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.     

One‐pot synthesis of polymer/inorganic hybrids: toward readily accessible,low‐loss,and highly tunable refractive index materials and patterns

The realization that modulated light pulses can be transported in a confined fashion over long distances within a structure that comprises a controlled spatial distribution of the refractive index n—as in optical fibres and waveguides—has, without doubt, underpinned the telecommunications revolution witnessed during the 20th century. The refractive index n, quantifying how light propagates in a given medium, as a consequence, has become one of the most important materials properties in designing photonics products. The other key characteristic for most optical and photonic applications is the amount of light that is absorbed by a material, expressed as the extinction coefficient κ. Although a range of organic/inorganic hybrid materials have been advanced with tunable refractive index, only a few systems combine a high n, sufficiently low κ and straightforward sample preparation to allow simple fabrication of highly transparent, low‐loss structures. Here, we present a hybrid material that can be readily produced in water via a one‐pot synthesis directly from commercially available, low‐cost precursors. Moreover, our hybrid material can be solution‐processed, yielding systems of an extinction coefficient <0.01, and a refractive index, which can be controlled to adopt values between 1.5 to at least 2.1. Unprecedentedly, simple post‐deposition procedures such as thermal annealing or irradiation with high‐intensity UV‐light allow adjusting n also after film fabrication, offering an exceptional degree of freedom in designing and tailoring also more complex photonic architectures or planar wave‐guides, for example, through creation of in‐plane refractive index patterns. As a proof‐of‐concept, we demonstrate fabrication of waveguides based on local heating. The versatility of our materials is further illustrated by the production of lenses and dielectric filters of ～100% reflectivity in a given wavelength regime. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 000: 000–000, 2011     

Chitosan/anionic surfactant microparticles synthesized by high pressure spraying method for removal of phenolic pollutants

Biopolymeric microparticles were prepared by rapid expansion of high pressure CO₂-chitosan (Chi) solution in sodium bis-(2-ethyl hexyl) sulfosuccinate (AOT) solution. At pressures higher than 2 MPa, ultrafine particles were formed while under this value, wires were obtained. The formation of Chi/AOT complex was confirmed by Fourier Transform Infrared (FTIR) Spectroscopy, whereas scanning electron microscopy was used to characterize the morphology, size and shape of the particles. The FTIR spectrum proved the interaction between the sulfonate groups of AOT and the amino groups of Chi. Microparticles are quasi-spherical in wet conditions and irregular after freeze drying, presenting a rough surface with many pores. Lyophilized hydrophobic microparticles were used to remove phenol and o-cresol from aqueous solution, and the adsorption process showed a maximum efficiency in the 7–8 pH range. The uptake of phenol and o-cresol increased with the amount of particles and decreased with increasing the pollutant concentration. The adsorption occurred rapidly in the first 60–120 minutes, and leveled off thereafter.      

Facile Synthesis of Various Nitro-Substituted Derivatives of Semaxinib (SU5416)

The synthesis of novel nitro-substituted derivatives of the tyrosine kinase inhibitor Semaxinib (SU5416) is described. The reaction of various substituted oxindoles with 3,5-dimethylpyrrol-2-carbaldehyde derivatives under Knoevenagel conditions gave an array of nitro-substituted derivatives of Semaxinib (SU5416) in high yields of 72–87%.     

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis,Characterization and Reactivity of the First Phosphinine Selenide

The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of ¹J_P,Se=883 Hz is in line with a P−Se bond of high s-character. The σ-electron donating Me₃Si-substituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C₅H₅P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I)Cl as well as ⁱPrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination.     

iMole,a web based image retrieval system from biomedical literature

iMole is a platform that automatically extracts images and captions from biomedical literature. Images are tagged with terms contained in figure captions by means of a sophisticate text‐mining tool. Moreover, iMole allows the user to upload directly their own images within the database and manually tag images by curated dictionary. Using iMole the researchers can develop a proper biomedical image database, storing the images extracted from paper of interest, image found on the web repositories, and their own experimental images. In order to show the functioning of the platform, we used iMole to build a 2DE database. Briefly, tagged 2DE gel images were collected and stored in a searchable 2DE gel database, available to users through an interactive web interface. Images were obtained by automatically parsing 16 608 proteomic publications, which yielded more than 16 500 images. The database can be further expanded by users with images of interest trough a manual uploading process. iMole is available with a preloaded set of 2DE gel data at http://imole.biodigitalvalley.com .     

