Origins and structures of background ions produced by fast-atom bombardment of glycerol

Accurate mass measurements were used to assign elemental compositions and tandem mass spectrometry was used to characterize the peak-at-every-mass background ions produced by kiloelectron-volt-particle bombardment of neat fast-atom bombardment matrices. The majority of the background ions observed in the mass spectrum of neat glycerol was identified. On the basis of the experiments with glycerol, a theory for the formation of background ions is presented. Results are discussed according to the chemical and physical changes that ygoe;on-volt-particle bombardment produces in the matrix.     

Effects of target gas in collision-induced dissociation using a double quadrupole mass spectrometer and radiofrequency

Collision-induced dissociation (CID) of polyatomic ions sampled from an rf-powered glow discharge is examined by using three target gases including atomic (Ar and Xe) and molecular species (N2). Collisions with these targets in the first quadrupole of the double quadrupole system result in the loss of discharge species by dissociation, symmetric and asymmetric charge exchange, and scattering, each to varying degrees. These processes are seen to be a function of the relative mass, size... and ionization potentials of the target species, as well as the collision center-of-mass energies. In light of the comparisons, xenon appears to be the best collision target for both CID and charge exchange because of its relatively low ionization potential and high dissociation efficiency of polyatornic species. Evidence for both symmetric and asymmetric charge exchange is presented for Ar and Xe target gases.     

The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

Day-side auroral signatures based on simultaneous, coordinatedobservations at Svalbard and Greenland

The height distribution of the dayside cusp aurora and the relation between optical emissions and net downward electron energy flux are discussed. These two important characteristics of day-side cusp aurora are still unknown. It is instructive to compare particle flux and optical luminosity because these two quantities should be proportional if the cusp aurora is caused by electron impact, as has been found for nighttime aurora in the oval. Furthermore, there should then be a direct relation between auroral altitudes and particle energy. Based on coordinated auroral observations at Svalbard and Greenland, together with simultaneous, overhead F-9 satellite measurements, these quantities have been evaluated     

Immobilized polysiloxanes as stationary phases for high-performance liquid chromatography and solid phase extraction

Polysiloxanes immobilized onto the surfaces of porous silica particles have proven to be good stationary phases for the separation of multiresidues of pesticides and their metabolic/degradation products by reversed-phase high-performance liquid chromatography (RP-HPLC). Similar materials have proven effective for pre-concentration and clean-up procedures using solid phase extraction. The present paper describes the preparation and some applications of several of these packing materials.     

A Note about the Appearance of Non-Hyperbolic Solutions in a Mechanical Pendulum System

The investigation of the behavior of a nonlinear system consists in theanalysis of different stages of its motion, where the complexity varieswith the proximity of a resonance region. Near this region the stabilitydomain of the system undergoes sudden changes due basically tocompetition and interaction between periodic and saddle solutions insidethe phase portrait, leading to the occurrence of the most differentphenomena. Depending of the domain of the chosen control parameter,these events can reveal interesting geometric features of the system sothat the phase portrait is not capable to express all them, since theprojection of these solutions on the two-dimensional surface can hidesome aspects of these events. In this work we will investigate thenumerical solutions of a particular pendulum system close to a secondaryresonance region, where we vary the control parameter in a restrictdomain in order to draw a preliminary identification about what happenswith this system. This domain includes the appearance of non-hyperbolicsolutions where the basin of attraction in the center of the phaseportrait diminishes considerably, almost disappearing, and afterwardsits size increases with the direction of motion inverted. Thisphenomenon delimits a boundary between low and high frequency of theexternal excitation.     

Analysis of some combination-overtone infrared bands of SO3

Several new infrared absorption bands for ³²S¹⁶O₃ have been measured and analyzed. The principal bands observed were ν₁+ν₂ (at 1561 cm⁻¹), ν₁+ν₄ (at 1594 cm⁻¹), ν₃+ν₄ (at 1918 cm⁻¹), and 3ν₃ (at 4136 cm⁻¹). Except for 3ν₃, these bands are very complicated because of (a) the Coriolis coupling between ν₂ and ν₄, (b) the Fermi resonance between ν₁ and 2ν₄, (c) the Fermi resonance between ν₁ and 2ν₂, (d) ordinary l-type resonance that couples levels that differ by 2 in both the k and l quantum numbers, and (e) the vibrational l-type resonance between the A₁^′ and A₂^′ levels of ν₃+ν₄. The unraveling of the complex pattern of these bands was facilitated by a systematic approach to the understanding of the various interactions. Fortunately, previous work on the fundamentals permitted good estimates of many constants necessary to begin the assignments and the fit of the measurements. In addition, the use of hot band transitions accompanying the ν₃ band was an essential aid in fitting the ν₃+ν₄ transitions since these could be directly observed for only one of four interacting states. From the hot band analysis we find that the A₁^′ vibrational level is 3.50 cm⁻¹ above the A₂^′ level, i.e., r₃₄=1.75236(7) cm⁻¹. In the case of the 3ν₃ band, the spectral analysis is straightforward and a weak Δk=±2, Δl₃=±2 interaction between the l₃=1 and l₃=3 substates locates the latter A₁^′ and A₂^′ “ghost” states 22.55(4) cm⁻¹ higher than the infrared accessible l₃=1 E^′ state.     

Finding Robust Solutions Using Local Search

This paper investigates how a local search metaheuristic for continuous optimisation can be adapted so that it finds broad peaks, corresponding to robust solutions. This is relevant in problems in which uncertain or noisy data is present. When using a genetic or evolutionary algorithm, it is standard practice to perturb solutions once before evaluating them, using noise from a given distribution. This approach however, is not valid when using population-less techniques like local search and other heuristics that use local search. For those algorithms to find robust solutions, each solution needs to be perturbed and evaluated several times, and these evaluations need to be combined into a measure of robustness. In this paper, we examine how many of these evaluations are needed to reliably find a robust solution. We also examine the effect of the parameters of the noise distribution. Using a simple tabu search procedure, the proposed approach is tested on several functions found in the literature. This revised version was published online in August 2006 with corrections to the Cover Date.