The comparison of detailed chemical kinetic mechanisms: Application to the combustion of methane

Detailed chemical kinetic mechanisms of complex chemical phenomena may be composed of hundreds of species and thousands of individual elementary reactions. It can be an extremely laborious and error‐prone procedure to compare two of these mechanisms, particularly if they come from different sources. We have created software tools which help to highlight the differences between mechanisms written in a Chemkin format and demonstrate their applicability to five literature mechanisms describing the high temperature oxidation of methane. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:467–471, 2004     

Vinyl‐type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts

Novel nickel(II) bisbenzimidazole complexes were prepared via a three‐step synthetic procedure consisting of aniline/diacid condensation, ligand N‐alkylation, and metal complexation. The complexes were characterized by X‐ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1‐butene) but were found to carry out the rapid and efficient polymerization of norbornene. The polynorbornene products were characterized by gel permeation chromatography/light scattering, ¹³C NMR, and IR, and their Mark–Houwink and dn/dc parameters were determined. The molecular weights of the polynorbornenes were very high (weight‐average molecular weight = 587,000–797,000 g/mol). ¹³C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3‐linked polymer); no ring‐opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2095–2106, 2003     

Uncertainty of the two-loop RG upper bound on the Higgs mass

A modified criterion of the SM perturbative consistency is proposed. It is based on the analytic properties of the two-loop SM running couplings. Under the criterion adopted, the Higgs mass up to 380 GeV might not give rise to strong coupling prior to the Planck scale. This means that the light Higgs boson is possibly preferred for reasons other than the SM perturbative consistency, i.e., for reasons beyond the SM.     

Bioengineering functional copolymers. III. Synthesis of biocompatible poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrocomplexes and their thermostabilization effect on the activity of the enzyme penicillin G acylase

Stimuli‐responsive poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrobranched macrocomplexes were synthesized by (1) the radical copolymerization of N‐isopropylacrylamide and maleic anhydride with α,α′‐azobisisobutyronitrile as an initiator in 1,4‐dioxane at 65 °C under a nitrogen atmosphere, (2) the polyesterification (grafting) of prepared poly(N‐isopropylacrylamide‐co‐maleic anhydride) containing less than 20 mol % anhydride units with α‐hydroxy‐ω‐methoxy‐poly(ethylene oxide)s having different number‐average molecular weights (M_n = 4000, 10,000, or 20,000), and (3) the incorporation of macrobranched copolymers with poly(ethylene imine) (M_n = 60,000). The composition and structure of the synthesized copolymer systems were determined by Fourier transform infrared, ¹H and ¹³C NMR spectroscopy, and chemical and elemental analyses. The important properties of the copolymer systems (e.g., the viscosity, thermal and pH sensitivities, and lower critical solution temperature behavior) changed with increases in the molecular weight, composition, and length of the macrobranched hydrophobic domains. These copolymers with reactive anhydride and carboxylic groups were used for the stabilization of penicillin G acylase (PGA). The conjugation of the enzyme with the copolymers significantly increased the thermal stability of PGA (three times at 45 °C and two times at 65 °C). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1580–1593, 2003     

Ionization of two-electron atom in ultrashort laser pulse

The method of numerical integration of the classical equations of motion was used to study interaction of a model two-electron atom with ultrashort laser pulses. Mechanisms and specific features of the ionization process were analyzed in a broad range of laser-field parameters.     

Independence and graph homomorphisms graph homomorphisms

A graph with n vertices that contains no triangle and no 5-cycle and minimum degree exceeding n/4 contains an independent set with at least (3n)/7 vertices. This is best possible. The proof proceeds by producing a homomorphism to the 7-cycle and invoking the No Homomorphism Lemma. For k ≥ 4, a graph with n vertices, odd girth 2k+1, and minimum degree exceeding n/(k+1) contains an independent set with at least kn/(2k+1) vertices; however, we suspect this is not best possible. © 1993 John Wiley & Sons, Inc.     

On Improvements to the Analytic Center Cutting Plane Method

In this paper, we explore a weakness of a specific implementation of the analytic center cutting plane method applied to convex optimization problems, which may lead to weaker results than Kelley's cutting plane method. Improvements to the analytic center cutting plane method are suggested, and tested on some example problems.     

Synthesis of 4H-pyrans by O-cyclization of 1,5-diketones

Substituted 4H-pyrans were obtained in high preparative yields by the reaction of 1,5-diketones with acetic anhydride and boron trifluoride etherate in diethyl ether. It is assumed that the heterocyclization of 1,5-diketones includes a step involving the formation and transformations of an acyloxy carbonium ion.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 320–322, March, 1992.     

Large-scale computer simulation of fully developed turbulent channel flow with heat transfer

Recently, with the advent of supercomputers, there has been considerable interest in the use of direct numerical simulation to obtain information about turbulent shear flow at low Reynolds number. This paper presents a pseudospectral technique to solve the full three-dimensional time-dependent Navier-Stokes and advection-diffusion equations without the use of subgrid-scale modelling. The technique has not been previously used for fully developed turbulent channel flow simulation and is based on methods applied in other contexts. The emphasis of this paper is to provide a reasonably detailed account of how the simulation is done rather than to present new calculations of turbulence. The details of an algorithm for turbulent channel flow simulation and the grid and time step sizes needed to integrate through transient behaviour to steady state turbulence have not been published before and are presented here. Results from a Cray-2 simulation of fully developed turbulent flow in a channel with heat transfer are presented along with a critical comparison between experiment and computation. The first- and second-order moments agree well with experimental measurements; the agreement is poor for higher-order moments such as the skewness and flatness near the walls of the channel. Detailed information given about the effects of spatial grid resolution on a computed results is important for estimating the size of the computation required to study various aspects of a turbulent flow.