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.     

Detection performance of the reduced-rank linear predictor ROCKET

This paper assesses the frequency detection capabilities of a new signal-dependent reduced-rank linear predictor applied to autoregressive spectrum estimation. The new technique is called reduced-order correlation kernel estimation technique (ROCKET). Its detection performance is examined by comparison to a full-rank autoregressive (FR-AR) estimator and two reduced-rank principal component autoregressive (PC-AR) estimators based on both the standard signal-independent version and a modified signal-dependent method. The performance of the new autoregressive estimator is also compared as a function of rank to the popular pseudo-spectrum estimator MUSIC. The performance metrics examined are the probability of detection (P/sub D/) and the false alarm rate (FAR) of detecting the spatial frequencies of plane waves impinging on a uniform line array in additive white Gaussian noise. These metrics are studied as a function of subspace rank, sample support, and signal-to-noise ratio (SNR). Simulations show that the signal-dependent reduced-rank estimators significantly outperform both the signal-independent version of PC-AR and the FR-AR estimator for low sample support and low SNR environments. One notable characteristic of ROCKET that highlights its distinct subspace selection is its performance as a function of subspace rank. It is observed that for equal powered signals, its peak performance is nearly invariant to signal rank and that at almost any subspace rank ROCKET meets or exceeds FR-AR performance. This provides an extra degree of robustness when the signal rank is unknown.     

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.     

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.     

Information and asymptotic efficiency of the case-cohort sampling design in Cox's regression model

Efficiencies of the maximum pseudolikelihood estimator and a number of related estimators for the case-cohort sampling design in the proportional hazards regression model are studied. The asymptotic information and lower bound for estimating the parametric regression parameter are calculated based on the effective score, which is obtained by determining the component of the parametric score orthogonal to the space generated by the infinite-dimensional nuisance parameter. The asymptotic distributions of the maximum pseudolikelihood and related estimators in an i.i.d. setting show that these estimators do not achieve the computed asymptotic lower bound. Simple guidelines are provided to determine in which instances such estimators are close enough to efficient for practical purposes.     

Nonlinear dynamics of charged particles interacting with combined ac-dc electromagnetic fields

A nonlinear Lorenz model describing interactions between charged particles and combined ac-dc electromagnetic fields is studied for various combinations of frequencies, field strengths and relative angle (θ) between the ac and dc magnetic fields. Strong directional effects on the magnitude and location of resonant particle motion are observed when θ is varied and the regular resonance windows in the aligned field (θ = 0) and linear version of the model studied previously by Durney etaal., break up to form irregular and less well pronounced regions of large and small particle displacements when nonlinearities are taken into account. The length of time takne to achieve resonant behaviour also becomes larger and more variable when nonlinearities are present. The possible relevance of these effects to interactions between electromagnetic fields and biological media is briefly discussed.     

Interferometric noise limitations in fibre-amplifier cascades

Phase-induced intensity noise from weak multiple reflectors is evaluated theoretically and experimentally in amplifier cascades without isolators. Rayleigh backscattering alone significantly limits the number of amplifiers in the span. Theory and experiment agree closely for a six-amplifier cascade.<>     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006