Rapid screening of selective serotonin re-uptake inhibitors in urine samples using solid-phase microextraction gas chromatography–mass spectrometry

In this paper a solid-phase microextraction–gas chromatography–mass spectrometry (SPME–GC–MS) method is proposed for a rapid analysis of some frequently prescribed selective serotonin re-uptake inhibitors (SSRI)—venlafaxine, fluvoxamine, mirtazapine, fluoxetine, citalopram, and sertraline—in urine samples. The SPME-based method enables simultaneous determination of the target SSRI after simple in-situ derivatization of some of the target compounds. Calibration curves in water and in urine were validated and statistically compared. This revealed the absence of matrix effect and, in consequence, the possibility of quantifying SSRI in urine samples by external water calibration. Intra-day and inter-day precision was satisfactory for all the target compounds (relative standard deviation, RSD, <14%) and the detection limits achieved were <0.4 ng mL^–1 urine. The time required for the SPME step and for GC analysis (30 min each) enables high throughput. The method was applied to real urine samples from different patients being treated with some of these pharmaceuticals. Some SSRI metabolites were also detected and tentatively identified.     

Synthesis,Structure and Reactivity of [1, 2‐Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I) with Reactions of Phosphites,Phosphonites. and Phosphinites

The manganese carbonyl complex [MnBr(CO)₃ L ] ( 1 ), where L = Ph₂POCH₂CH₂OPPh₂, was prepared by reacting [MnBr(CO)₅] with the bidentate ligand 1, 2‐Bis(diphenylphosphinite)ethane. From this compound and the appropriate phosphite, phosphinite or phosphonite ligands were synthesized the complexes [MnBr(CO)₂ LL ′], where L ′ = P(OMe)₃ ( 2 ) or P(OEt)₃ ( 3 ) and [MnBr(CO)₃ L ′₂], where L ′ =PPh(OEt)₂ ( 4 ) or PPh₂(OEt) ( 5 ). The obtained compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR (¹H, ¹³C and ³¹P) spectroscopies and X‐ray diffractometry for the complexes 1 , 4 and 5 .     

Effect of the ZnNi y Mn2– y O4 (0 ≤ y ≤ 1) spinel composition on electrochemical lithium insertion

The electrochemical insertion of lithium in the spinel-type manganite with the formula ZnNi _y Mn_{2– y} O₄ has been studied. The galvanostatic discharge curves show that the best performance is obtained for y = 0.25, where a tetragonal to cubic structural transformation occurs. The thermodynamics and kinetics of the process of insertion of the lithium into the tetragonal spinel Li _x ZnNi_0.25Mn_1.75O₄ (x = 0.05–1.3) have been studied. The molar thermodynamic quantities, such as enthalpy, entropy and free energy determined by EMF-T measurements, varied with the lithium concentration in the oxide structure, and a major variation was observed around x = 0.8. The chemical diffusion coefficient of lithium in these spinels was also determined. Structural analysis, degree of oxidation and magnetic susceptibility measurements were carried out for the lithiated oxides in order to obtain the cationic distribution as a function of x. It has been possible to demonstrate that, upon lithium insertion, Mn⁴⁺ ions on B sites are reduced to Mn³⁺ and then to Mn²⁺. A cooperative Jahn-Teller effect is present in these spinel manganese-nickel oxides. Received: 4 February 1997 / Accepted: 11 April 1997     

Exploring the Influence of Intermolecular Interactions in Prebiotic Chemistry Using Laser Spectroscopy and Calculations

One of the most fascinating questions in chemistry is why nature chose CGAT as the alphabet of life. Very likely, such selection was the result of multiple factors and a long period of refinement. Here, we explore how the intermolecular interactions influenced such process, by characterizing the formation of dimers between adenine, theobromine and 4-aminopyrimidine. Using a combination of mass-resolved excitation spectroscopy and DFT calculations, we determined the structure of adenine-theobromine and 4-aminopyrimidine-theobromine dimers. The binding energy of these dimers is very close to the canonical adenine-thymine nucleobases. Likewise, the dimers are able to adopt Watson-Crick conformations. These findings seem to indicate that there were many options available to build the first versions of the informational polymers, which also had to compete with other molecules, such as 4-aminopyrimidine, which does not have a valid attaching point for a saccharide. For some reason, nature did not select the most strongly-bonded partners or if it did, such proto-bases were later replaced by the nowadays canonical CGAT.     

Reentrant quantum Hall effect and anisotropic transport in a bilayer system at high filling factors

We report on the measurements of the quantum Hall effect states in double quantum well structures at the filling factors nu=4N+1 and nu=4N+3, where N is the Landau index number, in the presence of the in-plane magnetic field. The quantum Hall states at these filling factors vanish and reappear several times and exhibit anisotropy. Repeated reentrance of the transport gap occurs due to the periodic vanishing of the tunneling amplitude in the presence of the in-plane field. Anisotropy demonstrates the existence of the stripes in the ground states.     

