Identification of fentanyl derivatives at trace levels with nonaqueous capillary electrophoresis-electrospray-tandem mass spectrometry (MS(n), n = 2, 3): analytical method and forensic applications.

The identification of fentanyl derivatives at trace levels employing capillary electrophoresis coupled to electrospray ionization tandem mass spectrometry (CE-ESI-MS(n) , n = 2, 3) is presented. The studied synthetic opioid fentanyl and its derivatives have an exceeding analgesic potency which can be up to 8000 times higher that of morphine. Apart from their therapeutical applications, there is an abuse of them in the drug scene as a heroin substitute. The identification of these opioids at trace levels is of further significant forensic interest with respect to recent seizures of clandestine fentanyl laboratories in Germany. In this work, a nonaqueous capillary electrophoresis (NACE)-ESI-MS(n) procedure was developed for the separation and identification of six fentanyl derivatives including fentanyl, cis- and trans-methylfentanyl, sufentanil, alfentanil, and carfentanil. Their fragmentation pattern in MS(n) experiments were investigated as well as the influence of the sheath-liquid mixture and the influence of the inside diameter of the fused silica capillary on the peak shape and the signal to noise ratio. Method validation included determination of the detection limits (about 1-2 nmol/L) and the repeatability of migration time (at most 0.07% relative standard deviation). The NACE-MS procedure was successfully applied for the analysis of real samples from seizures in illegal fentanyl laboratories.

Investigation of the photoionization properties of pharmaceutically relevant substances by resonance-enhanced multiphoton ionization spectroscopy and single-photon ionization spectroscopy using synchrotron radiation.

The photoionization properties of the pharmaceutically relevant substances amantadine, diazepam, dimethyltryptamine, etomidate, ketamine, mescaline, methadone, and propofol were determined. At beamline U125/2-10m-NIM of the BESSY II synchrotron facility (Berlin, Germany) vacuum ultraviolet (VUV) photoionization spectra were recorded in the energy range 7.1 to 11.9 eV (174.6 to 104.2 nm), showing the hitherto unknown ionization energies and fragmentation appearance energies of the compounds under investigation. Furthermore, (1+1)-resonance-enhanced multiphoton ionization (REMPI) spectra of selected compounds (amantadine, diazepam, etomidate, ketamine, and propofol) were recorded by a continuous scan in the energy range between 3.6 and 5.7 eV (345 to 218 nm) using a tunable optical parametric oscillator (spectral resolution: 0.1 nm) laser system. The resulting REMPI wavelength spectra of these compounds are discussed and put into context with already known UV absorption data. Time-of-flight mass spectrometry was used for ion detection in both experiments. Finally, the implications of the obtained physical-chemical results for potential analytical applications are discussed. In this context, fast detection approaches for the considered compounds from breath gas using photoionization mass spectrometry and a rapid pre-concentration step (e.g., needle trap device) are of interest.

Identification of toxic oligopeptides in Amanita fungi employing capillary electrophoresis-electrospray ionization-mass spectrometry with positive and negative ion detection.

The identification of toxic oligopeptides employing CE-ESI-MS is presented. The analytes studied ama- and phallotoxins are of significant forensic interest because over 90% of the lethal cases of fungus poisoning in man are caused by species of Amanita which contain these toxins. A CE method was developed to separate the toxins alpha-, beta- and gamma-amanitin, phalloidin and phallacidin. Their fragmentation patterns in MS(n) experiments were investigated in the positive and in the negative ion mode, also the influence of the sheath liquid mixture of the used interface on the S/N. Method validation included the determination of the LOD and the repeatability of the migration time and peak area for both detection modes. With the optimized method LODs of 13-79 ng/mL (17-87 nmol/L) were reached. The CE-MS procedure was successfully applied to the identification of ama- and phallotoxins in extracts of air-dried mushroom samples.