Determination of anabolic androgenic steroids as imidazole carbamate derivatives in human urine using liquid chromatography–tandem mass spectrometry

Anabolic androgenic steroids are widely abused substances in sports doping. Their detection present limitations regarding the use of soft ion sources such as electrospray or atmospheric pressure chemical ionization by liquid chromatography–tandem mass spectrometry. In the current study, a novel derivatization method was developed for the ionization enhancement of selected anabolic androgenic steroids. The proposed method aims at the introduction of an easily ionizable moiety into the steroid molecule by converting the hydroxyl groups into imidazole carbamates using 1,1′‐carbonyldiimidazole as derivatization reagent. The proposed method was applied to water and urine samples spiked with exogenous anabolic androgenic steroids in various concentration levels. Steroid imidazole carbamate derivatives have shown intensive [M+H]⁺ signals under electrospray ionization and common fragmentation patterns in tandem mass spectrometry mode with [M‐CO₂+H]⁺ and [M‐ΙmCO₂+H]⁺ as major ions with low collision energy. The obtained results showed that the majority of steroids were detectable at concentrations equal or lower to their minimum required performance level according to the World Anti‐Doping Agency technical document. The proposed method is sensitive with a preparation procedure that could be easily applied to the analysis of doping control samples.     

Surface Tension of the 4-Methyl-2-Pentanone/Ethyl Benzoate Binary System in the Temperature Range from 278.15 to 308.15K

Surface tensions (σ) and densities (ρ) of 4-methyl-2-pentanone/ethyl benzoate binary mixtures have been measured over the entire composition range at 278.15, 288.15, 298.15, and 308.15 K. Values of the excess surface tensions (σ^E) and excess molar volumes (V^E) have been calculated. The σ^E and V^E values were fitted by to the Redlich–Kister polynomial equation and the A_k coefficients have been derived. The standard deviations between the calculated and the experimental excess properties have also been derived. The surface tension values have been further used to calculate the surface entropies (S^S) and surface enthalpies (H^S) per unit surface area. The lyophobicity (β) and the surface mole fractions (x₁^S) of the surfactant 4-methyl-2-pentanone have been derived using the extended Langmuir model. The obtained results are discussed from the viewpoint of the existence of specific interactions between unlike molecules in the bulk region and the surface.     

A Comparative Study of Various Pretreatment Approaches for Bio-Ethanol Production from Willow Sawdust,Using Co-Cultures and Mono-Cultures of Different Yeast Strains

The effect of different pretreatment approaches based on alkali (NaOH)/hydrogen peroxide (H₂O₂) on willow sawdust (WS) biomass, in terms of delignification efficiency, structural changes of lignocellulose and subsequent fermentation toward ethanol, was investigated. Bioethanol production was carried out using the conventional yeast Saccharomyces cerevisiae, as well as three non-conventional yeasts strains, i.e., Pichia stipitis, Pachysolen tannophilus, Wickerhamomyces anomalus X19, separately and in co-cultures. The experimental results showed that a two-stage pretreatment approach (NaOH (0.5% w/v) for 24 h and H₂O₂ (0.5% v/v) for 24 h) led to higher delignification (38.3 ± 0.1%) and saccharification efficiency (31.7 ± 0.3%) and higher ethanol concentration and yield. Monocultures of S. cerevisiae or W. anomalus X19 and co-cultures with P. stipitis exhibited ethanol yields in the range of 11.67 ± 0.21 to 13.81 ± 0.20 g/100 g total solids (TS). When WS was subjected to H₂O₂ (0.5% v/v) alone for 24 h, the lowest ethanol yields were observed for all yeast strains, due to the minor impact of this treatment on the main chemical and structural WS characteristics. In order to decide which is the best pretreatment approach, a detailed techno-economical assessment is needed, which will take into account the ethanol yields and the minimum processing cost.     

CO(2) capture by a task-specific ionic liquid

Reaction of 1-butyl imidazole with 3-bromopropylamine hydrobromide, followed by workup and anion exchange, yields a new room temperature ionic liquid incorporating a cation with an appended amine group. The new ionic liquid reacts reversibly with CO2, reversibly sequestering the gas as a carbamate salt. The new ionic liquid, which can be repeatedly recycled in this role, is comparable in efficiency for CO2 capture to commercial amine sequestering reagents, and yet is nonvolatile and does not require water to function.     

Sweet success: Ionic liquids derived from non-nutritive sweeteners

The anions of the sweeteners saccharin and acesulfame form ionic liquids when paired with a variety of organic cations.     

