Highly Site-Selective Epoxidation of Polyene Catalyzed by Metal–Organic Frameworks Assisted by Polyoxometalate

Ectropis obliqua Prout is one of the most severe defoliator insects of tea plants. Sex pheromones method has been widely used for monitoring and controlling the insect pest of E. obliqua Prout due to their relative safety, low cost, and environmental friendliness. However, conventional preparing sex pheromones of E. obliqua Prout has been criticized by the costly and/or low efficiency procedure. Herein, we report a series of Fe-based metal–organic frameworks (MOFs) as efficient heterogeneous catalysts for the site-selective epoxidation of 3Z,6Z,9Z-octadecatriene to its monoepoxides. Particularly, MIL-100(Fe) combined with polyoxometalate (POM) as cocatalyst appears as the best catalyst for the oxidation of 3Z,6Z,9Z-octadecatriene to a high site selectivity to the corresponding 6,7-epoxide with good yields. 3Z,6Z,9Z-octadecatriene and its corresponding 6,7-epoxide are the primary sex pheromone components of the E. obliqua Prout. Significantly, the field bioassay experiments showed that the mixed products were highly effective in attracting E. obliqua Prout male moths. This work provides a general method to fast and clean synthesis of sex pheromones and opens new avenues for the application of Fe-based MOFs in the pest control with environmental friendliness.     

Highly Enantioselective α-aminoxylation Reactions Catalyzed by Isosteviol-proline Conjugates in Buffered Aqueous Media

Abstract  

Chiral amphiphilic conjugate catalysts were designed and synthesized by covalently connecting l-proline with an inexpensive natural product, isosteviol. These catalysts demonstrated remarkable efficiency in the asymmetric α-aminoxylation of aldehydes and ketones using nitrosobenzene in phosphate buffer solution, resulting in good to high yields and excellent enantioselectivities without using any additives. At pH 9.1, the amphiphilic catalysts showed a pH responsive ability in phosphate buffer solution, which facilitated the excellent O-selectivity reactions, illustrating a viable approach for the development of asymmetric supra-molecular catalysts.     

Synthesis of Vitamin A Esters by Immobilized Candida sp. Lipase in Organic Media

Vitamin A ester was synthesized in organic solvents with immobilized lipase from Candida sp. The types of lipases, influences of solvent, the molar ratio of substrates, the reaction temperature and the water activity in the reaction were studied in detail in order to obtain the optimum conditions for Vitamin A palmitate synthesis. In a system of hexane, 100mg immobilized Candida sp. lipase was used in the presence of 1.2mmol vitamin A acetate and 3.6mmol palmitic acid. The yield of vitamin A palmitate reached 81% in 12h at 25℃. The immobilized Candida sp. lipase was prepared by adsorbing Cand/da sp. fermentation broth on pretreated textile and could be reused for at least six batches.     

Creating Oxidase–Peroxidase Fusion Enzymes as a Toolbox for Cascade Reactions

A set of bifunctional oxidase–peroxidases has been prepared by fusing four distinct oxidases to a peroxidase. Although such fusion enzymes have not been observed in nature, they could be expressed and purified in good yields. Characterization revealed that the artificial enzymes retained the capability to bind the two required cofactors and were catalytically active as oxidase and peroxidase. Peroxidase fusions of alditol oxidase and chitooligosaccharide oxidase could be used for the selective detection of xylitol and cellobiose with a detection limit in the low-micromolar range. The peroxidase fusions of eugenol oxidase and 5-hydroxymethylfurfural oxidase could be used for dioxygen-driven, one-pot, two-step cascade reactions to convert vanillyl alcohol into divanillin and eugenol into lignin oligomers. The designed oxidase–peroxidase fusions represent attractive biocatalysts that allow efficient biocatalytic cascade oxidations that only require molecular oxygen as an oxidant.     

Dual Inhibition of Pyruvate Dehydrogenase Complex and Respiratory Chain Complex Induces Apoptosis by a Mitochondria-Targeted Fluorescent Organic Arsenical in vitro and in vivo

Based on the potential therapeutic value in targeting mitochondria and the fluorophore tracing ability, a fluorescent mitochondria-targeted organic arsenical PDT-PAO-F16 was fabricated, which not only visualized the cellular distribution, but also exerted anti-cancer activity in vitro and in vivo via targeting pyruvate dehydrogenase complex (PDHC) and respiratory chain complexes in mitochondria. In details, PDT-PAO-F16 mainly accumulated into mitochondria within hours and suppressed the activity of PDHC resulting in the inhibition of ATP synthesis and thermogenesis disorder. Moreover, the suppression of respiratory chain complex I and IV accelerated the mitochondrial dysfunction leading to caspase family-dependent apoptosis. In vivo, the acute promyelocytic leukemia was greatly alleviated in the PDT-PAO-F16 treated group in APL mice model. Our results demonstrated the organic arsenical precursor with fluorescence imaging and target-anticancer efficacy is a promising anticancer drug.     