Molecular Targets Implicated in the Antiparasitic and Anti-Inflammatory Activity of the Phytochemical Curcumin in Trichomoniasis

Trichomoniasis, is the most prevalent non-viral sexually transmitted disease worldwide. Although metronidazole (MDZ) is the recommended treatment, several strains of the parasite are resistant to MDZ, and new treatments are required. Curcumin (CUR) is a polyphenol with anti-inflammatory, antioxidant and antiparasitic properties. In this study, we evaluated the effects of CUR on two biochemical targets: on proteolytic activity and hydrogenosomal metabolism in Trichomonas vaginalis. We also investigated the role of CUR on pro-inflammatory responses induced in RAW 264.7 phagocytic cells by parasite proteinases on pro-inflammatory mediators such as the nitric oxide (NO), tumor necrosis factor α (TNFα), interleukin-1beta (IL-1β), chaperone heat shock protein 70 (Hsp70) and glucocorticoid receptor (mGR). CUR inhibited the growth of T. vaginalis trophozoites, with an IC₅₀ value between 117 ± 7 μM and 173 ± 15 μM, depending on the culture phase. CUR increased pyruvate:ferredoxin oxidoreductase (PfoD), hydrogenosomal enzyme expression and inhibited the proteolytic activity of parasite proteinases. CUR also inhibited NO production and decreased the expression of pro-inflammatory mediators in macrophages. The findings demonstrate the potential usefulness of CUR as an antiparasitic and anti-inflammatory treatment for trichomoniasis. It could be used to control the disease and mitigate the associated immunopathogenic effects.     

Optimal quantum cloning on a beam splitter

We demonstrate how a beam splitter in combination with different light sources can be used as an optimal universal 1-->2 quantum cloner and as an optimal universal quantum NOT machine for the polarization qubit of a single photon. For the cloning a source of single photons with maximally mixed polarization is required and for the NOT operation a source of maximally entangled photon pairs. We demonstrate both operations with near optimal fidelity. Our scheme can be generalized in a natural way to clone and NOT the spin state of electrons.     

Sorbent trapping solid-phase microextraction of fragrance allergens in indoor air

Exposure to fragrance substances is exponentially increasing in our daily life due to the enhanced use of scented products. Some fragrances are known to be important sensitizers, inhalation being an important exposure pathway in indoor environments. A simple and sensitive method based on solid-phase enrichment and solid-phase microextraction (SPME) followed by gas chromatography–mass spectrometry (GC–MS) has been developed for the analysis of 24 volatile fragrance allergens in indoor air. Suspected allergens present in the air (0.2 m³) were adsorbed onto a very small quantity of florisil (25 mg) and then transferred to a SPME fiber in the headspace mode (HS). To the best of our knowledge, this paper describes the first application of SPME for the determination of these compounds in air samples. The experimental parameters affecting the microextraction process have been optimized using a multifactor experimental design strategy. Accuracy, linearity, precision and detection limits (LODs) were evaluated to assess the performance of the proposed method. External calibration, using spiked sorbent standards, and not requiring the complete sampling process (only the SPME step), demonstrated to be suitable for the quantification of all suspected allergens. Recovery studies were performed at three concentration levels (0.04, 1.00 and 50 μg m⁻³), obtaining quantitative recoveries (≥85%) in most cases. LOD values at the low ng m⁻³ level were achieved for all the target compounds. The application of the method to daily home air samples demonstrated the ubiquity of this kind of fragrance ingredients in quotidian indoor environments, finding 18 of the 24 considered compounds in concentrations ranging from 0.01 to 56 μg m⁻³. Benzyl alcohol, linalool, citronellol, ionone and lilial were found in most analyzed samples.     

Development of a solid phase dispersion-pressurized liquid extraction method for the analysis of suspected fragrance allergens in leave-on cosmetics

A new method based on solid phase dispersion-pressurized liquid extraction (PLE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed for the determination of 26 suspected fragrance allergens (all the regulated in the EU Cosmetics Directive amenable by GC, as well as pinene and methyleugenol) in cosmetic samples. The effects of the temperature, extraction time and solvent, and dispersing sorbent, affecting the whole proposed procedure, have been evaluated using a multifactor strategy. The optima conditions after the analysis of main and second order effects entailed the extraction at 120°C for 15 min, using hexane/acetone as solvent, and florisil as dispersing sorbent. The method performance has been studied, showing good linearity (R≥0.996) as well as good precision (RSD≤10%). Detection limits (S/N=3) ranged from 0.000001 to 0.0002% (w/w), values far below the established restrictions as regard labelling in the European Cosmetics Regulation. Reliability was demonstrated through the quantitative recoveries of all the studied compounds. The absence of matrix effects allowed quantification of the compounds by calibration with standard solutions. The analysis of 10 samples (several moisturizing and anti-wrinkle creams and lotions, hand creams, and sunscreen and after-sun creams), covering very different matrices, showed the presence of suspected allergens in all the analyzed samples; in fact, half of the samples contained an elevated number of them. Although the ubiquity of these compounds was demonstrated, labelling was in all cases in consonance with the European Cosmetics Regulation.     

Tracing (r)bST in cattle: Liquid-based options for extraction and separation

Growth hormone (GH) or somatotropin (ST) is a species-specific polypeptide hormone produced in the pituitary gland of vertebrates. When administered exogenously to dairy cattle, it has galactopoietic effects and is capable of increasing the milk yield. The beginning of the commercial production of recombinant variants of bovine somatotropin (rbST), by the end of the 20th century, had a major economic impact in the dairy industry. Recombinant bST enabled large-scale applications in farms, enhancing significantly milk production. While it is banned in the European Union (EU), several countries permit the trade and use of recombinant somatotropins in animal husbandry. Also, rbST-free dairy products can be frequently found in the market of those countries, even though these labels are not actually verified in a laboratory. In this context, effective analytical methods are needed for residue control to avoid an illegal use of rbST but also to prevent fraudulent labeling in some cases. The present review includes studies published in the last 5 years (from 2012 to 2017) to monitor rbST in bovine animals, using liquid-based applications. It is then intended to serve as a practical guide to help those laboratories interested in developing analytical methods to detect rbST use and abuse.