Mechanisms of radical removal by SO2

It is well established from experiments in premixed, laminar flames, jet-stirred reactors, flow reactors, and batch reactors that SO₂ acts to catalyze hydrogen atom removal at stoichiometric and reducing conditions. However, the commonly accepted mechanism for radical removal, SO₂ + H(+M) ? HOSO(+M), HOSO + H/OH ? SO₂ + H₂/H₂O, has been challenged by recent theoretical and experimental results. Based on ab initio calculations for key reactions, we update the kinetic model for this chemistry and re-examine the mechanism of fuel/SO₂ interactions. We find that the interaction of SO₂ with the radical pool is more complex than previously assumed, involving HOSO and SO, as well as, at high temperatures also HSO, SH, and S. The revised mechanism with a high rate constant for H + SO₂ recombination and with SO + H₂O, rather than SO₂ + H₂, as major products of the HOSO + H reaction is in agreement with a range of experimental results from batch and flow reactors, as well as laminar flames.     

Fusion multiplicities as polytope volumes: -point and higher-genus su(2) fusion

We present the first polytope volume formulas for the multiplicities of affine fusion, the fusion in Wess–Zumino–Witten conformal field theories, for example. Thus, we characterise fusion multiplicities as discretised volumes of certain convex polytopes, and write them explicitly as multiple sums measuring those volumes. We focus on su(2), but discuss higher-point ( ) and higher-genus fusion in a general way. The method follows that of our previous work on tensor product multiplicities, and so is based on the concepts of generalised Berenstein–Zelevinsky diagrams, and virtual couplings. As a by-product, we also determine necessary and sufficient conditions for non-vanishing higher-point fusion multiplicities. In the limit of large level, these inequalities reduce to very simple non-vanishing conditions for the corresponding tensor product multiplicities. Finally, we find the minimum level at which the higher-point fusion and tensor product multiplicities coincide.     

A general synthetic route to 4-substituted-2,2′-bithiophenes

A new synthetic route to 4-substituted-2,2′-bithiophenes has been developed utilizing 4-bromo-2,2′-bithiophene ( 1 ). Formation of the bithienyllithium adduct via halogen-metal exchange was found to be problematic and resulted in complex mixtures of products. The Grignard reagent of 1 can be obtained easily via the “entrainment” method, allowing the production of 4-substituted-2,2′-bithiophenes (where sub-stituent = octyl, hydroxyethyl, hydroxymethyl, carboxy, carbomethoxy, acetoxyethyl, and acetoxymethyl).     

On the bursting of linear polymer melts in inflation processes

Molten LLDPE and HDPE plates (thickness 2 mm) have been inflated into a circular cylinder (inner radius 31 mm) under isothermal conditions. Low deformation rates allow the plates to be inflated considerably into the cylinder, and at high inflation rates an early burst is observed.Axis-symmetric numerical simulation of the inflations have been performed, using a constitutive equation in the form of a separable memory integral where the strain dependence is described by the Linear Molecular Stress Function (L-MSF) model with dissipative convective constraint release. The material parameters in the constitutive model are obtained using liner viscoelastic (oscillatory shear) and uni-axial elongational measurements.The numerical simulations were performed for inflation of a flat plate and a perturbed plate, where a small circular cone was removed from the centre of the surface of the plate. This was done in order to investigate the stability of the inflations. It is shown that all of the inflations are hydrodynamically unstable, though the effect on the occurrence of the burst is limited. One exception is at slow inflation, where an unexpected burst may appear as a consequence of minute deviations from an ideal flat plate. All of the numerical calculations show quantitative agreement with the experiments for a wide range of experimental conditions. This strongly suggests that the initiation of the burst is a hydrodynamic phenomenon.The critical parameters in the inflation of molten linear polymers have been investigated using the Gel equation as a memory function (M(s)=Ans ^–(1+n)) and inflating the plate with a constant velocity for the top of the plate. The hydrodynamic burst in a linear polymer is mainly associated with the linear viscoelastic properties and only slightly with the non-linear strain dependence. Increased (linear) elasticity reduces the inflated volume, at the same inflation velocity, before the burst occurs. Furthermore, the critical parameter for the occurrence of the burst (whether or not the burst occurs) is related to the crossover point (G=G) in linear viscoelasticity.     

