Stable isotope dilution assay for the accurate determination of tricaine in fish samples by HPLC–MS–MS

Tricaine methanesulfonate is one of most commonly used anesthetics in fish during blood sampling, artificial propagation and long‐distance transportation. In this study, an accurate method for the quantitative determination of tricaine in fish samples by a stable isotope dilution assay coupled with high‐performance liquid chromatography–triple quadrupole mass spectrometry was developed. Tricaine‐D₅ was synthesized and used as an isotopically labeled internal standard for the determination of tricaine. The analytical performance of the method was validated for tricaine determination in marine fish and freshwater fish. The determination of tricaine was linear in the range of 2.0–200.0 μg L^?1. The limit of detection and limit of quantitation for fish muscle tissues were 1.0 and 4.0 μg kg^?1, respectively. Good recoveries were obtained in the range of 92.08–97.50%. The inter‐ and intra‐assay relative standard deviations (RSD values) were investigated, and the values were 0.39–3.01 and 0.85–2.77%, respectively. The values of CCα and CCβ were 10.21–10.43 and 10.42–10.87 μg kg^?1, respectively. The clearance of MS‐222 from grass carp was further studied using our method. The results demonstrate that MS‐222 could be well absorbed and rapidly eliminated after bath administration.     

Interaction of Phosphoric Anhydride with CH-, NH-, PH-, SH-Acids

Abstract

Phosphoric anhydride interacts with different CH-, NH-, PH-, SH-acids with the formation of corresponding amidophosphates and esters.     

Influence of Earthworms on the Sulfur Turnover in the Soil

Abstract

The effects of earthworm activity on the concentration and isotopic composition of total sulfur in soils was investigated using batch experiments. Two ecologically different lumbricid species, the anecic Lumbricus terrestris and the endogeic Aporrectodea caliginosa, were used. The earthworms were fed birch leaves, beech leaves, cattle manure or mixed plant litter. All food sources differed isotopically (δ³⁴S) from the soil (Parabraunerde). As a reference, one experiment was carried out without additional food.

The experimental results show, that both earthworm species influence the total S-content and the δ³⁴S-values in the soil by digestion of the different food sources. The differences in the total S-content of the earthworm tissues and in the S-isotopic composition of the casts can be attributed to the ecological differences between the earthworm species.     

Sensitivity analysis for a type of statically stable sailcrafts

Two types of sensitivities are proposed for statically stable sailcrafts.One type is the sensitivities of solar-radiation-pressure force with respect to position of the center of mass,and the other type is the sensitivities of solar-radiation-pressure force with respect to attitude.The two types of sensitivities represent how the solar-radiationpressure force changes with the position of mass center and the attitude.Sailcrafts with larger sensitivities undergo larger error of the solar-radiation-pressure force,leading to larger orbit error,as demonstrated by simulation.Then as a case study,detailed formulas are derived to calculate the sensitivities for sailcrafts with four triangular sails.According to these formulas,in order to reduce both types of sensitivities,the angle between opposed sails should not be too large,and the center of mass should be as close to the axis of symmetry of the four sails as possible and as far away from the center of pressure of the sailcraft as possible.     

ORGANOPHOSPHORUS COMPOUNDS,XXXIII THE REACTION OF PHOSPHITE ESTERS WITH QUINISATIN

Abstract

Trialkyl phosphites react with quinisatin (1) and its monohydrate 3 to give the corresponding phosphate derivatives 2a-c. The same compounds are obtained upon reacting 1 and/or 3 with the proper dialkyl phosphite. Structural reasonings based on IR, MS and NMR spectral data, are presented.     

A Simple Synthesis of Stable Phosphorus Ylides Derived from 2-Benzoxazolinone and 2-Mercaptobenzoxazole

The reaction of triphenylphosphine with dialkyl acetylenedicarboxylates in the presence of a strong SH-acid or NH-acid, such as 2-mercaptobenzoxazole and 2-benzoxazolinone, has been studied. In some cases, stable phosphorus ylides are obtained in excellent yields. The ylide moiety of these compounds is strongly conjugated with the adjacent carbonyl group, and the rotation about the partial double bond in (E) and (Z) geometrical isomers is slow on the NMR time scale at an ambient temperature. Thus, these exist as a mixture of geometrical isomers.     

Synthesis and Characterization of Silicone Modified Polyurethane Surfactant Useable at High Temperature

A series of novel silicone modified polyurethane (Si-PU) surfactants were successfully synthesized by using hydroxypropyl-terminated polydimethylsiloxane (HPMS), polyethylene glycol (PEG), dimethylolpropionic acid (DMPA) and isophoronediisocyanate (IPDI). The chemical structure of the surfactant was confirmed by FTIR and ¹H-NMR. TEM photographs showed that the micelles of the Si-PU surfactants dispersed in aqueous solution were spherical with the particle size in the range of 100–400 nm. Surface tension measurements indicated that these surfactants had low surface tension to 29.9 mN·m^?1and a definite critical micelle concentration to, approximately 5.0×10^?4–7.5×10^?4mol·L^?1. When the content of HPMS was 20 wt%, the surfactant's, emulsifying performance was superior to the traditionally available Span80/Tween80 mixed emulsifiers. In addition to that, no phase transition temperature was detected from 20°C to 90°C by fluorescence probe and DSC measurements, confirming the high thermal stability of the micelles.     

