capacitance MOF-based electrode material, which showed great promise in the future design of high-performance materials for advanced energy production.

In the title compound, [Cu(C

A series of chitosan (CS)-coated metal–organic-framework (MOF) nanoparticles, which combined excellent chemical stability, thermal stability, and recyclability, were synthesized by an in situ growt...

The development of green solid polymer materials bearing multiple active sites as highly efficient heterogeneous catalysts with cooperative effects toward the conversion of carbon dioxide (CO2) to ...

Herein, we reported a facile strategy for the preparation of trifunctional ionic metal-organic frameworks (MOFs) incorporating imidazolium cation functionalities. This strategy exploits the Debus-Radziszewski reaction to create the cationic imidazole ring by postsynthetic modification, meanwhile introducing exchangeable counteranions. On the basis of this strategy, MIL-101-IMOH-Br

Bifunctional Cr-MOF catalysts containing palladium nanoparticles (NPs) have been prepared. Combining the high activity of Pd NPs and base sites in MIL-101-NH2, the catalysts (Pd@MIL-101-NH2) exhibited distinct catalytic activity in a one-pot Suzuki-Knoevenagel reaction. Pd@MIL-101-NH2 has been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and fourier transform infrared spectroscopy (FT-IR). Various substituted phenylboronic acids were used to research the one-pot reaction. The results were highly satisfactory, not only got high yield, but reduced reaction time. Leakage experiments further demonstrated that there is no leaching of active palladium nanoparticles during the reactions. Catalysts could be reused for at least five cycles and activity is not significantly decreased.

A universal strategy is developed to construct metal-organic framework (MOF)-based superhydrophobic/superoleophilic materials by the reaction of activated MOFs and octadecylamine. In particular, S-MIL-101(Cr) composite can efficiently separate chloroform, toluene, petroleum ether, and n-hexane from water with excellent oil-water separation performance, with potential application in the environmental field.

A series of different amount of Pd nanoparticles were successfully loaded on the metal-organic frameworks UiO-66-NH2 using a simple solution impregnation method and applied as efficient catalysts for epoxidation of styrene. In this work, the best reaction efficiency can be explored by altering Pd loadings of Pd/UiO-66-NH2, solvents, reaction temperatures and the molar ratios of styrene to tert-butyl hydroperoxide. Interestingly, when Pd loadings of Pd/UiO-66-NH2 is 3.69 wt%, the target product can be obtained in high yield and selectivity.

A novel strategy has been developed to construct a highly stable core-shell MOF@COF (PCN-222-Co@TpPa-1) bifunctional catalyst through strong π-π stacking interaction. This hybrid material with spatially isolated antagonistic acid-base sites can effectively catalyze the deacetalization-Knoevenagel condensation cascade reaction.

A stable fluorescent nanofibrous membrane was fabricated by in situ growing Eu-MOF crystals on electrospun polyacrylonitrile nanofibers modified with γ-aminobutyric acid. This nanofibrous membrane can be used as a convenient fluorescent test paper for rapid and cyclic detection of nitrobenzene.

A bifunctional catalyst, Pd nanoparticles (NPs) encapsulated in MIL-101, has been synthesized by capillary impregnation. The as-prepared Pd@MIL-101 was characterized by powder X-ray diffraction, N2 physisorption, X-ray photoelectron spectroscopy, transmission electron microscopy, and high-angle annular dark field scanning transmission electron microscopy, indicating that Pd NPs were highly dispersed in the pores of MIL-101 without deposition of the nanoparticles on the external surface or aggregation. The bifunctional catalyst of Pd@MIL-101 exhibited highly catalytic activity for alcohol oxidation and aldimine condensation one-pot reactions, where Pd NPs affords good oxidation activity and MIL-101 offers Lewis acidity. In particular, Pd@MIL-101 yielded an effective catalytic performance with toluene as the solvent, K2CO3 as the co-catalyst, and 353 K as the optimum reaction temperature for the one-pot reaction. After five cycles of reuse, Pd@MIL-101 still shows high catalytic performance. Above all, it is found that the enhanced catalytic performance was achieved via the synergistic cooperation of MIL-101 and Pd NPs.

