Evaluation of a new solid-phase cartridge for the preconcentration of phenolic compounds in water

The aim of this study is to evaluate the efficiency of a new solid-phase extraction cartridge, Spe-ed Advanta, in the extraction and preconcentration of four phenolic compounds (phenol, 2-chlorophenol, 2-nitrophenol, and 2,4-dichlorophenol) from water. The solid phase is a polystyrene-divinylbenzene resin modified with carboxylic groups, these polar groups improve the contact between the matrix and the aqueous solutions in the extraction of polar analytes. We studied several elution solvents in order to find the most efficient one. Sample concentration, sample volume, and sample pH are also investigated as well as the best method for drying the cartridge. Recoveries achieved with the new phase are compared with those obtained with Isolute ENV+, a non-modified polystyrene-divinylbenzene stationary bed. The best experimental conditions were then used for determination of the phenols in spiked environmental waters.     

On the Number of 4‐Cycles in a Tournament

If T is an n‐vertex tournament with a given number of 3‐cycles, what can be said about the number of its 4‐cycles? The most interesting range of this problem is where T is assumed to have cyclic triples for some and we seek to minimize the number of 4‐cycles. We conjecture that the (asymptotic) minimizing T is a random blow‐up of a constant‐sized transitive tournament. Using the method of flag algebras, we derive a lower bound that almost matches the conjectured value. We are able to answer the easier problem of maximizing the number of 4‐cycles. These questions can be equivalently stated in terms of transitive subtournaments. Namely, given the number of transitive triples in T, how many transitive quadruples can it have? As far as we know, this is the first study of inducibility in tournaments.     

The “Historical Materials BAG”: A New Facilitated Access to Synchrotron X-ray Diffraction Analyses for Cultural Heritage Materials at the European Synchrotron Radiation Facility

The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the “block allocation group” (BAG) mode. Here, we present the recently implemented “historical materials BAG”: a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines—ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses—with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood.     

Maximum Conditional Probability Stochastic Controller for Linear Systems with Additive Cauchy Noises

Journal of Optimization Theory and Applications - Motivated by the sliding mode control approach, a stochastic controller design methodology is developed for discrete-time, vector-state linear...     

Two polydimethylsiloxane rod extraction methods for the sensitive determination of phenolic compounds in water samples

Simple, precise, and low‐cost methods for the simultaneous determination of phenolic endocrine disrupting compounds such as bisphenol A, trichlorophenol, pentachlorophenol, 4‐nonylphenol, and 4‐octylphenol in water samples were developed. The Direct, in situ derivatization methods are based on polydimethylsiloxane rod extraction followed by liquid desorption and chromatographic analysis by liquid chromatography and diode array detection. Several parameters affecting the extraction and desorption of the phenolic compounds and their acetylated derivates were studied, as well as the chromatographic and detection conditions. For the direct method, determination coefficients (r²) > 0.990 and LODs in the 0.6–2 μg/L range were obtained for all compounds except bisphenol A (9.5 μg/L). With the derivatization‐based method, based on in situ acetylation, lower limits of detection (0.3–0.9 μg/L) were obtained for all the compounds with r² > 0.988 and RSDs in the 2–9% range. The developed methods were applied to the analysis of spiked water samples obtaining recoveries of between 60.2 and 131.7% for the direct method, and of between 76.6 and 108.2% for the derivatization‐based method. The results demonstrate the feasibility of using these two methods for determining bisphenol A, trichlorophenol, pentachlorophenol, 4‐nonylphenol, and 4‐octylphenol in water.     

Extraction and Preconcentration of the Herbicide Glyphosate and its Metabolite AMPA Using Anion-Exchange Solid Phases

An extraction and preconcentration method has been developed for the determination of glyphosate and its degradation product, aminomethylphosphonic acid (AMPA), over a broad range of concentrations (0.1–500 μg · L⁻¹) in various aqueous matrices which differ in their ionic content. Two anion-exchange resins (the microporous Amberlite^?IRA-416 and the macroporous Amberlite^?IRA-900) and a commercial silica modified cartridge, ISOLUTE-NH₂, were evaluated and compared. The effect of flow-rate, composition and volume of the elution solution, analyte concentration, sample volume and porosity of the sorbents were investigated and the best experimental conditions were then used in the recovery of the analytes from spiked natural waters. Determination of the analytes was performed by HPLC with fluorescence detection, using FMOC-Cl as a pre-column derivatisation agent. Enrichment factors of up to 125 were achieved with the protonated ISOLUTE-NH₂ cartridge allowing the determination of glyphosate at a level of 0.1 μg · L⁻¹. Recovery rates of 99% for glyphosate and 77% for AMPA and relative standard deviations for repeatability of <10% for both analytes were determined with the Amberlite^?IRA-900 macroporous resin.     

Lipophilicity of some guaianolides isolated from two endemic subspecies of Amphoricarpos neumayeri (Asteraceae) from Montenegro

In this study 10 guaianolide-type sesquiterpene gamma-lactones named amphoricarpolides, isolated from the aerial parts of two endemic subspecies of Amphoricarpos neumayeri (ssp. neumayeri and ssp. murbeckii Bosnjak), were investigated by means of reversed-phase thin-layer chromatography. Methanol-water and tetrahydrofuran-water binary mixtures were used as mobile phase in order to determine lipophilicity parameters R (0) (M) and C(0). Some of the investigated compounds were screened for their cytotoxic activity against HeLa and B16 cells. Chromatographically obtained lipophilicity parameters were correlated with calculated logP values and IC(50) values. Principal component analysis identified the dominant pattern in the chromatographically obtained data.     

Comparison of two extraction methods for the determination of selective serotonin reuptake inhibitors in sewage sludge by hollow fiber liquid-phase microextraction

This paper presents two procedures for the determination of four selective serotonin reuptake inhibitors (citalopram, paroxetine, fluoxetine, and sertraline) and one metabolite (norfluoxetine) in sewage sludge utilizing three-phase hollow fiber liquid-phase microextraction (HF-LPME). First, direct HF-LPME was used for extraction, clean-up, and preconcentration. The pharmaceuticals were extracted from slurry samples into an organic phase and then back-extracted into an aqueous phase in the lumen of the hollow fiber. Second, a procedure combining pressurized hot water extraction and HF-LPME for clean-up and preconcentration was developed for the same analytes and matrix. The extracts were subsequently analyzed by liquid chromatography-mass spectrometry. For direct HF-LPME, limits of detection were between 1 and 12 ng g(-1) (dry weight) and the relative standard deviation (RSD) values were 3-12%. For the second method, limits of detection were approximately 6 ng g(-1) for all the compounds and RSD values were 8-12%. The methods were validated by comparison of results for the same samples. Sewage sludge from a Swedish wastewater treatment plant was analyzed by both methods; average concentrations were similar for citalopram, paroxetine, and fluoxetine with values of approximately 530, 40, and 200 ng g(-1) , respectively.     

Capillary Electrophoresis of Water-Soluble Vitamins: An Undergraduate Experiment

Capillary electrophoresis (CE) is a relatively new analytical separation technique that is not usually introduced in the undergraduate analytical chemistry curriculum. The techniques growing popularity in research, industrial, and commercial laboratories, however, should be a reason to consider its introduction at this level. Here, we describe an exercise utilizing capillary zone electrophoresis and micellar electrokinetic chromatography. This exercise provides a suitable introduction to capillary electrophoresis and illustrates the mechanism for the separation of ionized and nonionized water-soluble vitamins (B1, B2 phosphate, B3 niacinamide, and B12). Joule heating can also be easily introduced as part of the exercise.