Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

We report a supramolecular strategy for promoting the selective reduction of O₂ for direct electrosynthesis of H₂O₂. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H₂O₂ from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H₂O₂ and H₂O. Bimolecular pathways have been implicated in facilitating H₂O formation, therefore, we attribute this high H₂O₂ selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.     

A Language for Teaching Discrete-event Simulation

Courses which teach discrete-event simulation are based on many different simulation languages. The requirements for a language to support teaching simulation are discussed. In particular, it is recommended that such languages separate into distinct modules those aspects of simulation which are taught as separate topics. Implementation of the separation is discussed. The SEESIM language, developed as a teaching aid, is described, and examples of its use are given. Straightforward use of SEESIM can be learned quickly, yet the language provides facilities for a staged introduction to advanced concepts of simulation.     

The study and applications of photochemical-dynamical gravity wave model I

A two-dimensional, nonlinear, compressible, diabatic, nonhydrostatic photochemical-dynamical gravity wave model has been advanced. The model includes diabetic process produced by photochemistry and the effect of gravity wave on atmospheric chemical species. In the horizontal direction, the pseudospectral method is used. The finite difference approximations are used in vertical direction z and time t. The FICE method is used to solve the model. The model results on small amplitude fluctuation are very close to those of linear theory, which demonstrates the correctness of the model.

     

Stability of vertices in random boolean cellular automata

Based on computer simulations, Kauffman (Physica D, 10, 145-156, 1984) made several generalizations about a random Boolean cellular automaton which he invented as a model of cellular metabolism. Here we give the first rigorous proofs of two of Kauffman's generalizations: a large fraction of vertices stabilize quickly, consequently the length of cycles in the automaton's behavior is small compared to that of a random mapping with the same number of states; and reversal of the states of a large fraction of the vertices does not affect the cycle to which the automaton moves.     

Lagrangian and Eulerian models for simulating turbulent dispersion and coalescence of droplets within a spray

Lagrangian and Eulerian modelling approaches are compared for simulating turbulent dispersion and coalescence of droplets within a spray. Both models predict similar droplet dispersion rates and shifts in droplet size distribution due to coalescence within the spray, over a wide range of droplet and gas flows, and for sprays with different droplet-size distributions at the nozzle exit. The computer time required for simulating coalescence within a steady axisymmetric spray is of a similar order of magnitude regardless of which formulation, Eulerian or Lagrangian, is adopted. However, the Lagrangian formulation is more practical in terms of the range of applicability and ease of implementation.     

An expedient route to diaza-spirocycles utilizing a sequential multicomponent α-aminoallylation/ring-closing metathesis strategy

A general method for the preparation of diaza-spirocycles is reported. This method used an olefin metathesis in order to construct the desired spirocyclic framework. Beginning with commercially available protected amino ketones, this strategy ultimately produced pharmacologically relevant diaza-scaffolds in an efficient and high-yielding process.     

The study and applications of photochemical-dynamical gravity wave model II

A nonlinear, compressible, non-isothermal gravity wave model that involves photochemistry is used to study the effects of gravity wave on atmospheric chemical species distributions in this paper. The changes in the distributions of oxygen compound and hydrogen compound density induced by gravity wave propagation are simulated. The results indicate that when a gravity wave propagates through a mesopause region, even if it does not break, it can influence the background distributions of chemical species. The effect of gravity wave on chemical species at night is larger than in daytime.