Calculation of chemical potentials of chain molecules by the incremental gauge cell method

The gauge cell Monte Carlo method is extended to calculations of the incremental chemical potentials and free energies of linear chain molecules. The method was applied to chains of Lennard-Jones beads with stiff harmonic bonds up to 500 monomers in length. We show that the suggested method quantitatively reproduces the modified Widom particle insertion method of Kumar et al. [S. K. Kumar, I. Szleifer, and A. Z. Panagiotopoulos, Phys. Rev. Lett. 66(22), 2935 (1991)], and is by an order of magnitude more efficient for long chains in terms of the computational time required for the same accuracy of chemical potential calculations. The chain increment ansatz, which suggests that the incremental chemical potential is independent of the chain length, was tested at different temperatures. We confirmed that the ansatz holds only for coils above the θ temperature. Special attention is paid to the effects of the magnitude of adsorption potential and temperature on the behavior of single chains in confinements that are comparable in size with the free chain radius of gyration. At sufficiently low temperatures, the dependence of the incremental chemical potential on the chain length in wetting pores is superficially similar to a capillary condensation isotherm, reflecting monolayer formation following by pore volume filling, as the chain length increases. We find that the incremental gauge cell method is an accurate and efficient technique for calculations of the free energies of chain molecules in bulk systems and nanoconfinements alike. The suggested method may find practical applications, such as modeling polymer partitioning on porous substrates and dynamics of chain translocation into nanopores.     

Analysis of high-molecular-weight fructan polymers in crude plant extracts by high-resolution LC-MS

The main water-soluble carbohydrates in temperate forage grasses are polymeric fructans. Fructans consist of fructose chains of various chain lengths attached to sucrose as a core molecule. In grasses, fructans are a complex mixture of a large number of isomeric oligomers with a degree of polymerisation ranging from 3 to >100. Accurate monitoring and unambiguous peak identification requires chromatographic separation coupled to mass spectrometry. The mass range of ion trap mass spectrometers is limited, and we show here how monitoring selected multiply charged ions can be used for the detection and quantification of individual isomers and oligomers of high mass, particularly those of high degree of polymerization (DP > 20) in complex plant extracts. Previously reported methods using linear ion traps with low mass resolution have been shown to be useful for the detection of fructans with a DP up to 49. Here, we report a method using high-resolution mass spectrometry (MS) using an Exactive Orbitrap MS which greatly improves the signal-to-noise ratio and allows the detection of fructans up to DP = 100. High-sugar (HS) Lolium perenne cultivars with high concentrations of these fructans have been shown to be of benefit to the pastoral agricultural industry because they improve rumen nitrogen use efficiency and reduce nitrous oxide emissions from pastures. We demonstrate with our method that these HS grasses not only contain increased amounts of fructans in leaf blades but also accumulate fructans with much higher DP compared to cultivars with normal sugar levels.     

Relaxation oscillations in spruce–budworm interactions

We review and complement the study of the mathematical properties of the predator–prey dynamical system for spruce–budworm interactions studied in Ludwig et al. [D. Ludwig, D. Jones, C.S. Holling, Qualitative analysis of insect outbreak systems: the spruce budworm and forest, Journal of Animal Ecology 47 (1978), 315–332]. We use the singular perturbation method to identify parameter regimes which permit relaxation oscillations. The leading order contribution to the period of these oscillations is computed by means of this method and compared with the outcome of direct numerical simulations.     

Vibrational Spectra of Ethylenediamine Salts. I. Tentative Assignments of Infrared and Far Infrared Spectra

Abstract

We wish to report on some hitherto partly unnoticed and unexplained features in the infrared spectra of hydrogen halides of ethylenediamine. We have prepared normal, C-, N-, and perdeuterated ethylenediammonium chlorides and bromides and measured their infrared spectra in the range 4000–10 cm^?1.     

Scars of discrete rotational bands in hot nuclei

Rotational motion loses its coherence as a function of the nuclear internal excitation energy. The damping process does not proceed in a continuous fashion and scars of discrete rotational bands are found, inbedded in a background of damped rotational states, regardless whether the calculations are carried out using effective or “random” forces. The complexity of the damping mechanism is revealed in the lineshape of the ridges in the γ-γ correlation spectrum.     

Collective bands in 104,106,108Mo

We have used our analysis of γ-γ-γ data (5.7 × 10¹¹ triples and higher folds) taken with Gammasphere from prompt γ rays emitted in the spontaneous fission of ²⁵²Cf to study the collective bands in ^104,106,108Mo. The one-phonon and two-phonon γ-vibrational bands and known two-quasiparticle bands in neutron-rich ^104,106Mo were extended to higher spins. The one-and two-phonon γ-vibrational bands have remarkably close energies for transitions from the same spin states and identical moments of inertia. Several new bands are observed and are proposed as quasiparticle bands in ^104,106Mo, along with the first β-type vibrational band in ¹⁰⁶Mo. The quasiparticle bands have essentially constant moments of inertia near the rigid-body value that indicate blocking of the pairing interaction. Candidates for chiral doublet bands in ¹⁰⁶Mo are strong. These are the first reported chiral vibrational bands in an even-even nucleus. The text was submitted by the authors in English.