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.     

An approach to triquinane synthesis using the Pauson-Khand reaction

Tricyclic skeletons have been generated from acyclic enyne precursors by using an intramolecular Pauson-Khand reaction in combination with aldol, Michael and alkylation reactions.     

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.

     

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.     

Analysis of tunable diode-laser spectra of Q(J,0) lines in CH3F near 1475 cm using a multispectrum fitting technique

We have analyzed the methyl fluoride ^RQ(J,0)Q branch lines located near 1475 cm⁻¹ using a simultaneous multi-spectrum fitting technique. In this analysis we have used previously recorded diode-laser data in which we collected many data points covering only one or two Q branch lines in a particular run. The analysis consists of simultaneously fitting 57 spectra collected with numerous pressure and path length conditions for all absorption lines. The data are concatenated to create one continuous spectrum of the Q branch. We have determined the intensity and self-broadened widths at 296 K for 23 ^RQ(J,0) lines.     

On Congruence of Complex Matrices

For each of a standard set of normal forms for (n × n) complex matrices under the relation of congruence, explicit matrices are exhibited which transform, via congruence, the normal form to its transpose.