Analysis of terbutaline in human plasma by high-performance liquid chromatography with electrochemical detection using a micro-electrochemical flow cell.

A high-performance liquid chromatographic method is described for the determination of terbutaline in human plasma in the range 1-35 ng/ml. Detection was achieved using a carbon fibre micro-electrochemical detector and a column-switching system. The microelectrode cell has advantages over conventional glassy carbon electrode-based detection systems in that it is easy to prepare, flexible in its operation and suffers less trouble from problems such as air bubbles and leaks. Furthermore, it has a better detection limit for terbutaline (0.8 ng/ml) to that obtained using a conventional glassy carbon electrode flow detector (2 ng/ml). Sample clean-up was by on-line solid-phase extraction with column switching, providing a method which was sensitive and reproducible, where the mean overall coefficient of variation was 5.60% and drug recovery in excess of 86% at the concentration levels studied.     

Determination of kinetic parameters for the inhibitory effects of organic sulphides on an amperometric peroxide biosensor in non-aqueous media

The amperometric detection of some organic sulphides in non-aqueous media using a horseradish peroxidase modified platinum electrode is reported. The performance of the electrode is based on the inhibitory effect of sulphides on the activity of peroxidase. The electrode responds rapidly to micromolar concentrations of the sulphides with linearities extending up to 0.4, 0.25 and 0.8 mmol/dm(3) for thiourea, ethylenethiourea, and mercaptoethanol, respectively. The current as peroxide concentration approaches infinity in the absence of any inhibitor (I(max)), and the apparent inhibition constant (K'(i)) for each inhibitor were evaluated. I(max)/K'(i), i.e. the percentage inhibition of sensor response per millimolar of each inhibitor, was calculated and used as a measure of the performance of the sensor in the determination of the organic sulphides. From these values the sensitivity trend of the biosensor for the organic sulphides is ethylenethiourea > thiourea > mercaptoethanol. The kinetic effects of other operational parameters such as mediator concentration, water content of the solvent and working potential were also evaluated to assess analytical performance.     

Radical concentration measurements in hydrocarbon diffusion flames

Absolute OH· concentrations and relative H-atom and O-atom profiles have been measured in a laminar, co-flowing methane/air diffusion flame burning at atmospheric pressure. Laser absorption and laser-induced fluorescence methods were used to probe the A ² X ²II_itransition in OH·. The maximum OH· concentration is found to be 1.8±0.2 ×10¹⁶ cm^–3 (mole fraction =5.0×10^–3) at a temperature of 2080 K, which is twice the value calculated assuming local total equilibrium but less than half that predicted from partial equilibrium (O₂+H₂ 2OH·). Multiphoton ionization (2+1 process at 243 nm) has been used to detect H atoms, while laser-induced fluorescence at 845 nm excited by two-photon absorption at 226 nm was employed to observe O atoms. In both cases it was found that low photon intensities (2×10⁸W/cm²) and a retroreflected beam, Doppler-free geometry was required in order to avoid the photolytic production of the species of interest. For all of the concentration profile data it is necessary to correct the raw signals for variations in collisional quenching. In the case of the multiphoton ionization measurements the variation in electron detection sensitivity as a function of flame position must be accounted for as well. Establishing absolute H-atom and O-atom concentrations is discussed in terms of partial equilibrium considerations and detailed flame structure calculations.Formerly the National Bureau of Standards     

Lagrange solution for three wavelength solitary wave clusters in nematic liquid crystals

We investigate the interaction of three optical solitary waves propagating with angular momentum in bulk nematic liquid crystals. The resulting cluster of solitary waves, or nematicons, is shown to orbit about its common centre of “mass”. An elongated isosceles triangle configuration is derived, this solution being the equivalent of the Lagrange solution of Newtonian gravitation. This triangle solution is found to be stable owing to diffractive radiation. A modulation theory explains the existence of the triangle solution as due to the non-monotonicity of an effective potential for the interaction of the solitary waves. This modulation theory also gives good agreement with numerical solutions for the trajectories of the nematicons in the three colours. Finally, it is shown that a cut-off in the shed diffractive radiation prevents the break-up of the triangle due to radiative losses.     

Assay of flurazepam in plasma by differential pulse polarography

Analytical and Bioanalytical Chemistry - A combination of differential solvent extraction based on physical chemical properties of the species involved and differential pulse polarography has been...     