Aromatic Halogenation by Using Bifunctional Flavin Reductase–Halogenase Fusion Enzymes

The remarkable site selectivity and broad substrate scope of flavin-dependent halogenases (FDHs) has led to much interest in their potential as biocatalysts. Multiple engineering efforts have demonstrated that FDHs can be tuned for non-native substrate scope and site selectivity. FDHs have also proven useful as in vivo biocatalysts and have been successfully incorporated into biosynthetic pathways to build new chlorinated aromatic compounds in several heterologous organisms. In both cases, reduced flavin cofactor, usually supplied by a separate flavin reductase (FR), is required. Herein, we report functional synthetic, fused FDH-FR proteins containing various FDHs and FRs joined by different linkers. We show that FDH-FR fusion proteins can increase product titers compared to the individual components for in vivo biocatalysis in Escherichia coli.     

Clean Baeyer–Villiger Oxidation Using Hydrogen Peroxide as Oxidant Catalyzed by Aluminium Trichloride in Ethanol

Baeyer–Villiger oxidation of ketones was carried out using AlCl₃ as catalyst, H₂O₂ (30%) as oxidant in innocuity and environmentally friendly ethanol conditions. Cyclic ketones and acyclic ketones were transformed into the corresponding lactones or esters in 5–24 h at 40–70 °C with very high conversion and selectivity. A possible reaction mechanism was also given.     

Two Supramolecular Microporous Metal–Organic Frameworks Templated by Keggin Polyoxometalates

Two new Keggin polyoxometalates (POM)-templated supramolecular metal–organic frameworks (MOF) with micropores, Cu₃(L)₆[H₃(PMo₁₂O₄₀)₂]·6H₂O (1) and Cu₃(L)₆[H₅(SiW₁₂O₄₀)₂]·6H₂O (2) (L?=?1,2-bis(imidazol-1-ylmethyl)ethane), have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and cyclic voltammetry. These two isostructural compounds are constructed by two distinct moieties, a Keggin polyanion and a linear [Cu(L)₂]⁺ subunit. The [Cu(L)₂]⁺ subunits further form a microporous MOF through supramolecular interactions. The Keggin polyanions act as templates inducing the micropores. The electrochemical and electrocatalytic behavior of compounds 1 and 2 bulk-modified carbon paste electrodes (1-, 2-CPE) was studied.     

Organic Vapor/Gas Mixture Separation by Membrane–-A Parametric Study

Abstract

A parametric study was carried out for the membrane separation of organic vapor-gas mixtures. Based on a set of basic transport equations, the effect of the concentration polarization on the membrane surface as a function of mass transfer coefficient is illustrated. It is shown that the concentration polarization is negligible for membranes of low permeability but would be significant for highly permeable and selective membranes. The effects of some operating parameters and membrane permselectivity on the separation performance are also discussed. The results demonstrate the utility of parametric analyses for exploring the effects of variations in the membrane separation of organic vapor-gas mixtures.     

Selective Oxidation of Cyclohexane to Cyclohexanone Catalyzed by Phenanthroline–CuCl2 Complex

A highly efficient oxidation of cyclohexane to cyclohexanone is accomplished over phenanthroline–CuCl₂ catalyst in relatively mild conditions. This study realized nearly 100% selectivity for cyclohexanone at 24.4% conversion of cyclohexane. The reaction has been studied by various parameters like performance of copper(II) salts, effect of solvents, influence of bases, the ratio of o-phenanthroline: CuCl₂, and reaction time. In order to further study this reaction system, the possible mechanism was proposed.     

Baeyer–Villiger Oxidation of Cyclohexanone in Aqueous Medium with In Situ Generation of Peracid Catalyzed by Perhydrolase CLEA

A perhydrolase, immobilized as a cross linked enzyme aggregate (CLEA), was employed to catalyze the in situ formation of peracetic acid (PAA) from ethylene glycol diacetate (EGDA) and hydrogen peroxide. The produced PAA was used for the Baeyer–Villiger oxidation of cyclohexanone, which afforded caprolactone in 63 % yield. The effect of type and amount of acyl donor, solvent, pH, temperature and ratio of cyclohexanone to hydrogen peroxide on the production of caprolactone was studied. The highest caprolactone yield was obtained with 100 mM EGDA as the acyl donor at pH 6 and room temperature using a ratio of cyclohexanone to hydrogen peroxide ratio of 1:4. Interestingly, the perhydrolase CLEA exhibited the highest activity in aqueous medium in contrast to the well studied lipase B from Candida antarctica. The perhydrolase CLEA proved to be a very efficient catalyst; the K _m and V_max values were 118 mM and 56.3 μmol min^?1, respectively.