Profiling primaquine metabolites in primary human hepatocytes using UHPLC‐QTOF‐MS with 13C stable isotope labeling

Therapeutic efficiency and hemolytic toxicity of primaquine (PQ), the only drug available for radical cure of relapsing vivax malaria are believed to be mediated by its metabolites. However, identification of these metabolites has remained a major challenge apparently due to low quantities and their reactive nature. Drug candidates labeled with stable isotopes afford convenient tools for tracking drug‐derived metabolites in complex matrices by liquid chromatography‐tandem mass spectrometry (LC‐MS‐MS) and filtering for masses with twin peaks attributable to the label. This study was undertaken to identify metabolites of PQ from an in vitro incubation of a 1:1 w/w mixture of ¹³C₆‐PQ/PQ with primary human hepatocytes. Acquity ultra‐performance LC (UHPLC) was integrated with QTOF‐MS to combine the efficiency of separation with high sensitivity, selectivity of detection and accurate mass determination. UHPLC retention time, twin mass peaks with difference of 6 (originating from ¹³C₆‐PQ/PQ), and MS‐MS fragmentation pattern were used for phenotyping. Besides carboxy‐PQ (cPQ), formed by oxidative deamination of PQ to an aldehyde and subsequent oxidation, several other metabolites were identified: including PQ alcohol, predictably generated by oxidative deamination of PQ to an aldehyde and subsequent reduction, its acetate and the alcohol's glucuronide conjugate. Trace amounts of quinone‐imine metabolites of PQ and cPQ were also detected which may be generated by hydroxylation of the PQ/cPQ quinoline ring at the 5‐position and subsequent oxidation. These findings shed additional light on the human hepatic metabolism of PQ, and the method can be applied for identification of reactive PQ metabolites generated in vivo in preclinical and clinical studies. Copyright © 2013 John Wiley & Sons, Ltd.     

Ultra high performance liquid chromatography-quadrupole-time of flight analysis for the identification and the determination of resveratrol and its metabolites in mouse plasma

Resveratrol is a polyphenol that has numerous interesting biological properties, but, per os, it is quickly metabolized. Some of its metabolites are more concentrated than resveratrol, may have greater biological activities, and may act as a kind of store for resveratrol. Thus, to understand the biological impact of resveratrol on a physiological system, it is crucial to simultaneously analyze resveratrol and its metabolites in plasma. This study presents an analytical method based on UHPLC-Q-TOF mass spectrometry for the quantification of resveratrol and of its most common hydrophilic metabolites. The use of ¹³C- and D-labeled standards specific to each molecule led to a linear calibration curve on a larger concentration range than described previously. The use of high resolution mass spectrometry in the full scan mode enabled simultaneous identification and quantification of some hydrophilic metabolites not previously described in mice. In addition, UHPLC separation, allowing run times lower than 10 min, can be used in studies that requiring analysis of many samples.     

Determination of 13C/12C-ratios of anthropogenic organic contaminants in river water samples by GC-irmMS

This study describes the application of a common analytical procedure adapted for compound-specific stable carbon isotope analyses of riverine contaminants. To evaluate the sensitivity of the analytical method and the precision of the isotopic data obtained, a set of numerous substances at different concentration levels were measured. For most of the anthropogenic contaminants investigated (including chlorinated aliphatics and aromatics, musk fragrances, phthalate-based plasticizers and tetrabutyl tin) acceptable carbon isotope analyses could be obtained down to amounts of approximately 5?ng absolutely applied to the gas chromatograph. These amounts correspond to concentrations in water samples at a natural abundance level of approximately 50–200?ng?L^?1 (low to medium contaminated river systems). However, it has to be considered that the precision and the sensitivity of the analytical method depend partially on the chemical properties of the substances measured. Five recovery experiments were conducted to assess changes in carbon isotope ratios during sample preparation and measurement. The compounds selected for these experiments are known riverine contaminants. Isotopic shifts or higher variations of the isotope ratios as a result of the analytical procedures applied were observed only for a couple of contaminants. Furthermore, compound-specific carbon isotope analyses were performed on eight water extracts of the Rhine river. By comparing the variation of the data of several individual compounds with the deviations obtained from the recovery experiments, it was possible to differentiate contaminants with unaffected isotope ratios and substances with significant alterations of the δ¹³C-values.