Synergies between micropreparative high-performance liquid chromatography and an instrumental optical biosensor

The recent development of an automated surface plasmon resonance technology for the measurement of biomolecular interactions (Pharmacia BIAcore) has provided new opportunities for the detection and analysis of protein-protein interactions. In the BIAcore, detection is based on changes in surface plasmon resonance which are monitored optically. Changes in surface plasmon resonance correspond to changes in surface concentration of macromolecules and can be monitored in real time.

We have found that the detection sensitivity obtainable with this technology (ng/ml concentrations of specific ligands are readily detectable for many applications) is complementary “in a bidirectional manner” to micropreparative HPLC. Thus micropreparative HPLC may be used to purify and characterise reagents for the biosensor, whilst the biosensor may be used to define chromatographic parameters such as elution conditions for affinity chromatography or serve as an affinity detector for fractions obtained during chromatographic purification.

Examples of such applications, including the potential of the biosensor to search for and monitor the purification of unknown ligands for which the target molecule has been identified, are shown. In particular, the use of the biosensor to monitor the purification of soluble epidermal growth factor receptor from A431 cell conditioned media is demonstrated.     

High-performance liquid chromatographic analysis of ampicillin and cloxacillin and its application to an intramammary veterinary preparation

Summary Reverse phase high-performance liquid chromatography with ultra-violet detection has been used for the simultaneous identification and determination of ampicillin, cloxacillin and some of their degradation products following their extraction from an intramammary preparation used in veterinary medicine. Extraction of the intramammary base into petroleum ether (40–60°C) and partition of the penicillins into the mobile phase gave a mean recovery of 100.8% for ampicillin with coefficient of variation of 1.0 and 103.4% for cloxacillin with coefficient of variation of 1.2 (n=6). Using optimised HPLC conditions ampicillin eluted in approximately 2 min and cloxacillin in approximately 8 min. The overall method was found to be stability indicating, since cloxacillin and ampicillin eluted independently of their degradation products.     

A journey through quality control

The Euroanalysis VII conference in Vienna included a two-day session: Quality Assurance in Analytical Chemistry. The contributions comprised 15 lectures devoted to: intra-laboratory quality measures, inter-laboratory control, formal aspects and accreditation and implementation. The paper presents an overview of the main items developed by the contributors.A survey on the session on Quality Assurance in Analytical Chemistry of Euroanalysis VIIThe authors thank the organizers of EUROANALYSIS VII and in particular Dr. B. Griepink and Dr. E. Maier of the Community Bureau of Reference (BCR) of the CEC for their support and considerable contributions.     

Monensin carry-over into unmedicated broiler feeds.

European Union Member States are now required to monitor poultry meat for the presence of coccidiostat residues. Among other factors contributing to the production of residue-free food is the ability of animal feed manufacturers to produce medication-free feedstuffs, ensuring the proper observance of withdrawal periods prior to slaughter. Carry-over of medication was investigated in a local poultry feed mill that was using monensin as its principal coccidiostat for broilers. Monensin, at levels in excess of 5% of the therapeutic dose (approximately 110 mg kg-1), was present in 22.5% of 40 withdrawal feeds. Subsequent studies in the mill indicated that most of the contamination occurred during the processing of feeds after the mixing stage. The mill altered its manufacturing process as a result of this study. The consequence of this was that the incidence of monensin withdrawal feeds, at levels greater than 5% of the therapeutic dose, fell from 22.5 to 2.5%. This collaborative study has helped the feed compounder to produce more effective withdrawal feeds, thereby reducing the potential exposure of consumers to unwanted residues of monensin in poultry meat.     

Application of electrospray mass spectrometry in the detection and determination of Remazol textile dyes.

The electrospray (ES) behaviour of selected Remazol textile dyes, their hydrolysis products and the latters' reaction, following elution from a strong anion-exchange cartridge, with 30% concentrated HCl in MeOH, is studied and applied to the direct analysis of dye containing effluent. For unambiguous identification and determination of these textile dyes in effluents, it is necessary to resort to ES utilising MS-MS and MS3. Further, a tabular review of recent applications of HPLC-ES-MS and, to a lesser extent, CE-ES-MS with reference to drug and pesticide analysis is presented.