In recent years, large numbers of hydrophobic/superhydrophobic metal-organic frameworks (MOFs) have been developed. These hydrophobic MOFs not only retain rich structural variety, highly crystalline frameworks, and uniform micropores, but they also have lower affinity towards water and boosted hydrolytic stability. Until now, there were two main strategies to prepare hydrophobic MOFs, including a one-step method and post-synthesis modification (PSM). PSM was an often-used strategy for preparing hydrophobic MOFs. Hydrophobic MOFs showed unique advantages when used as catalysts for various categories of reactions. Herein, recent research advances relating to hydrophobic MOFs in the catalytic field are presented. The catalytic activities of hydrophobic MOFs and corresponding hydrophilic ones are also compared, and the superiority of hydrophobic MOFs or MOF materials as catalysts in 10 reactions is discussed. Finally, the advantages of hydrophobic MOFs as catalysts or auxiliary materials are summarized and promising future developments of hydrophobic MOFs are highlighted.

By immobilizing Ag nanoparticles to UiO-66, a series of nanocatalysts (Ag/UiO-66) were synthesized and used as catalysts for oxidation of styrene. The catalytic efficiency could be optimized by altering Ag loadings of Ag/UiO-66, solvents, the molar ratios of styrene to tert-butyl hydroperoxide (TBHP) and reaction temperatures. Interestingly, the Ag loadings 1.86 wt% of Ag/UiO-66 exhibited high conversion, selectivity and recyclability in the selective oxidation of styrene.

A series of 12-connected lanthanide cluster based metal–organic frameworks (MOFs) have been constructed by [Ln6(μ3-OH)8(COO−)12] secondary building units (SBUs) and 2-aminobenzenedicarboxylate (BDC-NH2) ligands. These obtained materials exhibit high chemical stability and generic thermal stability, especially in acidic and basic conditions. They also present commendable CO2 adsorption capacity, and Yb-BDC-NH2 was further confirmed by a breakthrough experiment under both dry and wet conditions. Moreover, these materials possess both Lewis acid and Bronsted base sites that can catalyze one-pot tandem deacetalization–Knoevenagel condensation reactions.

Two new three-dimensional metal–organic frameworks {[(CH3)2NH2]2[TM2(L)2]}n·x(solvent) (FJI-Y7, FJI = Fujian Institute, TM = Zn; FJI-Y8, TM = Cd) have been solvothermally prepared based on multifunctional pyridyl–tricarboxylate ligand 5-(5-carboxypyridin-3-yl)benzene-1,3-dicarboxylic acid (H3L). Single crystal X-ray analysis reveals that they possess non-interpenetrating binodal (4,4)-connected three-dimensional PtS-type networks with the Schlafli point symbol of {42·84}. Interestingly, both FJI-Y7 and FJI-Y8 can be used as highly efficient size-selective heterogeneous catalysts for the solvent-free cyanosilylation of acetaldehydes under mild conditions.

Novel three-dimensional (3D) interconnected hierarchical sponge-like porous carbons (PCs) using Zn-based MOFs (Zn(tbip)) with two distinct particle sizes as precursors were prepared via a one-step pyrolysis process. The size effect of the precursor on the porous architecture has been evaluated in detail. The porous carbon derived from small-sized Zn(tbip) at 900 °C (denoted as C-S-900) possesses a hierarchical porous structure with the highest specific surface area (1356 m2 g−1), which benefits ion immersion and retention. C-S-900 demonstrates an ultrahigh specific capacitance of 369 and 226 F g−1 at 10 and 400 mV s−1 in a 6 mol L−1 KOH electrolyte, respectively. In addition, a symmetric flexible all-solid-state supercapacitor device was assembled with the electrode of C-S-900 and PVA/KOH gel electrolyte. The device can offer 96% capacity after 2000 stretching–bending cycles and operate micro-electronic devices displaying excellent mechanical robustness and cycling stability. The present work explored the relationship between the size effect of MOF precursors and the porous carbon architectures to optimize the performance of supercapacitors.

Two porous metal-organic frameworks (MOFs) incorporating pentanuclear Yb(III) clusters and pyridyl-supported tetracarboxylates or pyridyl carboxylic acid-supported tetracarboxylates, Yb-DDPY and Yb-DDIA, are presented, in which the pentanuclear Yb(III) cluster shows uncommon trigonal bipyramidal geometry. Furthermore, the pentanuclear Yb(III) clusters are extended by tetracarboxylates to form a 3D porous framework with uniform M12L8-cages constructed by 12 pentanuclear Yb(III) clusters and 8 tetracarboxylates with the size of ca. 20 A × 17 A. Their highly CO2 uptake capacity and the existence of Lewis acidic sites make these MOFs promising catalysts for the chemical conversion of CO2. These MOFs demonstrate good catalytic activities and recyclability in the cycloaddition of CO2 and epoxides at 60 °C under 1.0 MPa pressure or at room temperature and atmospheric pressure. In addition, the synergistic effect of the Bronsted acidic –COOH groups and the Lewis acidic Yb(III) sites makes Yb-DDIA exhibit higher catalytic activity towards the cycloaddition of CO2 and epoxides.

