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.     

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.     

Variations in T(2)* and fat content of murine brown and white adipose tissues by chemical-shift MRI

Purpose

The purpose was to compare T₂* relaxation times and proton density fat-fraction (PDFF) values between brown (BAT) and white (WAT) adipose tissue in lean and ob/ob mice.

Materials and Methods

A group of lean male mice (n=6) and two groups of ob/ob male mice placed on similar 4-week (n=6) and 8-week (n=8) ad libitum diets were utilized. The animals were imaged at 3 T using a T₂*-corrected chemical-shift-based water–fat magnetic resonance imaging (MRI) method that provides simultaneous estimation of T₂* and PDFF on a voxel-wise basis. Regions of interest were drawn within the interscapular BAT and gonadal WAT depots on co-registered T₂* and PDFF maps. Measurements were assessed using analysis of variance, Bonferroni-adjusted t test for multigroup comparisons and the Tukey post hoc test.

Results

Significant differences (P<.01) in BAT T₂* and PDFF were observed between the lean and ob/ob groups. The ob/ob animals exhibited longer BAT T₂* and greater PDFF than lean animals. However, only BAT PDFF was significantly different (P<.01) between the two ob/ob groups. When comparing BAT to WAT within each group, T₂* and PDFF values were consistently lower in BAT than WAT (P<.01). The difference was most prominent in the lean animals. In both ob/ob groups, BAT exhibited very WAT-like appearances and properties on the MRI images.

Conclusion

T₂* and PDFF are lower in BAT than WAT. This is likely due to variations in tissue composition. The values were consistently lower in lean mice than in ob/ob mice, suggestive of the former's greater demand for BAT thermogenesis and reflective of leptin hormone deficiencies and diminished BAT metabolic activity in the latter.     

Nanostructural organization and anion effects in the optical Kerr effect spectra of binary ionic liquid mixtures

This article reports a study of the effect of anions on the optical Kerr effect (OKE) spectra of binary ionic liquid mixtures with one mixture comprising the 3-methyl-1-pentylimidazolium ([C 5mim] (+)) cation and the anions PF 6 (-) and CF 3CO 2 (-) (TFA (-)), and another mixture comprising the [C 5mim] (+) cation and the anions Br (-) and bis(trifluomethanesulfonyl)imide (NTf 2 (-)). The spectra were obtained by the use of optical heterodyne-detected Raman-induced Kerr Effect Spectroscopy at 295 K. The OKE spectra of the mixtures are compared with the calculated mole-fraction weighted sum of the normalized OKE spectra of the neat liquids. The OKE spectra are nearly additive for [C 5mim]Br/[C 5mim][NTf 2] mixtures, but nonadditive for [C 5mim][PF 6]/[C 5mim][TFA] mixtures. In the case of the equimolar [C 5mim][PF 6]/[C 5mim][TFA] mixture, the nonadditivity is such that the experimental OKE spectrum is narrower than the calculated OKE spectrum. The additivity or nonadditivity of OKE spectra for IL mixtures can be explained by assuming ionic liquids are nanostructurally organized into nonpolar regions and ionic networks. The ionic networks in mixtures will be characterized by "random co-networks" for anions that are nearly the same in size (PF 6 (-) and TFA (-)) and by "block co-networks" for anions that differ greatly in size (Br (-) and NTf 2 (-)).     

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.     

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.     

Using ionic liquids to trap unique coordination environments: polymorphic solvates of ErCl3(OH2)(4).2([C2mim]Cl)

Two polymorphs of ErCl(3)(OH(2))(4).2([C(2)mim]Cl) solvates were isolated from the same solution of 1-ethyl-3-methylimidazolium chloride when HCl(aq) was added, while [C(2)mim](3)[ErCl(6)] was isolated without HCl addition, illustrating how ionic liquids can be used to trap unusual coordination environments in the solid state.