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.     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Flow-induced beam steering in a single laser hot spot

The transmitted angular distribution of a 527 nm nearly diffraction-limited laser is measured after it propagates through a plasma with supersonic transverse flow. The laser beam is deflected by as much as 10 degrees and exhibits bowlike features in the flow direction, which is attributed to flow-induced beam steering. The finite interaction volume allows for direct comparison with a 3D hydrodynamic simulation, which is in good agreement with details of the experiment.     

High-power, kilojoule class laser channeling in millimeter-scale underdense plasma

Experiments were performed using the Omega EP laser, operating at 740 J of energy in 8 ps (90 TW), which provides extreme conditions relevant to fast ignition studies. A carbon and hydrogen plasma plume was used as the underdense target and the interaction of the laser pulse propagating and channeling through the plasma was imaged using proton radiography. The early time expansion, channel evolution, filamentation, and self-correction of the channel was measured on a single shot via this method. A channel wall modulation was observed and attributed to surface waves. After around 50 ps, the channel had evolved to show bubblelike structures, which may be due to postsoliton remnants.     

Non-linear shallow water theory

The equations controlling the three dimensional motion of a viscous, incompressible fluid in shallow water, are derived for use in any orthogonal coordinate system. Simplified equations for two dimensional motion are also developed. The equations are developed in terms of special coordinate dependent functions.