Rapid determination of natural and synthetic hormones in biosolids and poultry manure by isotope dilution GC–MS/MS

The release of hormones into the environment due to land application of biosolids and manure is a cause of concern for their potential impacts. This paper presents the development of a rapid and sensitive method, based on extraction, for the analysis of 13 hormones in biosolids and poultry manure. A simultaneous derivatization of hydroxyl and ketone groups was carried out for the determination of hormones by GC–MS/MS. The method was validated in three matrices (sewage sludge, manure, and broiler litter). Recoveries from spiked samples at three concentration levels (50, 25, and 10 ng/g) ranged from 76 to 124% with relative SDs ≤ 16%. Method detection limits for the three matrices were in the range of 0.5–3.0 ng/g dry weight. The optimized method was applied to biosolid and poultry manure samples collected in Spain. Only seven of the 13 studied hormones were detected in the different samples. trans‐Androsterone was detected at high levels (up to 3.1 μg/g in biosolid samples). Estrone and estradiol were the two hormones detected at higher levels in layer manure, whereas estrone and 4‐androstene‐3,17‐dione presented the highest levels in broiler litter.     

Detecting authorized and unauthorized genetically modified organisms containing vip3A by real-time PCR and next-generation sequencing

The growing number of biotech crops with novel genetic elements increasingly complicates the detection of genetically modified organisms (GMOs) in food and feed samples using conventional screening methods. Unauthorized GMOs (UGMOs) in food and feed are currently identified through combining GMO element screening with sequencing the DNA flanking these elements. In this study, a specific and sensitive qPCR assay was developed for vip3A element detection based on the vip3Aa20 coding sequences of the recently marketed MIR162 maize and COT102 cotton. Furthermore, SiteFinding-PCR in combination with Sanger, Illumina or Pacific BioSciences (PacBio) sequencing was performed targeting the flanking DNA of the vip3Aa20 element in MIR162. De novo assembly and Basic Local Alignment Search Tool searches were used to mimic UGMO identification. PacBio data resulted in relatively long contigs in the upstream (1,326 nucleotides (nt); 95 % identity) and downstream (1,135 nt; 92 % identity) regions, whereas Illumina data resulted in two smaller contigs of 858 and 1,038 nt with higher sequence identity (>99 % identity). Both approaches outperformed Sanger sequencing, underlining the potential for next-generation sequencing in UGMO identification.

UVB Radiation Affects Growth,Reproduction and Tissue Structure of Daphnia magna Across Several Temperatures

We examined the effects of daily exposure to UVB on growth, reproduction and histological characteristics of Daphnia magna over two generations at 20, 22, 25 and 30°C. Animals were exposed to 16 h of UVA and photosynthetically active radiation daily. Treated animals received 6 h of UVB during the light phase. Parental (P) generation growth and reproduction was impaired by exposure to UVB at all temperatures, with the poorest production at 30°C. First brood size decreased with UVB exposure; it was lowest at 30°C. Although F1 length at birth increased with P generation age, F1 produced by UVB‐exposed mothers were smaller at all temperatures. The F1 generation was followed at 20 and 25°C; at both temperatures UVB exposure reduced F1 growth and reproduction. F1 growth and F2 production were lowest when both P and F1 generations were exposed to UVB. UVB exposure damaged ovarian and gut tissue at both 25 and 30°C; the consequences of this exposure were more severe at 30°C. The observed tissue damage may relate directly to the UVB‐induced impairment of growth and reproduction. This study provides new insights into the effects of UVB on an important component of the pelagic zooplankton.     

Solvent and Media Effects on the Photophysics of Naphthoxazole Derivatives

The photophysical properties of 2‐phenyl‐naphtho[1,2‐d][1,3]oxazole, 2(4‐N,N‐dimethylaminophenyl)naphtho[1,2‐d][1,3]oxazole and 2(4‐N,N‐diphenylaminophenyl) naphtho[1,2‐d][1,3]oxazole were studied in a series of solvents. UV–Vis absorption spectra are insensitive to solvent polarity whereas the fluorescence spectra in the same solvent set show an important solvatochromic effect leading to large Stokes shifts. Linear solvation energy relationships were employed to correlate the position of fluorescence spectra maxima with microscopic empirical solvent parameters. This study indicates that important intramolecular charge transfer takes place during the excitation process. In addition, an analysis of the solvatochromic behavior of the UV–Vis absorption and fluorescence spectra in terms of the Lippert–Mataga equation shows a large increase in the excited‐state dipole moment, which is also compatible with the formation of an intramolecular charge‐transfer excited state. We propose both naphthoxazole derivatives as suitable fluorescent probes to determine physicochemical microproperties in several systems and as dyes in dye lasers; consequence of their high fluorescence quantum yields in most solvents, their large molar absorption coefficients, with fluorescence lifetimes in the range 1–3 ns as well as their high photostability.     

