Gold Supported on Hydroxyapatite as a Versatile Multifunctional Catalyst for the Direct Tandem Synthesis of Imines and Oximes

Two birds with one auric stone : The title system acts as a highly efficient heterogeneous catalyst for the one‐pot tandem synthesis of imines or oximes from alcohols and the corresponding amines under mild conditions (see scheme; HAP= hydroxyapatite).

     

Linking Phospholipase Mobility to Activity by Single‐Molecule Wide‐Field Microscopy

Many of the biological processes taking place in cells are mediated by enzymatic reactions occurring in the cell membrane. Understanding interfacial enzymatic catalysis is therefore crucial to the understanding of cellular function. Unfortunately, a full picture of the overall mechanism of interfacial enzymatic catalysis, and particularly the important diffusion processes therein, remains unresolved. Herein we demonstrate that single‐molecule wide‐field fluorescence microscopy can yield important new information on these processes. We image phospholipase enzymes acting upon bilayers of their natural phospholipid substrate, tracking the diffusion of thousands of individual enzymes while simultaneously visualising local structural changes to the substrate layer. We study several enzyme types with different affinities and catalytic activities towards the substrate. Analysis of the trajectories of each enzyme type allows us successfully to correlate the mobility of phospholipase with its catalytic activity at the substrate. The methods introduced herein represent a promising new approach to the study of interfacial/heterogeneous catalysis systems.     

Modelling of the High-Impact Polystyrene Morphogenesis

Summary: High-impact polystyrene (HIPS) is a hetero-phase polymer with the so-called salami morphology. Salami morphology is formed by a continuous PS phase containing micron-sized PB domains. PB domains contain submicron-sized irregular PS occlusions. In our modeling work we addressed several weak points of Cahn-Hilliard model of HIPS salami morphology evolution. The weakest point of Cahn-Hilliard model is the inherently present Ostwald ripening destabilizing or competing with graft-stabilized domains. Two mechanism of formation of HIPS morphology are supported by the model: (i) encapsulation of graft-stabilized PS-rich domains in PB particles, and (ii) polymerization of styrene dissolved in PB-rich phase and subsequent phase separation leading to PS occlusions in PB domains.     

On the multi-phase M/G/1 queueing system with random feedback

In this paper we consider an M/G/1 queue with k phases of heterogeneous services and random feedback, where the arrival is Poisson and service times has general distribution. After the completion of the i-th phase, with probability θ _i the (i + 1)-th phase starts, with probability p _i the customer feedback to the tail of the queue and with probability 1 − θ _i − p _i  = q _i departs the system if service be successful, for i = 1, 2 , . . . , k. Finally in kth phase with probability p _k feedback to the tail of the queue and with probability 1 − p _k departs the system. We derive the steady-state equations, and PGF’s of the system is obtained. By using them the mean queue size at departure epoch is obtained.     

Synthesis, crystal structure, and catalytic properties of MgCo6Ge6

The ternary compound MgCo6Ge6 represents a novel member of the RM6X6 phases, which contains a graphite-type Ge network, Kagomé nets of Co atoms, and Ge2 dumbbells with an unexpected short Ge-Ge contact in the range of a localized Ge-Ge single bond. The title compound shows a large variety of chemical bonding, which ranges from metallic to multicenter and covalent bonding. The role of polar intermetallic alloys as promising candidates for the application as catalysts for the selective hydrogenation of alpha,beta-unsaturated aldehydes is discussed. MgCo6Ge6 possesses a remarkable activity and selectivity for the hydrogenation of cis/trans-citral to geraniol and nerol.     

Multiple-functional capsule catalysts: a tailor-made confined reaction environment for the direct synthesis of middle isoparaffins from syngas

A capsule catalyst for isoparaffin synthesis based on Fischer-Tropsch reaction was designed by coating a H-ZSM-5 membrane onto the surface of the pre-shaped Co/SiO(2) pellet. Morphological and chemical analysis showed that the capsule catalyst had a core-shell structure. A compact, integral shell of H-ZSM-5 crystallized firmly on the Co/SiO(2) substrate without crack. Syngas passed through the zeolite membrane to reach the Co/SiO(2) catalyst to be converted, and all hydrocarbons formed with straight chain structure must enter the zeolite channels to undergo hydrocracking as well as isomerization in this tailor-made confined reaction environment. A narrow, anti-Anderson-Schultz-Flory law product distribution was observed on these capsule catalysts. Contrary to a mechanical mixture of H-ZSM-5 and Co/SiO(2), C(10+) hydrocarbons were suppressed completely on this novel capsule catalyst, and the selectivity of middle isoparaffins was considerably improved. The carbon number distribution of the products depended on the thickness of the zeolite membrane, and it was possible to selectively synthesize specified distillates, such as gasoline-range, or heavier hydrocarbons from syngas directly, by simply adjusting the thickness of the zeolite membrane of the capsule catalyst. This kind of capsule catalysts can be extended to various consecutive reaction systems as the shell and core components are independent catalysts for different reactions. At the same time, shape selectivity and space-confined effects can be expected for the reactant, intermediates and product of the sequential reactions.     

Aerobic oxidation of alcohols in carbon dioxide with silica-supported ionic liquids doped with perruthenate

The replacement of toxic Cr(VI) for O2 and of chlorinated solvents for supercritical carbon dioxide (or ionic liquids) in the oxidation of alcohols remains hindered by the low selectivity and activity of the current heterogeneous catalysts. Using an integrated approach that combines sol-gel entrapped perruthenate as aerobic catalyst, an encapsulated ionic liquid as solubility promoter, and scCO2 as the reaction solvent, we have developed a system capable of rapidly converting different alcohols into carbonyl compounds with complete selectivity, including substrates which are otherwise difficult to oxidise. The methodology is generally applicable and may easily be extended to other waste-free, catalytic syntheses of fine chemicals.