An active allylic amine N-oxide (ANO) molecule was cocrystallized with pyrogallol[4]arene through intermolecular hydrogen bonds and π···π interactions. Interestingly, [2,3]-Meisenheimer rearrangement of the ANO was suppressed, which was analyzed in detail in the solid state by single crystal X-ray crystallography in varying temperatures. Additionally, this work provides not only a new strategy to stabilize reactive chemicals, but also a unique method to elucidate their structures.

In this work, porous decatungstate-TiO 2 composite thin film has been prepared by the electrodeposition method. The advantages of decatungstate as electrochromic material are discussed and the electrochromic performances of the composite film have also been systematically investigated. The transmittance decreased from 98.0% down to 50.8% at the wavelength of 550 nm under an applied potential of − 0.8 V. Good reversibility and reproducibility also can be observed in the composite electrochromic film. The porous structure of the composite film not only provides a large surface area for loading W 10 polyanions but is also beneficial for the fast diffusion of H + , which results in high electrochromic performances.

A stable metal-organic framework (MOF) nanofibrous membrane (NFM) was successfully fabricated by in situ growing H3PW12O40 (PW12) @UiO-66 crystals onto crosslinked polyacrylic acid (PAA)-poly (vinyl alcohol) (PVA) nanofibers prepared through electrospinning. Characterization with High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), Fourier transform infrared (FT-IR), Powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed that the crystallinity and structure of PW12@UiO-66 crystals maintained well on the PAA-PVA NFM. The as-prepared PAA-PVA/PW12@UiO-66 NFM can be used as a photocatalyst for simultaneous photocatalytic degradation of methyl orange (MO) and formaldehyde (FA) in aqueous solution. The possible mechanism was that electrons transferred from FA to MO via PAA-PVA/PW12@UiO-66 NFM, made the photodegradation of MO driven by the reductive pathway. At the same time, FA was oxidized due to the loss of electrons. PAA-PVA/PW12@UiO-66 NFM presented a satisfactory stability and reusability, mainly because the partially crosslinked PAA-PVA NFM can provide sufficient carboxyl groups for anchoring PW12@UiO-66 particles. Due to no separation process was needed for electrospun NFM after each photocatalytic cycle, the reuse process of PAA-PVA/PW12@UiO-66 NFM can be conducted more conveniently and rapidly compared with powdered MOFs photocatalysts. This work will be useful for the design of MOFs NFMs photocatalysts based on electrospinning applied to comprehensive treatment of organic pollutant wastewater.

A bifunctional MOF@POP core-shell catalyst (NH2-UiO-66(Hf)@CoTPy-CAP) constructed by amino functionalized NH2-UiO-66(Hf) and ionic porphyrin-based CoTPy-CAP was first reported to be applied in the cycloaddition of CO2. Because NH2-UiO-66(Hf)@CoTPy-CAP both possess abundant Lewis acidic sites and nucleophilic centers in one system, the catalyst can efficiently catalyze CO2 fixation with epoxides without homogeneous cocalyst under mild conditions, achieving propylene oxide (PO) conversion of 98 % at 80 °C and 0.5 MPa. Furthermore, the bifunctional synergetic catalyst was easy to be recovered and recycled for five runs, and the reduction of activity was not obvious. This present work provides a viable direction for the fabrication of bifunctional synergetic catalysts for high-efficient CO2 fixation without cocatalyst under mild conditions.

A stable benzimidazole-containing Co(II) coordination polymer namely [Co(L)0.5(oba)]n (1) (H2oba = 4,4′-oxybis(benzoate), L = 1,6-bis(5,6-dimethylbenzimidazolyl) hexane) was successfully synthesized by ultrasonic technique under mild conditions. In especial, the effects of initial reagent concentration, irradiation time and ultrasonic power on the morphology and size of micron scale 1 were discussed in detail. Micron scale 1 appeared exceptional solvent and pH stabilities. Further, as a heterogeneous Lewis catalyst, 1 exhibited a highly activity and recyclability for CO2 transformation by cycloaddition with epoxide under room temperature.

