Copper(II) Triflate Catalyzed Amination of 1,3‐Dicarbonyl Compounds

A method to prepare α,α‐acyl amino acid derivatives efficiently by Cu(OTf)₂+1,10‐phenanthroline (1,10‐phen)‐catalyzed amination of 1,3‐dicarbonyl compounds with PhI?NSO₂Ar is described. The mechanism is thought to initially involve aziridination of the enolic form of the substrate, formed in situ through coordination to the Lewis acidic metal catalyst, by the putative copper–nitrene/imido species generated from the reaction of the metal catalyst with the iminoiodane source. Subsequent ring opening of the resultant aziridinol adduct under the Lewis acidic conditions then provided the α‐aminated product. The utility of this method was exemplified by the enantioselective synthesis of a precursor of 3‐styryl‐2‐benzoyl‐L ‐alanine.     

Copper(II) triflate catalyzed amination and aziridination of 2-alkyl substituted 1,3-dicarbonyl compounds

A method to prepare α-acyl-β-amino acid and 2,2-diacyl aziridine derivatives efficiently from Cu(OTf)(2) + 1,10-phenanthroline (1,10-phen)-catalyzed amination and aziridination of 2-alkyl substituted 1,3-dicarbonyl compounds with PhI═NTs is described. By taking advantage of the orthogonal modes of reactivity of the substrate through slight modification of the reaction conditions, a divergence in product selectivity was observed. In the presence of 1.2 equiv of the iminoiodane, amination of the allylic C-H bond of the enolic form of the substrate, formed in situ through coordination to the Lewis acidic metal catalyst, was found to selectively occur and give the β-aminated adduct. On the other hand, increasing the amount of the nitrogen source from 1.2 to 2-3 equiv was discovered to result in preferential formal aziridination of the C-C bond of the 2-alkyl substituent of the starting material and formation of the aziridine product.     

Elucidating the relationship between the spreading coefficient, surface-mediated partial coalescence and the whipping time of artificial cream

We studied the whipping of artificial creams composed of a blend of sunflower oil and hydrogenated palm fat stabilized by protein or a mixture or protein and low molecular weight (lmw) surfactant. It was found that an increased whipping speed, decreased protein concentration, and the addition of lmw surfactant leads to shorter whipping times. Further, shorter whipping times were observed for WPI-stabilized cream compared to cream stabilized by sodium caseinate. In all cases, the decrease in whipping time was due to a decrease in the length of the second stage of whipping, the stage characterized by the adhesion of fat droplets to the air bubble surface. The decrease in whipping time could be accounted for by considering the influence of the experimental variables on the fraction of bubble surface area at which fat droplet spreading is possible. The same changes in parameters that promote droplet spreading at the air/water interface cause a decrease in the whipping time of our model creams. Correlating the whipping time of cream with the spreading behavior of fat droplets at the air/water interface represents a new insight into the mechanisms involved in the whipping of cream.     

Tandem queueing networks with neighbor blocking and back-offs

We introduce a novel class of tandem queueing networks which arise in modeling the congestion behavior of wireless multi-hop networks with distributed medium access control. These models provide valuable insight in how the network performance in terms of throughput depends on the back-off mechanism that governs the competition among neighboring nodes for access to the medium. The models fall at the interface between classical queueing networks and interacting particle systems, and give rise to high-dimensional stochastic processes that challenge existing methodologies. We present various open problems and conjectures, which are supported by partial results for special cases and limit regimes as well as simulation experiments.     

Conversion of methanol to hydrocarbons: how zeolite cavity and pore size controls product selectivity

Liquid hydrocarbon fuels play an essential part in the global energy chain, owing to their high energy density and easy transportability. Olefins play a similar role in the production of consumer goods. In a post-oil society, fuel and olefin production will rely on alternative carbon sources, such as biomass, coal, natural gas, and CO(2). The methanol-to-hydrocarbons (MTH) process is a key step in such routes, and can be tuned into production of gasoline-rich (methanol to gasoline; MTG) or olefin-rich (methanol to olefins; MTO) product mixtures by proper choice of catalyst and reaction conditions. This Review presents several commercial MTH projects that have recently been realized, and also fundamental research into the synthesis of microporous materials for the targeted variation of selectivity and lifetime of the catalysts.     

Numerical simulations of high-speed chemically reacting flow

The essentially nonoscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacing flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.This work has been supported by the Aerospace Corporation through a Corporate Fellowship, by NASA Dryden Flight Research Center under Grant NCC 2-374, by ONR Grant N00014-86-K-0691, by NSF Grant DMS 88-11863, and by a DARPA Grant in the ACMP Program.     

Dynamics of species in a model with two predators and one prey

In this paper, we study a predator-prey model which has one prey and two predators with Beddington-DeAngelis functional responses. Firstly, we establish a set of sufficient conditions for the permanence and extinction of species. Secondly, the periodicity of positive solutions is studied. Thirdly, by using Liapunov functions and the continuation theorem in coincidence degree theory, we show the global asymptotic stability of such solutions. Finally, we give some numerical examples to illustrate the behavior of the model.     

Identification of non-optimal arcs for the travelling salesman problem

Conditions are presented for the identification of (directed) arcs for the traveling salesman problem, that can be eliminated with at least one optimal solution remaining. The conditions are not based on lower or upper bounds; the presence of an identified arc in a solution implies that the solution is not 3-optimal. An example illustrates how to use the conditions.     

The mixed and multi model line balancing problem: a comparison

The balancing problem deals with the assignment of tasks to work stations. We can distinguish two approaches in the literature on the mixed model line balancing problem, that both transform this problem into a single model line balancing problem. These approaches use combined precedence diagrams and adjusted task processing times, respectively.An experiment was carried out to compare several heuristics based on the combined precedence diagram. A new optimisation method has been developed. The results indicate that the position of common tasks in the precedence diagram of the different models has a significant effect on both the CPU time and the unequal distribution of the total work content of single models among work stations. Moreover, good solutions with respect to the number of required stations go together with long CPU times. For several instances, we decreased the CPU times considerably without deteriorating the performance of the methods, by using a reversed combined precedence diagram.