Liquid Extraction Surface Analysis (LESA) Electron-Induced Dissociation and Collision-Induced Dissociation Mass Spectrometry of Small Molecule Drug Compounds

Here, we present liquid extraction surface analysis (LESA) coupled with electron-induced dissociation (EID) mass spectrometry in a Fourier-transform ion cyclotron resonance mass spectrometer for the analysis of small organic pharmaceutical compounds directly from dosed tissue. First, the direct infusion electrospray ionisation EID and collision-induced dissociation (CID) behaviour of erlotinib, moxifloxacin, clozapine and olanzapine standards were compared. EID mass spectra were also compared with experimental or reference electron impact ionisation mass spectra. The results show that (with the exception of erlotinib) EID and CID result in complementary fragment ions. Subsequently, we performed LESA EID MS/MS and LESA CID MS/MS on singly charged ions of moxifloxacin and erlotinib extracted from a thin tissue section of rat kidney from a cassette-dosed animal. Both techniques provided structural information, with the majority of peaks observed for the drug standards also observed for the tissue-extracted species. Overall, these results demonstrate the feasibility of LESA EID MS/MS of drug compounds from dosed tissue and extend the number of molecular structures for which EID behaviour has been determined.

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Analysis of glyphosate and glufosinate by capillary electrophoresis-mass spectrometry utilising a sheathless microelectrospray interface

The potential of capillary electrophoresis combined with mass spectrometry for the simultaneous determination of two herbicides (glyphosate and glufosinate) and their metabolites (aminomethylphosphonic acid and methylphosphinicopropionic acid) as the native species is demonstrated utilising a simple microelectrospray interface. The interface uses the voltage applied to the CE capillary to drive separation and generate the electrospray, avoiding sample dilution associated with the use of a sheath liquid interface. The chemistry of the internal walls of the capillary has a marked influence on peak shape, and appropriate choice is essential to successful operation of the interface. A linear polyacrylamide coated capillary, which has no electroosmotic flow, gave best reproducibility, with precision of migration time and peak area in the range 1-2 and 7-12% RSD, respectively, for the four analytes. Limits of detection, low-pg on-column, are substantially better than for previous methods and calibration curves over the range 1-100 microM have R2 values greater than 0.97. The observed concentration limit of detection for glyphosate in water is 1 microM and for a water-acetone extract of wheat is 2.5 microM, allowing the underivatised herbicide to be detected at 10% of the maximum residue limit in wheat.     

On-site monitoring of trace levels of free manganese in sea water via sonoelectroanalysis using a boron-doped diamond electrode

Cathodic stripping voltammetry at a boron-doped diamond electrode utilising an insonated accumulation protocol is shown to be possible for the on-site trace detection of free manganese in seawater samples. No sample pre-treatment is required with the application of ultrasound providing a sensitive and selective protocol for the analysis of manganese. The protocol is used in the evaluation of manganese in seawater samples taken near the site of a former ferromanganese factory in the town Šibenik, Croatia.     

Exploration of gas sensing possibilities with edge plane pyrolytic graphite electrodes: nitrogen dioxide detection

The voltammetric response of nitrogen dioxide in aqueous sulfuric acid using an edge plane pyrolytic graphite electrode has been explored and contrasted with that from basal plane pyrolytic graphite, glassy carbon or boron-doped diamond electrodes. Edge plane graphite electrode is found to produce an excellent voltammetric signal in comparison with other carbon-based electrodes exhibiting a well-defined analytically useful voltammetric redox couple in 2.5 M sulfuric acid which is absent on the alternative electrodes.     

A portable, photon analysis spectrometer for the assay of X- and gamma-ray emitting radionuclides

A portable, battery-powered, multichannel analyzer (MCA) for use with Ge spectrometers has been developed for in-field use for the assay of x-and γ-ray emitting radionuclides. The spectrometer is capable of operating to rates greater than 150,000 counts per second. The analyzer is a Canberra InSpector MCA, that is equipped with the INEEL ultra-stable dual-energy pulser, and pulse injection with subsequent removal (PISR) circuitry. PCGAP, a set of MCA control and spectral analysis programs, was developed for use on a PC with a Windows NT Operating System. It includes an interactive peak analysis program as well as automatic spectral analysis programs for the X- and γ-ray regions, and a number of utility programs. The pulser peaks are calibrated with radioactive sources in terms of energy (i.e., their energy equivalents are measured) using the PCGAP spectral analysis package so that energy shifts, including those due to changes in temperature or count rate, do not cause a loss of energy calibration. The number of injected low- and high-energy-equivalent pulses is known so the stored pulser pulses can be used for a dead-time and random summing correction. The pulser peaks are also used to monitor any deterioration in spectral quality caused by noise, ground loops, etc. The results of performance tests to demonstrate the capabilities of this pulser-equipped InSpector are reported.     

The influence of the amount of stationary phase and nature of solid support on retention indices

Summary It is shown that the retention indices of polar solutes are affected by the amount of stationary phase in the column. The retention indices increase with decreasing stationary phase loadings. The reasons for this behavior are most likely due to the existence of mixed retention mechanisms. At low amounts of stationary phases, adsorption on the support or column walls can take place. Studies were made using four supports, two of which were Chromosorb W and the other two Chromosorb P. The effects of changing the liquid phase loadings are more pronounced when using Chromosorb P.