Fragmentation pathways of 2,3‐dimethyl‐2,3‐dinitrobutane cations in the gas phase

2,3‐Dimethyl‐2,3‐dinitrobutane (DMNB) is an explosive taggant added to plastic explosives during manufacture making them more susceptible to vapour‐phase detection systems. In this study, the formation and detection of gas‐phase [M+H]⁺, [M+Li]⁺, [M+NH₄]⁺ and [M+Na]⁺ adducts of DMNB was achieved using electrospray ionisation on a triple quadrupole mass spectrometer. The [M+H]⁺ ion abundance was found to have a strong dependence on ion source temperature, decreasing markedly at source temperatures above 50°C. In contrast, the [M+Na]⁺ ion demonstrated increasing ion abundance at source temperatures up to 105°C. The relative susceptibility of DMNB adduct ions toward dissociation was investigated by collision‐induced dissociation. Probable structures of product ions and mechanisms for unimolecular dissociation have been inferred based on fragmentation patterns from tandem mass (MS/MS) spectra of source‐formed ions of normal and isotopically labelled DMNB, and quantum chemical calculations. Both thermal and collisional activation studies suggest that the [M+Na]⁺ adduct ions are significantly more stable toward dissociation than their protonated analogues and, as a consequence, the former provide attractive targets for detection by contemporary rapid screening methods such as desorption electrospray ionisation mass spectrometry. Copyright © 2009 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.     

On the Hausdorff Dimension of Regular Points of Inviscid Burgers Equation with Stable Initial Data

Consider an inviscid Burgers equation whose initial data is a Lévy α-stable process Z with α>1. We show that when Z has positive jumps, the Hausdorff dimension of the set of Lagrangian regular points associated with the equation is strictly smaller than 1/α, as soon as α is close to 1. This gives a partially negative answer to a Conjecture of Janicki and Woyczynski (J. Stat. Phys. 86(1–2):277–299, 1997). Along the way, we contradict a recent Conjecture of Z. Shi () about the lower tails of integrated stable processes.     

The synthesis and self‐assembly of ABA amphiphilic block copolymers containing styrene and oligo(ethylene glycol) methyl ether methacrylate in dilute aqueous solutions: Elevated cloud point temperatures for thermoresponsive micelles

A series of ABA amphiphilic triblock copolymers possessing polystyrene (PS) central hydrophobic blocks, one group with “short” PS blocks (DP = 54–86) and one with “long” PS blocks (DP = 183–204) were synthesized by atom transfer radical polymerization. The outer hydrophilic blocks were various lengths of poly(oligoethylene glycol methyl ether) methacrylate, a comb‐like polymer. The critical aggregation concentrations were recorded for certain block copolymer samples and were found to be in the range circa 10⁻⁹ mol L⁻¹ for short PS blocks and circa 10⁻¹² mol L⁻¹ for long PS blocks. Dilute aqueous solutions were analyzed by transmission electron microscopy (TEM) and demonstrated that the short PS block copolymers formed spherical micelles and the long PS block copolymers formed predominantly spherical micelles with smaller proportions of cylindrical and Y‐branched cylindrical micelles. Dynamic light scattering analysis results agreed with the TEM observations demonstrating variations in micelle size with PS and POEGMA chain length: the hydrodynamic diameters (D_H) of the shorter PS block copolymer micelles increased with increasing POEGMA block lengths while maintaining similar PS micellar core diameters (D_C); in contrast the values of D_H and D_C for the longer PS block copolymer micelles decreased. Surface‐pressure isotherms were recorded for two of the samples and these indicated close packing of a short PS block copolymer at the air–water interface. The aggregate solutions were demonstrated to be stable over a 38‐day period with no change in aggregate size or noticeable precipitation. The cloud point temperatures of certain block copolymer aggregate solutions were measured and found to be in the range 76–93 °C; significantly these were ∼11 °C higher in temperature than those of POEGMA homopolymer samples with similar chain lengths. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7739–7756, 2008     

Electron pairing mechanism in incipient ferroelectric BaPb1−x Bi x O3

The lattice dynamical properties of BaPb_1–x Bi _x O₃ are described within the polarizability model for perovskite oxides, but extended to take into account the valence instability of Bi. In a quantitative investigation it is found that a mode softening to a ferroelectric state is excluded, but a transition to a paired electron state is possible. The transformation of the classical Hamiltonian to its quantum-mechanical equivalent shows the parameter regimes for which pairing of electrons and thus possibly superconductivity occur.     

Neutral pion production at 350 MeV/u in the system20Ne +27Al

π⁰ -production probability of (9± 2)· 10^{? 3} per²⁰Ne+Al reaction has been measured at 350 MeV/u using the Two Arm Photon Spectrometer TAPS. This yield is consistent with an interpolation of published π-production rates in heavy ion collisions.