Synthesis and characterization of the novel diamine‐functionalized Fe3O4@SiO2 nanocatalyst and its application for one‐pot three‐component synthesis of chromenes

Fe₃O₄@SiO₂@propyltriethoxysilane@o‐phenylendiamine as an environmentally‐benign functionalized silica‐coated magnetic organometallic nanomaterial has been synthesized and characterized by Fourier transforms infrared (FT‐IR) spectroscopy, scanning electron microscopy (SEM) images and energy dispersive X‐ray (EDX) and vibrating sample magnetometer (VSM) analyses. Then, its catalytic activity was investigated for the one‐pot three‐component condensation reaction between dimedone, malononitrile and various substituted aromatic aldehydes to afford the corresponding 2‐amino‐4H‐chromene derivatives under mild reaction conditions. This nanocatalyst can be easily recovered from the reaction mixture by using a magnet and reused for at least five times without significant decrease in catalytic activity.     

Spin-polarized current and tunnel magnetoresistance in heterogeneous single-barrier magnetic tunnel junctions

Current in heterogeneous tunnel junctions is studied in the framework of the parabolic conduction-band model. The developed model of the electron tunneling takes explicitly into account the difference of effective masses between ferromagnetic and insulating layers and between conduction subbands. Calculations for Fe/MgO/Fe-like structures have shown the essential impact of effective mass differences in regions (constituents) of the structure on the tunnel magnetoresistance of the junction.     

Adhesive fracture of heterogeneous interfaces

We have studied the effect of interface heterogeneity on fracture, at both local and global scales. The single cantilever beam adhesion test was used to investigate interfacial fracture between polycarbonate plates and an elastic/fragile epoxy adhesive. Two surface treatments were applied to a (given) polycarbonate plate giving zones of strong and weak adhesion parallel to the crack direction. Calculated fracture energies differed from those expected from a simple rule-of-mixtures. A perturbation method, proposed by Rice, was used and results compared with crack fronts observed in situ. The technique was applied successfully but the difference in values of stress intensity factor between the zones was found substantially different from the experimental value. In an attempt to explain discrepancies, specimens with discontinuous crack fronts (adhesive and/or plates severed along the strong/weak adhesion frontier) were tested. Good agreement was found with the rule-of-mixtures predictions raising questions about the role of crack front continuity in load transfer.     

Pd nanoparticles supported on amphiphilic porous organic polymer as an efficient catalyst for aqueous hydrodechlorination and Suzuki-Miyaura coupling reactions

Developing efficient and recyclable heterogeneous catalysts for organic reactions in water is important for the sustainable development of chemical industry. In this work, Pd nanoparticles supported on DABCO-functionalized porous organic polymer was successfully prepared through an easy copolymerization and successive immobilization method. Characterization results indicated that the prepared catalyst featured big surface area, hierarchical porous structure, and excellent surface amphiphilicity. We demonstrated the use of this amphiphilic catalyst in two case reactions, i.e. the aqueous hydrodechlorination and Suzuki-Miyaura coupling reactions. Under mild reaction conditions, the catalyst showed high catalytic activities for the two reactions. In addition, the catalyst could be easily recovered and reused for several times. Also, no obvious Pd leaching and aggregation of Pd nanoparticles occurred up during the consecutive reactions.     

Pd(0)-guanidine@MCM-41: a very effective catalyst for rapid production of bis (pyrazolyl)methanes

In this research, a rapid, green and efficient protocol for synthesis of bis (pyrazolyl)methane derivatives in the presence of Pd(0)-guanidine@MCM-41 catalysts under solvent-free conditions by the following two methods has been reported: (i) via the one-pot pseudo five-component reaction among phenylhydrazine (2 equivalents), ethyl acetoacetate (2 equivalents) and aromatic aldehydes (1 equivalent); and (ii) the one-pot pseudo three-component reaction between 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (2 equivalents) and aromatic aldehydes (1 equivalent). Some advantages of this protocol include: green conditions, extremely short times, high efficiency, proper one-pot operation, generality of method, easy work-up and recyclability, and reusability of the catalyst up to five times without significant loss in catalytic activity.     

Switching from linear to cyclic δ‐Polyvalerolactone synthesized via zeolitic imidazolate framework as a catalyst: A promising approach

A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF‐8, ZIF‐67, and Zn/Co‐ZIF) are used as a catalyst for the bulk ring‐opening polymerization of δ‐valerolactone without any co‐catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ‐VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF‐8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF‐67 or Zn/Co‐ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity.     

Topotactic Conversion of Alkali-Treated Intergrown Germanosilicate CIT-13 into Single-Crystalline ECNU-21 Zeolite as Shape-Selective Catalyst for Ethylene Oxide Hydration

The conversion of the alkali-treated intergrowth germanosilicate CIT-13 into the single-crystalline high-silica ECNU-21 (named after East China Normal University) zeolite, with a novel topology and a highly crystalline zeolite framework, has been realized through a creative top-down strategy involving a mild alkaline-induced multistep process consisting of structural degradation and reconstruction. Instead of acid treatment, hydrolysis in aqueous ammonia solution not only readily cleaved the chemically weak Ge(Si)−O−Ge bonds located within the interlayer double four ring (D4R) units of CIT-13, but also cleaved the metastable Si−O−Si bonds therein. This led to extensive removal of the D4R units, and also generated silanol groups on adjacent silica-rich layers, which then condensed to form a novel daughter structure upon calcination. Individual oxygen bridges in the reassembled ECNU-21 replaced the germanium-rich D4R units in CIT-13, thereby eliminating the original intergrowth phenomenon along the b axis. With an ordered crystalline structure of 10-ring (R) channels as well as suitable germanium-related Lewis acid sites, ECNU-21 serves as a stable solid Lewis acid catalyst for the shape-selective hydration of ethylene oxide (EO) to ethylene glycol (EG) at greatly reduced H₂O/EO ratios and reaction temperature in comparison with the noncatalytic industrial process.