Analysis of photo-chemical degradation behaviour of polyethylene mulching film with pro-oxidants

It is generally accepted that polyolefins are bioinert. The last years, a new class of photodegradable polyethylene films with pro-oxidants has been developed, exhibiting optimised operational properties in terms of controlled UV and/or thermal ageing leading to an abrupt, predefined to some extent, rapid fragmentation into very small fragments. These photodegradable or fragmentable polyethylene films are promoted in the market for various commercial applications. In some cases, these materials are presented as, or are claimed to be, biodegradable materials. Such materials are already used in agriculture in the form of photodegradable mulching films which become fragmented into small remains after the end of their useful lifetime and are incorporated into the soil. However, it has not been verified yet beyond any doubt, that these remains do in fact biodegrade in natural soil, under what conditions, at which rate and what are their effects in agricultural production, the soil and the environment. An experimental investigation has been carried out focusing on the combined effects of critical factors on the controlled (predefined) photo-chemical degradation of photodegradable mulching LLDPE films with pro-oxidants and the behaviour of their remains in the soil. The analysis of the photo-chemical degradation behaviour presented in this paper was carried out through parallel experiments performed under real field and controlled laboratory conditions. The main factors investigated include materials, exposure time, temperature and UV radiation.     

Platinum group metals bulk analysis in automobile catalyst recycling material by laser-induced breakdown spectroscopy

Development and application of an in-situ applicable method to provide rapid determination of platinum group metals (platinum, palladium, and rhodium) elemental concentration in automobile catalyst scrap is reported. Application is based on laser-induced breakdown spectroscopy (LIBS). Actual automobile catalyst slurry in powder form was used to develop the application. With a method requiring approximately 1.5 min of examination per sample, calibration curves are presented with linear regression coefficients close to 0.99 and stability better than 3.0%.     

Benzodiazepine biosynthesis in Streptomyces refuineus

Anthramycin is a benzodiazepine alkaloid with potent antitumor and antibiotic activity produced by the thermophilic actinomycete Streptomyces refuineus sbsp. thermotolerans. In this study, the complete 32.5 kb gene cluster for the biosynthesis of anthramycin was identified by using a genome-scanning approach, and cluster boundaries were estimated via comparative genomics. A lambda-RED-mediated gene-replacement system was developed to provide supporting evidence for critical biosynthetic genes and to validate the boundaries of the proposed anthramycin gene cluster. Sequence analysis reveals that the 25 open reading frame anthramycin cluster contains genes consistent with the biosynthesis of the two halves of anthramycin: 4 methyl-3-hydroxyanthranilic acid and a "dehydroproline acrylamide" moiety. These nonproteinogenic amino acid precursors are condensed by a two-module nonribosomal peptide synthetase (NRPS) terminated by a reductase domain, consistent with the final hemiaminal oxidation state of anthramycin.     

Equilibria of two-sided matching games with common preferences

Problems of matching have long been studied in the operations research literature (assignment problem, secretary problem, stable marriage problem). All of these consider a centralized mechanism whereby a single decision maker chooses a complete matching which optimizes some criterion. This paper analyzes a more realistic scenario in which members of the two groups (buyers–sellers, employers–workers, males–females) randomly meet each other in pairs (interviews, dates) over time and form couples if there is mutual agreement to do so. We assume members of each group have common preferences over members of the other group. Generalizing an earlier model of Alpern and Reyniers [Alpern, S., Reyniers, D.J., 2005. Strategic mating with common preferences. J. Theor. Biol. 237, 337–354], we assume that one group (called males) is r   times larger than the other, r?1$r?1$. Thus all females, but only 1/r$1/r$ of the males, end up matched. Unmatched males have negative utility -c$-c$. We analyze equilibria of this matching game, depending on the parameters r   and c$c$. In a region of (r,c)$(r\text{,}c)$ space with multiple equilibria, we compare these, and analyze their ‘efficiency’ in several respects. This analysis should prove useful for designers of matching mechanisms who have some control over the sex ratio (e.g. by capping numbers of males at a ‘singles event’or by having ‘ladies free’ nights) or the nonmating cost c (e.g. tax benefits to married couples).     

Transport of Pseudomonas putida in a 3-D Bench Scale Experimental Aquifer

This study is focused on the transport of Pseudomonas (P.) putida bacterial cells in a 3-D model aquifer. The pilot-scale aquifer consisted of a rectangular glass tank with internal dimensions: 120?cm length, 48?cm width, and 50?cm height, carefully packed with well-characterized quartz sand. The P. putida decay was adequately represented by a first-order model. Transport experiments with a conservative tracer and P. putida were conducted to characterize the aquifer and to investigate the bacterial behavior during transport in water saturated porous media. A 3-D, finite-difference numerical model for bacterial transport in saturated, homogeneous porous media was developed and was used to successfully fit the experimental data. Furthermore, theoretical interaction energy calculations suggested that the extended-DLVO theory seems to predict bacteria attachment onto the aquifer sand better than the classical DLVO theory.