Mechanical Force Induced Formation of Extrinsic Micropores in Coordination Polymers.

Mechanical force can be employed not only to efficiently synthesize new materials under environmentally friendly conditions but also to change the macroscopic and microscopic properties of materials. Although coordination polymers (CPs) are attractive functional materials because they possess high structural designability and diversity, mechanical force-induced structural and functional changes of CPs are challenging issues. In this study, two one-dimensional CPs, one a densely packed nonporous CP [Cu(bza)(pyr)] () and the other a porous CP [Cu(1-nap)(pyr)] () (bza = benzoate, 1-nap = 1-naphthoate and pyr = pyrimidine), were subjected to ball-milling to assess the effect of mechanical force on their porosities.

Solvent-Activated Hafnium-Containing Zeolites Enable Selective and Continuous Glucose-Fructose Isomerisation.

The isomerisation of glucose to fructose is a critical step towards manufacturing petroleum-free chemicals from lignocellulosic biomass. Herein we show that Hf-containing zeolites are unique catalysts for this reaction, enabling true thermodynamic equilibrium to be achieved in a single step during intensified continuous operation, which no chemical or biological catalyst has yet been able to achieve. Unprecedented single-pass yields of 58 % are observed at a fructose selectivity of 94 %, and continuous operation for over 100 hours is demonstrated.

Facile Preparation of 3-Acetamido-5-acetylfuran from N-Acetyl-d-glucosamine by using Commercially Available Aluminum Salts.

3-Acetamido-5-acetylfuran (3A5AF) is a promising intermediate obtained from chitin for the production of N-containing value-added chemicals. However, the synthetic method is complicated so far, which has limited further investigation using 3A5AF. Herein, a facile method was developed for synthesizing 3A5AF from N-acetyl-d-glucosamine (NAG), including a simple isolation procedure.

Porous metallosilicates for heterogeneous, liquid-phase catalysis: perspectives and pertaining challenges.

Porous silicates containing dilute amounts of tri-, tetra- and penta-valent metal sites, such as TS-1, Sn-β and Fe-ZSM-5, have recently emerged as state of the art catalysts for a variety of sustainable chemical transformations. In contrast with their aluminosilicate cousins, which are widely employed throughout the refinery industry for gas-phase catalytic transformations, such metallosilicates have exhibited unprecedented levels of performance for a variety of liquid-phase catalytic processes, including the conversion of biomass to chemicals, and sustainable oxidation technologies with HO. However, despite their unique levels of performance for these new types of chemical transformations, increased utilization of these promising materials is complicated by several factors.

New azo-decorated N-pyrrolidinylthiazoles: synthesis, properties and an unexpected remote substituent effect transmission.

New 5-azo substituted thiazole derivatives have been obtained, under mild conditions and in good yields, by the reaction between 2-N-pyrrolidinylthiazole and a series of aryldiazonium salts bearing, mainly in the para position, groups with different electronic effects. The NMR spectra of the products show broad signals of the methylene groups in the alpha position to the pyrrolidinyl nitrogen, suggesting a hindered rotation around the C2-N bond, of which a double bond character was also evidenced by X-ray diffraction analyses. The free energies of activation for the rotational processes have been obtained from (1)H NMR experiments and computer simulations at different temperatures and provided good correlation with the σ constants of the substituents on the 'remote' benzene ring.

Identification of Active and Spectator Sn Sites in Sn-β Following Solid-State Stannation, and Consequences for Lewis Acid Catalysis.

Lewis acidic zeolites are rapidly emerging liquid-phase Lewis acid catalysts. Nevertheless, their inefficient synthesis procedure currently prohibits greater utilization and exploitation of these promising materials. Herein, we demonstrate that Sn-containing zeolite beta can readily be prepared both selectively and extremely rapidly by solid-state incorporation (SSI) method.