MOF-templated nitrogen-doped porous carbon materials (NPCs) have been prepared by employing the previously reported MOF, [(CH3)2NH2]6[Ni(H2O)6]3{Ni6(η6-TATAT)4(H2O)12}, as a precursor, which can act as efficient electrocatalysts for oxygen reduction reactions (ORRs). The carbonized MOF acts as the carbon source, and urea is employed as an additional nitrogen source. The urea modified carbon materials, carbonized at 800 °C, 900 °C and 1000 °C under Ar atmosphere, all show electrocatalytic activity for ORRs; the material carbonized at 900 °C exhibits a more appropriate nitrogen content, robust pore structure and an excellent degree of graphitization. In alkaline media, NPC-900 exhibits superior catalytic activity (the onset and half-wave potentials are −0.06 V and −0.23 V vs. Ag/AgCl, respectively), excellent long-term durability and outstanding methanol tolerance compared with the commercial Pt/C catalyst.

A microporous hexanuclear europium cluster based MOF, (DMA)2[Eu6(μ3-OH)8(BPDC)6(H2O)6]n·(solv)x (DMA = dimethylamine cation and H2BPDC = [1,1′-biphenyl]-4,4′-dicarboxylic acid), can be applied as a highly selective and sensitive bifunctional luminescence sensor to detect nitrobenzene and 4-aminophenol through an energy competition mechanism. More interestingly, this MOF can detect nitrobenzene and 4-aminophenol with low detection limits of 5–70 ppm and 5–110 ppm, respectively.

Two series of chemically and thermally stable rare-earth MOFs were constructed using trinuclear [M3(μ3-OH)(COO)6] SBUs and linear dicarboxylate linkers, which feature three-dimensional 12-connected frameworks with an hcp topology. These materials contain a large density of Lewis acidic sites, leading to high catalytic activity towards the cycloaddition of CO2 and epoxides under mild conditions.

Cd(II)-organic coordination polymer with the formula [Cd 3 (btdc) 3 (DMF) 2 (EtOH) 2 ]·2EtOH·2H 2 O were solvothermally synthesized by treating Cd(II) nitrates with 2,2′-bithiophene-5,5′-dicarboxylic acid (H 2 btdc) and characterized by single crystal X-ray diffraction, elemental analysis, thermogravimetric analyses, IR spectroscopy and X-ray powder diffraction. Single-crystal X-ray diffraction studies indicate that the Cd(II) complex exhibits a 3D supramolecular framework, in which trinuclear Cd(II) clusters are connected by btdc ligands to form a 2D (4, 4) layer. Furthermore, the 2D (4, 4) layers stacked via AA mode. This complex displays strong fluorescent emission both in the solid state and in methanol suspension at room temperature, which can act as the fluorescent probe for selectively detecting Zn 2+ ions and nitrobenzene through luminescence enhancing and quenching, respectively.

Objectives The 2015 World Health Organization classification defines pulmonary large-cell neuroendocrine carcinoma (LCNEC) as a high-grade neuroendocrine carcinoma. However, the clinical characteristics and prognostic factors of pure LCNEC and combined LCNEC remain unclear. Hence, we performed a multi-center retrospective study to compare the clinical outcomes of pure versus combined LCNEC. Materials and methods Data from 381 patients with pulmonary LCNEC admitted to 17 Chinese institutes between 2009 and 2016 were collected retrospectively. Clinical characteristics and prognosis were analyzed among patients receiving adjuvant (adjuvant group; n = 56) and first-line (first-line group; n = 146) chemotherapy, as well as among patients receiving small cell lung cancer (SCLC) and non-SCLC (NSCLC) chemotherapy regimens. The Kaplan-Meier method and multivariable Cox regression were used to identify clinicopathological variables that might influence patient outcomes. Results Expression levels of neuroendocrine markers (synaptophysin, chromogranin-A, CD56) were associated with patients' prognosis in the total study cohort. In the adjuvant group, median disease-free survival was non-significantly longer for SCLC-based regimens than for NSCLC-based regimens (P = 0.112). In the first-line group, median progression-free survival was significantly longer for SCLC-based regimens than for NSCLC-based regimens (11.5 vs. 7.2 months, P = 0.003). Among patients with combined LCNEC, adenocarcinoma was the most common combined component, accounting for 70.0 % of cases. Additionally, median overall survival was non-significantly shorter for combined LCNEC than for pure LCNEC (P = 0.083). Conclusion The SCLC regimen is a more effective choice, as either first-line or adjuvant chemotherapy, when compared to the NSCLC regimen for LCNEC treatment. Further studies are needed to clarify the survival differences between patients with pure-, and combined LCNEC.

