Quantitative analysis of perchlorate in extracts of whole fish homogenates by ion chromatography: comparison of suppressed conductivity detection and electrospray ionization mass spectrometry

The perchlorate anion (ClO ₄ ^– ) is an anthropogenic contaminant of increasing concern in water supplies, and has been shown to disrupt thyroid activity. Most perchlorate analyses are currently carried out by ion chromatography (IC) with suppressed conductivity detection (SCD). While this procedure has been demonstrated to provide acceptable performance for analysis of water samples, the determination of perchlorate in high-conductivity aqueous extracts of plant or animal material is not readily accomplished by IC-SCD unless lengthy cleanup protocols are applied. With the addition of electrospray ionization mass spectrometry (ESI-MS) to IC, it was hypothesized that the interference imposed by various ionic species could be significantly reduced without the need for purification; however, the analysis of perchlorate in relatively unpurified extracts of biologically derived homogenates by IC-ESI-MS has not previously been described in the literature. The research presented here represents a comparison of the capabilities of IC-SCD and IC-ESI-MS to detect perchlorate in reagent water and in crude extracts of perchlorate-exposed fish (threespine stickleback, Gasterosteus aculeatus). ESI-MS was found to compare favorably to SCD for the detection of perchlorate in deionized water, and to exceed SCD performance in perchlorate analysis of fish-derived extracts.     

An automated method for the analysis of stable isotope labeling data in proteomics

An algorithm is presented for the generation of a reliable peptide component peak table from liquid chromatography-mass spectrometry (LC-MS) and subsequent quantitative analysis of stable isotope coded peptide samples. The method uses chemical noise filtering, charge state fitting, and deisotoping toward improved analysis of complex peptide samples. Overlapping peptide signals in mass spectra were deconvoluted by correlation with modeled peptide isotopic peak profiles. Isotopic peak profiles for peptides were generated in silico from a protein database producing reference model distributions. Doublets of heavy and light labeled peak clusters were identified and compared to provide differential quantification of pairs of stable isotope coded peptides. Algorithms were evaluated using peptides from digests of a single protein and a seven-protein mixture that had been differentially coded with stable isotope labeling agents and mixed in known ratios. The experimental results correlated well with known mixing ratios.     

Enhanced coding for exponentially distributed signals using suprathreshold stochastic resonance

Our previous work on stochastic resonance (SR) in threshold based systems proved that the SR effect is dependent on the nature of the input signal distribution; more specifically, for certain types of signal distribution SR is not observed [Das A, Stocks NG, Nikitin A, Hines EL. Quantifying stochastic resonance in a single threshold detector for random aperiodic signals. Fluctuation Noise Lett 2004;4:L247–65]. Here we show that suprathreshold stochastic resonance (SSR) – a novel and distinct form of SR – removes this limitation and hence leads to the conclusion that SSR can probably enhance the transmission of signals of any distribution and amplitude. SSR effects are studied in a parallel array of identical nonlinear threshold based devices. A double exponential signal distribution is chosen because this distribution did not demonstrate conventional SR effects in a single threshold device [Das A, Stocks NG, Nikitin A., Hines EL. Quantifying Stochastic resonance in a single threshold detector for random aperiodic signals. Fluctuation and Noise Letters 2004;4:L247-L265.]. SSR as a possible mechanism for enhancing transmission of speech signals in the human ear is also discussed.     

Upper Semicontinuity of Morse Sets of a Discretization of a Delay-Differential Equation: An Improvement

In this paper, we consider a discrete delay problem with negative feedback x(t)=f(x(t), x(t−1)) along with a certain family of time discretizations with stepsize 1/n. In the original problem, the attractor admits a nice Morse decomposition. We proved in (T. Gedeon and G. Hines, 1999, J. Differential Equations151, 36-78) that the discretized problems have global attractors. It was proved in (T. Gedeon and K. Mischaikow, 1995, J. Dynam. Differential Equations7, 141-190) that such attractors also admit Morse decompositions. In (T. Gedeon and G. Hines, 1999, J. Differential Equations151, 36-78) we proved certain continuity results about the individual Morse sets, including that if f(x, y)=f(y), then the individual Morse sets are upper semicontinuous at n=∞. In this paper we extend this result to the general case; that is, we prove for general f(x, y) with negative feedback that the Morse sets are upper semicontinuous.     

Food chain chaos due to Shilnikov's orbit

Assume that the reproduction rate ratio zeta of the predator over the prey is sufficiently small in a basic tri-trophic food chain model. This assumption translates the model into a singularly perturbed system of two time scales. It is demonstrated, as a sequel to the earlier paper of Deng [Chaos 11, 514-525 (2001)], that at the singular limit zeta=0, a singular Shilnikov's saddle-focus homoclinic orbit can exist as the reproduction rate ratio epsilon of the top-predator over the predator is greater than a modest value epsilon(0). The additional conditions under which such a singular orbit may occur are also explicitly given. (c) 2002 American Institute of Physics.     

Nuclear magnetic resonance study of In115 in B2-type PdIn

NMR measurements on In¹¹⁵ in B2-type PdIn from RT to 4.2°K are reported The low Knight shift is attributed to a reduction of the amount of s- character in wave functions at the In sites and not the density of states at the the Fermi level. The existence of a localized moment is considered.     

Acoustic backscatter measurements from littoral seabeds at shallow grazing angles at 4 and 8 kHz

Direct measurement of acoustic scattering from the seabed at shallow grazing angles and low kilohertz frequencies presents a considerable challenge in littoral waters. Specifically, returns from the air-water interface typically contaminate the signals of interest. To address this issue, DRDC Atlantic has developed a sea-going research system for measuring acoustic scatter from the seabed in shallow-water environs. The system, known as the wideband sonar (WBS), consists of a parametric array transmitter and a superdirective receiver. In this paper, backscatter measurements obtained with the WBS at two sandy, shallow-water sites off North America's Atlantic coast are presented. Data were collected at 4 and 8 kHz at grazing angles from 3 degrees-15 degrees. The backscattering strength is similar at both sites and, below about 8 degrees, it appears to be independent of frequency within the statistical accuracy of the data. The measurements show reasonable agreement with model estimates of backscatter from sandy sediments. A small data set was collected at one of the sites to examine the feasibility of using the WBS to measure the azimuthal variability of acoustic scatter. The data set--although limited--indicates that the parametric array's narrow beamwidth makes the system well-suited to this task.