Liquid chromatography–mass spectrometry applications for quantification of endogenous sex hormones

Liquid chromatography, coupled with tandem mass spectrometry, presents a powerful tool for the quantification of the sex steroid hormones 17‐β estradiol, progesterone and testosterone from biological matrices. The importance of accurate quantification with these hormones, even at endogenous levels, has evolved with our understanding of the role these regulators play in human development, fertility and disease risk and manifestation. Routine monitoring of these analytes can be accomplished by immunoassay techniques, which face limitations on specificity and sensitivity, or using gas chromatography–mass spectrometry. LC–MS/MS is growing in capability and acceptance for clinically relevant quantification of sex steroid hormones in biological matrices and is able to overcome many of the limitations of immunoassays. Analyte specificity has improved through the use of novel derivatizing agents, and sensitivity has been refined through the use of high‐resolution chromatography and mass spectrometric technology. This review highlights these innovations, among others, in LC–MS/MS steroid hormone analysis captured in the literature over the last decade.     

Dynamical versus variational symmetries: understanding Noether's first theorem

It is argued that awareness of the distinction between dynamical and variational symmetries is crucial to understanding the significance of Noether's 1918 work. Special attention is paid, by way of a number of striking examples, to Noether's first theorem, which establishes a correlation between dynamical symmetries and conservation principles.     

Validation of an analytical method to quantify the permeation and penetration of flurbiprofen into human pharynx tissue

The aim of this investigation was to develop receiver and extraction fluids, and subsequently validate an analytical method to quantify the permeation and penetration of flurbiprofen into human pharynx tissue using a Franz diffusion cell. The solubility and stability of flurbiprofen in a suitable receiver fluid, and a suitable extraction method and fluid to recover and quantitate flurbiprofen from human pharynx tissue, were investigated using high‐performance liquid chromatography (HPLC). The potential interference of human pharynx tissue in the receiver fluid was also investigated. The HPLC analytical method was successfully validated according to current guidelines. The final receiver fluid demonstrated sufficient solubility and stability, and the extraction method and fluid resulted in >95% recovery of flurbiprofen following exposure to human pharynx tissue. The lower limit of quantitation of flurbiprofen was 0.045 μg/mL in both the receiver and extraction fluids. There was no interference of the human pharynx tissue with the HPLC method. This investigation validated an analytical method for quantitating flurbiprofen, and determined a suitable receiver fluid and extraction method and fluid, which can be used to investigate the permeation and penetration of flurbiprofen through human pharynx tissue using the Franz diffusion cell method.     

Synthesis of Quadruply Carbon-13 Labeled Tetramethyltetrathiaful Valene

A short synthesis of tetramethyltetrathiafulvalene quadruply labeled with carbon-13 is described.     

THE PREPARATION OF TRIALKYL PHOSPHITES DIRECTLY FROM THE ELEMENT

Abstract

The reaction between finely divided white phosphorus and several alkoxide ions in the presence of tetrachloromethane and excess of alcohol has been investigated under a variety of conditions. High yields of trialkylphosphite are obtained when two equivalents of alkoxide are used. With one equivalent of alkoxide, dialkylphosphonate is formed in comparable yield. Maximum yields of triester are obtained within 1–3 h at room temperature. Prolonged treatment results in the conversion of trialkylphosphite to phosphate by reaction with tetrachloromethane. Phenolate ions are unreactive under the same experimental conditions. The mechanism of the reaction is discussed.