Membrane-assisted solvent extraction of seven phenols combined with large volume injection-gas chromatography-mass spectrometric detection

Membrane-assisted solvent extraction (MASE) was applied for the determination of seven phenols (phenol, 2-chlorophenol, 2,4-dimethylphenol, 2,4-dichlorophenol, 4-chloro-3-methylphenol, 2,4,6-trichlorophenol and pentachlorophenol) with log Kow (octanol-water-partition-coefficient) between 1.46 (phenol) and 5.12 (pentachlorophenol) in water. The extraction solvents cyclohexane, ethyl acetate and chloroform were tested and ethyl acetate proved to be the best choice. The optimisation of extraction conditions showed the necessity of adding 5 g of sodium chloride to each aqueous sample to give a saturated solution (333 g/L). The pH-value of the sample was adjusted to 2 in order to convert all compounds into their neutral form. An extraction time of 60 min was found to be optimal. Under these conditions the recovery of phenol, the most polar compound, was 11%. The recoveries of the other analytes ranged between 42% (2-chlorophenol) and 98% (2,4-dichlorophenol). Calibration was performed using large volume injection (100 microL injection volume). At optimised conditions the limits of detection were between 0.01 and 0.6 microg/L and the relative standard deviation (n = 3) was on average about 10%. After the method optimisation with reagent water membrane-assisted solvent extraction was applied to two contaminated ground water samples from the region of Bitterfeld in Saxony-Anhalt, Germany. The results demonstrate the good applicability of membrane-assisted solvent extraction for polar analytes like phenols, without the necessity of derivatisation or a difficult and time-consuming sample preparation.     

An original approach to determining traces of tetracycline antibiotics in milk and eggs by solid-phase extraction and liquid chromatography/mass spectrometry

An original and highly specific method able to identify and quantify traces of five tetracycline antibiotics (TCAs) in milk and eggs is presented. This method uses a single solid-phase extraction (SPE) cartridge for simultaneous extraction and purification of TCAs in the above matrices. After diluting 5 mL of intact whole milk or 2 g egg samples with Na(2)EDTA-containing water, samples are passed through a 0.5-g Carbograph 4 extraction cartridge. After analyte elution from the SPE cartridge, an aliquot of the final extract is injected into a liquid chromatography/mass spectrometry (LC/MS) instrument equipped with an electrospray ion source and a single quadrupole. MS data acquisition is performed in the positive-ion mode and by a time-scheduled multiple-ion selected ion-monitoring program. With methanol as organic modifier, the in-source collision-induced dissociation (CID) process generated fragment ions able to pick up one methanol molecule. In several cases, these methanol-adduct fragment ions have m/z values higher than those of the protonated molecules. This event is rarely encountered in MS, thus making the analysis of TCAs by this method extremely specific. Compared with a conventional published method, the present protocol extracted larger amounts of TCAs from both milk and egg and decreased the analysis time by a factor of 3. Recovery of TCAs in milk at the 25-ppb level ranged between 81 and 96% with relative standard deviation (RSD) no larger than 9%. Recovery of TCAs in egg at the 50-ppb level ranged between 72 and 92% with RSD no larger than 7%. Estimated limits of quantification(S/N = 10) of the method were 2-9 ppb TCAs in whole milk and 2-19 ppb TCAs in eggs.     

Synthesis of a New Series of Imidazo[1,5- d ]pyrido[2,3- b ][1,4]thiazines as Potential Ligands for the GABA Receptor Complex

 Starting from 2-chloro-3-nitropyridine, 1H-pyrido[2,3-b][1,4]thiazin-2(3H)-one was synthesized. This compound was reacted with potassium tert-butoxide and diethyl chlorophosphate to give the intermediate 1H-pyrido[2,3-b][1,4]thiazin-2-ylphosphate derivative, which in turn afforded the 1,2,4-oxadiazolylimidazo[1,5-d]pyrido[2,3-b]pyrazine derivatives. The title compounds are potential ligands for the γ-aminobutyric acid A/benzodiazepine receptor complex.     

Interlaboratory comparison study for the determination of methyl tert-butyl ether in water

This is the first publication which describes the evaluation of the analytical performance and state-of-the-art of the determination of methyl tert-butyl ether (MTBE) in water at ng L^–1 concentrations. An interlaboratory comparison study for the determination of MTBE in water was carried out. Twenty-eight laboratories from seven European countries participated in the study. Twenty of those finally transmitted results to the organiser. Italian spring water, containing no detectable amounts of MTBE was fortified to yield two samples with MTBE concentrations of 0.074±0.004 µg L^–1 and 0.256±0.010 µg L^–1. The laboratories applied their regular in-house methods to analyse the water samples. Static headspace, Purge & Trap, solid-phase microextraction (SPME) or direct aqueous injection were used as sample preparation techniques. Subsequent separation and detection of MTBE were performed by gas chromatography/mass spectrometry (GC/MS) or gas chromatography/flame ionisation detection (GC/FID). After rejection of outliers, the overall arithmetic mean of laboratory results corresponded to recoveries of 78±20% (Sample A) and 88±20% (Sample B) of the reference concentrations. The between laboratory coefficients of variation (CV) were 32% and 31%, respectively. The organisation of the study and quality assurance measures at the organiser's laboratory are described. Moreover, the measurement results of the participants and the analytical methods used for the determination of MTBE are presented and the correlation between selected method parameters and data quality is discussed.