High-performance liquid chromatographic determination of morphine and its 3- and 6-glucuronide metabolites: improvements to the method and application to stability studies

Improvements to previously reported methods for the determination of morphine, morphine-3-glucuronide (M3G) and morphine-6-glucuronide (M6G) in human plasma are described. The improved methods involve the use of a solid-phase extraction cartridge and a chromatographic system which uses paired-ion reversed-phase high-performance liquid chromatography with a radially compressed column. Only one cartridge is used to prepare each sample for chromatography and each cartridge may be used for at least fourteen 1-ml plasma samples. The recovery is greater than 85%. The improvements to the method of sample pretreatment and in the chromatographic conditions have allowed determination of morphine, M3G and M6G in human plasma down to 13.3 nmol/l (coefficient of variation = 9.3%), 108 nmol/l (6.6%) and 41 nmol/l (6.7%), respectively, using ultraviolet detection alone. It was shown that all three compounds were stable in plasma for up to 101 weeks when stored at -20 degrees C.     

Elucidating the mode of action of a corrosion inhibitor for iron

Two polymetallic iron(III) complexes 1 and 2 have been synthesised from the known corrosion inhibitor 3-(4-methylbenzoyl)-propionic acid HL1 and their crystal structures determined. Coordination geometries extracted from these structures have been used as the basis for molecular modelling onto idealised iron(III) oxide surfaces as an aid to understanding the efficacy of inhibitors of the 4-keto acid type. The proposed mode of action involves 1,3-bridging didentate coordination of the carboxylate function of L1 to two FeIII ions, hydrogen-bond formation between the 4-keto group of L1 and a bridging surface hydroxy group, as well as close packing of the aromatic end groups, which should generate a hydrophobic barrier on the surface. Adsorption isotherm experiments have been used to compare the strengths of binding of related carboxylic acids onto iron(III) oxide surfaces and indicate that the presence of the 4-keto function leads to the formation of significantly more stable surface complexes.     

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.     

Simple method for the assay of linezolid in Brain Heart Infusion broth by high-performance liquid chromatography

A simple HPLC method was developed and validated for quantification of linezolid in Brain Heart Infusion (BHI) broth. Eperezolid was employed as internal standard and the sample pre-treatment procedure was simple. Calibration standards ranged from 0.05 to 16 mg/L. Accuracy was within 7.8% and reproducibility (RSD) was less than 8.3%. Recovery was approximately 100% at all concentrations examined. Linezolid was stable in the autosampler insert for at least 24 h at ambient temperature and in BHI for 72 h at 37 degrees C. This assay is rapid and ideal for analysis of a large number of samples.     

Electron beam generation using a ferroelectric cathode

Data is presented on the production of electron beams from a ferroelectric cathode at voltages of order 0.5 MV and current densities of order 100 A/cm². In comparison with data at lower voltages, the beam current scales as the three-halves-power of the voltage. An interpretation of the voltage dependent scaling, based on the coupling of electrostatic energy from the ferroelectric to the gun, is presented     

Results from an X-band coaxial extended length cavity

Experiments and simulations demonstrate high-power microwave generation at 9 GHz in a coaxial geometry. The 9 cm diameter annular electron beam is propagated between inner and outer drift tube conductors, a configuration which increases the beam current and reduces the structure fields from existing high-power sources, Since the TEM mode of the coaxial guide reduces the quality factor of small-gap cavities, especially at high frequency, the interaction is provided by an extended length cavity loaded with dielectric. A single 16 cm cavity generates 200 MW of power from the 400 keV, 7 kA electron beam. Although the cavity can oscillate at a number of resonances, a single mode is selected with 10-30 kW of input power from a magnetron. A coupler samples 25 MW of the power from the interaction region, precisely measured using a single-shot calorimeter. Simulations indicate that the efficiency of the device is limited to 7% by saturation effects, and can be improved by reducing the length of the cavity