A unique 3D framework containing three different types of nanoscale polyhedron cages was constructed by incorporating dinuclear [M2(μ2-OH)(COO)4] (M = Co, Ni) secondary building units and pyridyl-c...

Rational design and synthesis of hollow core–shell hetero-structures with high complexity still remains challenging for high-performance supercapacitors. Here, a simple and effective strategy that involves a ‘root-etch-wrap’ process was developed to synthesize hollow core–shell hetero-structured electrodes. Specifically, ZnO hollow spheres take root on carbon cloth via an in situ growth routine, then are etched to aid the generation of a ZIF-8 shell. As-synthesized hollow core–shell ZnO@ZIF-8 is wrapped by PANI nanocoating, resulting in a flexible conductive porous electrode (denoted as PANI/ZnO@ZIF-8-CC). The optimized electrode exhibits an ultrahigh areal capacitance (4839–3987 mF cm−2 at 5–30 mA cm−2), which is at least 3 times higher than that of PANI-CC and ZnO@ZIF-8-CC owing to the synergistic effect. In addition, a symmetric flexible supercapacitor fabricated by PANI/ZnO@ZIF-8-CC exhibits a high energy density of 0.137–0.0891 mW h cm−3 (at a power density of 1.421–23.629 W cm−3) and a good long-term cycling ability (87% for 10 000 cycles at 5 mA cm−2). All of these results make unique core–shell structured PANI/ZnO@ZIF-8-CC a promising electrode material for advanced energy storage and conversion applications.

A new bifunctional acid-base catalyst, core-shell UiO-66@SNW-1, with robust chemical and thermal stability, recyclability, and durable catalytic activity is synthesized by a convenient, universal strategy. Interestingly, this hybrid material can effectively catalyze deacetalization-Knoevenagel condensation reaction in the presence of excellent compartmentalization to spatially isolate opposing acid-base sites.

Heterogeneous homocoupling reactions of phenylboronic acids were greatly accelerated via Suzuki homocoupling reactions. In this work, a tandem route was designed which firstly one part of phenylboronic acids reacted with iodine to form iodobenzenes, then another part of phenylboronic acids coupled with iodobenzenes to produce biaryl compounds. The tandem reaction were catalyzed by a bifunctional heterogeneous catalyst of metal organic frameworks encapsulated with palladium nanoparticles (Pd@MOFs). This strategy for forming symmetric C-C bond between benzene rings has obvious advantages such as high efficiency, easy separation, good recyclability and no addition of toxic halogenated benzene.

The development of sustainable heterogeneous catalysts in converting carbon dioxide (CO2) into value-added chemicals is a promising way to alleviate the environmental pressure caused by global warming. Here, two novel ionic polymers (IPs, namely IP-1 and IP-2) with high yield and excellent physiochemical stability have been synthesized facilely from the direct reaction of 1,3,5-tris(bromomethyl)benzene with 1,4-diazabicyclo[2.2.2]octane and 3,6-di(1H-imidazol-1-yl)pyridazine, respectively. Their catalytic abilities to convert CO2 into cyclic carbonates have been explored, and both IP-1 and IP-2 show excellent catalytic activity under solvent-free, cocatalyst-free, and mild reaction conditions, and can be recycled and reused six times without decreasing their catalytic abilities. These materials are easily synthesized, and there are no metals and other additives during the catalytic process, which provides a possibility for the industrial immobilization of CO2 to carbonate over heterogeneous catalysts.

An In-based metal-organic framework, with 1D nanotubular open channels, In2(OH)(btc)(Hbtc)0.4(L)0.6·3H2O (1), has been synthesized via an in situ ligand reaction, in which 1,2,4-H3btc is partially transformed into the L ligand. Compound 1 exhibits exceptional thermal and chemical stability, especially in water or acidic media. The activated 1 presents highly selective sorption of carbon dioxide (CO2) over dinitrogen. Interestingly, diffuse-reflectance infrared Fourier transform spectroscopy with a carbon monoxide probe molecule demonstrates that both Lewis and Brønsted acid sites are involved in compound 1. As a result, as a heterogeneous Lewis and Brønsted acid bifunctional catalyst, 1 possesses excellent activity and recyclability for chemical fixation of CO2 coupling with epoxides into cyclic carbonates under mild conditions. In addition, the mechanism for the CO2 cycloaddition reaction has also been discussed.