Solvent-free synthesis and crystal structures of s-cis and s-trans N,N′-bis(2-hydroxycyclohexyl)ethane-1,2-diamine

The symmetrical amino alcohol synthesis via ring opening of cyclohexene oxide with ethylendiamine is illustrated by synthesis and characterization of β-amino alcohols s-cis-(SSSS)-cy₂en (1) and s-trans-(SSRR)-cy₂en (2) (cy₂en = N,N′-bis(2-hydroxycyclohexyl)ethane-1,2-diamine) in one step and with high yield. The reaction was carried out in a microwave reactor under solvent-free conditions. These products were characterized by IR and Raman spectroscopy, elemental analysis, thermal methods (TGA, DTG and DTA), mass spectrometry and ¹H and ¹³C NMR spectroscopy. The crystal structures of 1 and 2 were determined by single crystal X-ray structural analysis, followed by DFT calculations. Intramolecular hydrogen bond was observed in 1 with C ₂ symmetry, but not in 2 with C _i symmetry. The nature of intramolecular hydrogen bond in 1 has been investigated by AIM and NBO analyses. The molecules in 1 are linked into an infinite chain along the [001] direction, giving rise to R ₄ ⁴ (8) graph-set motif, while the molecules in 2 are linked into a 2D network in the bc plane, giving rise to R ₂ ² (10) and R ₃ ³ (12) motifs. The protonation equilibria of 1 and 2 have been studied by pH-potentiometry, with pK ₁ 9.01 and pK ₂ 5.50 determined for 1 and pK ₁ 8.58 and pK ₂ 5.26 determined for 2.     

Highly Reactive Sulfinates. II1. The Solvolysis and Rearrangement of Benzyl Trifluoromethanesulfinates

Abstract

The stereochemistry of substitution at dihalomethylphosphonothioates is the same as for phosphorothioates whereas that for monohalomethylphosphono-thioates is similar to the unsubstituted phosphonothioates.     

Determination of chlorobenzenes in water samples based on fully automated microextraction by packed sorbent coupled with programmed temperature vaporization–gas chromatography–mass spectrometry

A fully automated method consisting of microextraction by packed sorbent (MEPS) coupled directly to programmed temperature vaporizer–gas chromatography–mass spectrometry (PTV–GC–MS) has been developed to determine the 12 chlorobenzene congeners (chlorobenzene; 1,2-, 1,3-, and 1,4-dichlorobenzene; 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzene; 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-tetrachlorobenzene; pentachlorobenzene; and hexachlorobenzene) in water samples. The effects of the variables on MEPS extraction, using a C18 sorbent, and the instrumental PTV conditions were studied. The internal standard 1,4-dichlorobenzene d4 was used as a surrogate. The proposed method afforded good reproducibility, with relative standard deviations (RSD %) lower than 12 %. The limits of detection varied between 0.0003 μg L^?1 for 1,2,3,4-tetrachlorobenzene and 0.07 μg L^?1 for 1,3- and 1,4-dichlorobenzene, while those of quantification varied between 0.001 μg L^?1 and 0.2 μg L^?1 for the same compounds. Accuracy of the proposed method was confirmed by applying it to the determination of chlorobenzenes in different spiked water samples, including river, reservoir, and effluent wastewater.

Water: How Does It Influence the CaCO3 Formation?

Nature produces biomineral‐based materials with a fascinating set of properties using only a limited number of elements. This set of properties is obtained by closely controlling the structure and local composition of the biominerals. We are far from achieving the same degree of control over the properties of synthetic biomineral‐based composites. One reason for this inferior control is our incomplete understanding of the influence of the synthesis conditions and additives on the structure and composition of the forming biominerals. In this Review, we provide an overview of the current understanding of the influence of synthesis conditions and additives during different formation stages of CaCO₃, one of the most abundant biominerals, on the structure, composition, and properties of the resulting CaCO₃ crystals. In addition, we summarize currently known means to tune these parameters. Throughout the Review, we put special emphasis on the role of water in mediating the formation of CaCO₃ and thereby influencing its structure and properties, an often overlooked aspect that is of high relevance.     

An Application of Capillary Electrophoresis for the Analysis of Algal Toxins from the Aquatic Environment

In this work capillary electrophoresis (CE) with UV detection has been applied to the analysis of different natural toxins produced in the aquatic environment. This technique is presented as an alternative to other chemical techniques such as HPLC, and the optimisation of analytical methodologies was carried out for diverse marine toxins including Paralytic and Amnesic and some polyether toxins, such as Yessotoxins, as well as for certain microcystin toxins produced by cyanobacteria present in freshwaters. Sample preparation steps were optimised and adequate electrophoretic conditions developed for achieving a complete separation of compounds with similar structures involved in such contamination. The influence of the biological matrices where they are involved has also been studied and the potential use of CE-UV as a tool for monitoring these aquatic toxins is also discussed.     

Hollow fibre liquid-phase microextraction of parabens from environmental waters

Parabens (alkyl-p-hydroxybenzoates) are antimicrobial preservatives widely used in cosmetics, toiletries, pharmaceuticals, and food. Nowadays, they are considered emerging pollutants and their determination is becoming increasingly important since they are continuously released into the environment. In this work, a hollow fibre liquid-phase microextraction method has been developed for the extraction of parabens from environmental waters. The parameters affecting the extraction of parabens (organic solvent used as liquid membrane; pH of both sample and acceptor solution; salting-out effect; extraction time and stirring speed) were carefully optimized in order to reach high recoveries for all tested analytes. Under optimum conditions, parabens were extracted from river, reservoir and sea water samples with recoveries ranging from 16.7 to 68.6% depending upon the analyte and the sample analyzed, leading to detection limits lower than 0.2?ng?mL^?1 using a simple HPLC-UV instrument.