Development and validation of an analytical method for detection of estrogens in water

An analytical procedure enabling routine analysis of four environmental estrogens at concentrations below 1 ng L^–1 in estuarine water samples has been developed and validated. The method includes extraction of water samples using solid-phase extraction discs and detection by gas chromatography (GC) with tandem mass spectrometry (MS–MS) in electron-impact (EI) mode. The targeted estrogens included 17- and 17-estradiol (aE2, bE2), estrone (E1), and 17-ethinylestradiol (EE2), all known environmental endocrine disruptors. Method performance characteristics, for example trueness, recovery, calibration, precision, accuracy, limit of quantification (LOQ), and the stability of the compounds are presented for each of the selected estrogens. Application of the procedure to water samples from the Scheldt estuary (Belgium – The Netherlands), a polluted estuary with reported incidences of environmental endocrine disruption, revealed that E1 was detected most frequently at concentrations up to 7 ng L^–1. aE2 was detected once only and concentrations of bE2 and EE2 were below the LOQ.Presented at the 9th FECS Conference on Chemistry and the Environment, Bordeaux, France, 29 August–1 September 2004     

Exact mass measurement of product ions for the structural confirmation and identification of unknown compounds using a quadrupole time-of-flight spectrometer: a simplified approach using combined tandem mass spectrometric functions

This article describes a simple method to perform lock mass corrected accurate mass measurements in tandem mass spectrometry (MS/MS) with a quadrupole time-of-flight (Q-TOF) mass spectrometer. The experimental approach consists of using the protonated molecule of a known compound, which is measured in a MS/MS function using low collision energy (no fragmentation), as mass calibrator. The unknown compound is acquired in MS/MS mode albeit using high collision energy. After the acquisition, the two MS/MS spectra of unknown and mass calibrator are combined, and the fragments of the unknown are lock mass corrected by using the protonated molecule of the mass calibrator. To prove this concept, 10 compounds were analyzed using this approach, the fragments interpreted and, where possible, related to structural data available in the literature. All the unequivocally assigned fragments were accurately mass measured with mass errors within appropriate limits, i.e. for m/z values <200 with a mass tolerance of 3 mDa while for m/z > 200 the mass tolerance is expressed as 10 ppm.     

Development and validation of an LC–MS/MS method for the quantification of artificial sweeteners in human matrices

Artificial sweeteners are widely used as substitutes for sugar. The sweeteners are generally considered safe, however their whereabouts during pregnancy and lactation and the effect on child development are poorly explored. There is a need for new tools to measure these substances during pregnancy and lactation. Here, we describe the development and validation of a sensitive liquid chromatography–tandem mass spectrometry method for the simultaneous quantification of acesulfame, cyclamate, saccharin and sucralose in human plasma, umbilical cord blood, amniotic fluid and breast milk. The samples were prepared by protein precipitation and separated on a Luna Omega Polar C₁₈ column (2.1 × 50 mm, 1.6 μm). Electrospray ionization in negative mode and multiple reaction monitoring were used to monitor the ion transitions. The validated concentration ranges were from 1 to 500 ng/ml (10–500 ng/ml for sucralose). Interassay precisions were all ≤15% and the accuracies were within ±15%. Stability, linearity, dilution integrity, carryover and recovery were also examined and satisfied the validation criteria. Finally, this analytical method was successfully applied on spiked samples of plasma, umbilical cord blood, amniotic fluid and breast milk, proving its suitability for use in clinical studies on artificial sweeteners, including during pregnancy and lactation.     

Aqueous enantioselective hydrogenation of methyl 2-acetamidoacrylate with Rh-MeDuPHOS occluded in PDMS

A new chiral heterogeneous catalytic system obtained by occlusion of the Rh-MeDuPHOS complex in a polydimethylsiloxane film was tested in the asymmetric hydrogenation of methyl 2-acetamidoacrylate in aqueous medium.     

Sucrose preculture to simplify cryopreservation of banana meristem cultures

A simple cryopreservation method is described for proliferating meristem cultures of banana (Musa spp.). It relies on a 2-week preculture on media containing 0.4 M sucrose followed by rapid cooling in liquid nitrogen. Different preculture media were screened for efficient protection of banana meristems against cryopreservation. Sucrose can be replaced by both fructose and glucose without significantly affecting post-thaw survival rates. A high BA concentration (0.1 mM) in the preculture medium results in less material available for cryopreservation, but does not affect cryoprotection. Culture in liquid media significantly improved post-thaw regeneration. The optimized cryopreservation protocol was applied on 36 banana accessions belonging to 8 different genomic groups. It is shown that post-thaw regeneration frequencies (ranging between 0 and 66 percent) are highly dependent on the genomic constitution of the banana cultivar.     

Axial non-uniformity of longitudinal hollow-cathode discharges for laser applications: numerical modeling and comparison with experiments

It is demonstrated by means of numerical modeling that longitudinal hollow-cathode discharges (HCDs) typically used for laser applications are strongly non-uniform in the axial direction. Two kinds of HCDs are investigated; those having one anode ring and those having two anode rings at opposite ends of the HCD tube. The HCD under study was made of copper and operated in a mixture of helium and argon. The calculated potential varied considerably in the axial direction. The densities of the major plasma species showed no maxima in the middle of the HCD, but rather at the anode side(s). The same applied to the sputtering rate at the cathode and the electron-impact ionization and excitation rates in the plasma. The calculation results for both configurations have been compared with measured data, i.e. with the electric current and the optical emission intensities of He (I) and Cu (I) lines as a function of axial position, and reasonable agreement has been reached. Received: 25 June 2002 / Revised version: 29 August 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +32-3/820-23-76, E-mail: annemie.bogaerts@ua.ac.be     

Patterns in the vocalizations of male harbor seals

Comparative analyses of the roar vocalization of male harbor seals from ten sites throughout their distribution showed that vocal variation occurs at the oceanic, regional, population, and subpopulation level. Genetic barriers based on the physical distance between harbor seal populations present a likely explanation for some of the observed vocal variation. However, site-specific vocal variations were present between genetically mixed subpopulations in California. A tree-based classification analysis grouped Scottish populations together with eastern Pacific sites, rather than amongst Atlantic sites as would be expected if variation was based purely on genetics. Lastly, within the classification tree no individual vocal parameter was consistently responsible for consecutive splits between geographic sites. Combined, these factors suggest that site-specific variation influences the development of vocal structure in harbor seals and these factors may provide evidence for the occurrence of vocal dialects.