Polarization of electronic transitions in aromatic hydorcarbon molecules and their mono- and di-valent ions

An overview of predictive chemical kinetics is presented, with an application to the simulation and design of homogeneous charge compression ignition (HCCI) engines. The engine simulations are sensitive to the details of hydroperoxyalkyl (QOOH) radical chemistry, which are only partially understood, and there is a significant discrepancy between the simulations and experiment that limits the usefulness of the simulations. One possible explanation is that QOOH decomposes by other channels not considered in existing combustion chemistry models. Rate constants for one of these neglected channels, the intramolecular radical attack on the QOOH peroxide linkage to form hydroxyalkoxyl (HOQO) radicals, are predicted using quantum chemistry (CBS-QB3), to test whether or not this proposed channel can explain the observed discrepancies in the engine simulations. Although this channel has a significant rate, the competing attack on the other O atom in the peroxide to form a cyclic ether+OH is computed to be an order of magnitude faster, so the HOQO channel does not appear to be fast enough to explain the discrepancy. Definitive judgement on the importance of this reaction channel will require a careful reconsideration of all the coupled chemically activated QOOH reaction channels using modern predictive chemical kinetics software.     

Complete characterization of almost Moore digraphs of degree three

It is well known that Moore digraphs do not exist except for trivial cases (degree 1 or diameter 1), but there are digraphs of diameter two and arbitrary degree which miss the Moore bound by one. No examples of such digraphs of diameter at least three are known, although several necessary conditions for their existence have been obtained. In this paper, we prove that digraphs of degree three and diameter k ≥ 3 which miss the Moore bound by one do not exist. © 2004 Wiley Periodicals, Inc. J Graph Theory 48: 112–126, 2005     

QUENCHING OF ENZYME GENERATED TRIPLET ACETONE BY 2-METHYL-1,4-NAPHTOQUINONE

Abstract 2-Methyl-1,4-naphtoquinone (vitamin K₃) quenches the phosphorescence from enzyme-generated triplet acetone. Concomitantly the vitamin undergoes a photochemical-like alteration as the result of transfer of the electronic energy ( k _ET– 1 ± 10⁵ M^-1). This transfer appears to be of the long-range type.     

QUENCHING OF CHEMICALLY and ENZYMICALLY-GENERATED TRIPLET ACETONE BY TYROSINE and 3,5-DIHALOGENODERIVATIVES

Tyrosine and especially its 3,5-dihalogenoderivatives quench acetone triplets. When the excited acetone is generated free in solution, the Stern-Volmer plots for the quenching by these species, monitored via the sensitized emission of the 9,10-dibromoanthracene-2-sulfonate ion, are linear. When triplet acetone is generated enzymically by the peroxidase-catalyzed aerobic oxidation of isobutyral-dehyde, the Stern-Volmer plots for the quenching of the acetone phosphorescence curve upwards in the case of 3,5-dibromotyrosine and even more markedly with 3,5-diiodotyrosine. Quenching appears likely to occur by triplet-triplet energy transfer and especially in the case of the phenoxide form, also by electron transfer. The curvature denotes a static contribution to quenching favoured by the enzyme.     

Tetracrystalline Tetrablock Quarterpolymers: Four Different Crystallites under the Same Roof

Multicrystalline block polymers having three or more crystalline segments are essential materials for the advancement of physics in the field of crystallinity. The challenging synthesis of multicrystalline polymers has resulted in only a limited number of tricrystalline terpolymers having been reported to date. We report, for the first time, the synthesis of polyethylene‐b‐poly(ethylene oxide)‐b‐poly(?‐caprolactone)‐b‐poly(l ‐lactide) (PE‐b‐PEO‐b‐PCL‐b‐PLLA), a tetracrystalline tetrablock quarterpolymer, by combining polyhomologation, ring‐opening polymerization, and an organic/metal “catalyst switch” strategy. ¹H NMR spectroscopy and gel‐permeation chromatography confirmed the formation of the tetrablock quarterpolymer, while differential scanning calorimetry, X‐ray diffraction, and wide‐line separation solid‐state NMR spectroscopy revealed the existence of four different crystalline domains.     

Initial Carbon−Carbon Bond Formation during the Early Stages of Methane Dehydroaromatization

Methane dehydroaromatization (MDA) is among the most challenging processes in catalysis science owing to the inherent harsh reaction conditions and fast catalyst deactivation. To improve this process, understanding the mechanism of the initial C?C bond formation is essential. However, consensus about the actual reaction mechanism is still to be achieved. In this work, using advanced magic‐angle spinning (MAS) solid‐state NMR spectroscopy, we study in detail the early stages of the reaction over a well‐dispersed Mo/H‐ZSM‐5 catalyst. Simultaneous detection of acetylene (i.e., presumably the direct C?C bond‐forming product from methane), methylidene, allenes, acetal, and surface‐formate species, along with the typical olefinic/aromatic species, allow us to conclude the existence of at least two independent C?H activation pathways. Moreover, this study emphasizes the significance of mobility‐dependent host–guest chemistry between an inorganic zeolite and its trapped organic species during heterogeneous catalysis.     

Polysulfonylamines. CXXXII.

The crystal structure of the title compound, C₅H₇N₂⁺·C₁₂H₁₀NO₄S₂⁻, consists of two independent cation–anion pairs, A and B. Within each pair, the H—N—C—N*—H grouping (N*—H is the pyridinium function) and one N—S—O moiety of the anion are linked by N*—H⃛N and N—H⃛O hydrogen bonds to form an antidromic ring motif of type R²₂(8). The remaining amino donors give rise to N—H⃛O hydrogen bonds, connecting the ion pairs into A–B–A–B– chains. The structure testifies to the persistence of the R²₂(8) motif in question, which was previously detected as a highly robust supramolecular synthon in a series of onium di(methane­sulfonyl)­amidates. The structure is pseudosymmetric; the anion positions correspond to space group P2₁/n, but those of the cations do not.