Headspace analysis of new psychoactive substances using a Selective Reagent Ionisation-Time of Flight-Mass Spectrometer

The rapid expansion in the number and use of new psychoactive substances presents a significant analytical challenge because highly sensitive instrumentation capable of detecting a broad range of chemical compounds in real-time with a low rate of false positives is required. A Selective Reagent Ionisation-Time of Flight-Mass Spectrometry (SRI-ToF-MS) instrument is capable of meeting all of these requirements. With its high mass resolution (up to m/Δm of 8000), the application of variations in reduced electric field strength (E/N) and use of different reagent ions, the ambiguity of a nominal (monoisotopic) m/z is reduced and hence the identification of chemicals in a complex chemical environment with a high level of confidence is enabled. In this study we report the use of a SRI-ToF-MS instrument to investigate the reactions of H3O+, O2+, NO+ and Kr+ with 10 readily available (at the time of purchase) new psychoactive substances, namely 4-fluoroamphetamine, methiopropamine, ethcathinone, 4-methylethcathinone, N-ethylbuphedrone, ethylphenidate, 5-MeO-DALT, dimethocaine, 5-(2-aminopropyl)benzofuran and nitracaine. In particular, the dependence of product ion branching ratios on the reduced electric field strength for all reagent ions was investigated and is reported here. The results reported represent a significant amount of new data which will be of use for the development of drug detection techniques suitable for real world scenarios

On-line detection in liquid phase with PTR-MS : fundamentals and applications in chemistry and biology

PTR-MS (Protonen-Tausch-Reaktion Massenspektrometrie) ist eine weit verbreitete Spurengasanalysemethode. Allerdings besitzt diese hochempfindliche Technologie einen nennenswerten Nachteil, da sie flüchtige Komponenten ausschließlich in der Gasphase detektieren kann. Obwohl viele volatile organische Komponenten (VOCs), die in Flüssigkeiten gelöst sind, via Headspace-Analyse nachweisbar sind, ist eine solche Vorgehensweise im Falle von Spurenstoffen mit einer hohen Henry- Konstante (z.B. Sprengstoffe und PCB`s) nicht möglich. Daher versuchte ich im Rahmen meiner Dissertationsarbeit eine neue Methode für eine Analyse dieser Komponenten mit PTR-MS, welche als DAI (direct aqueous injection) bezeichnet wird, zu entwickeln sowie an möglichen Applikationen zu testen.PTR-MS (proton transfer reaction mass spectrometry) is a unique and by now well-established technology for trace gas analysis. Nevertheless, it has one considerable drawback, namely that it can only detect volatile compounds in the gas phase. Although it is possible to detect many volatile organic compounds (VOCs) in liquids via headspace analysis, such analysis is not possible for trace compounds with a high Henrys law constant (e.g. explosives, PCB`s) when they are present at low concentrations. Consequently in the course of this thesis I tried to develop and to explore a new solution which we call direct aqueous injection (DAI).by Simone JürschikEnth. u.a. 7 Veröff. d. Verf. aus den Jahren 2010 - 2013Innsbruck, Univ., Diss., 2014OeBB(VLID)17422

Selective Reagent Ion-Time-of-Flight-Mass Spectrometric Investigations of the Intravenous Anaesthetic Propofol and Its Major Metabolite 2,6-Diisopropyl-1,4-benzoquinone

The first detailed selected reagent ion-time-of-flight-mass spectrometric fundamental investigations of 2,6-diisopropylphenol, more commonly known as propofol (C12H18O), and its metabolite 2,6-diisopropyl-1,4-benzoquinone (C12H16O2) using the reagent ions H3O+, H3O+.H2O, O2+• and NO+ are reported. Protonated propofol is the dominant product ion resulting from the reaction of H3O+ with propofol up to a reduced electric field strength (E/N) of about 170 Td. After 170 Td, collision-induced dissociation leads to protonated 2-(1-methylethyl)-phenol (C9H13O+), resulting from the elimination of C3H6 from protonated propofol. A sequential loss of C3H6 from C9H13O+ also through collision-induced processes leads to protonated phenol (C6H7O+), which becomes the dominant ionic species at E/N values exceeding 170 Td. H3O+.H2O does not react with propofol via a proton transfer process. This is in agreement with our calculated proton affinity of propofol being 770 kJ mol−1. Both O2+• and NO+ react with propofol via a charge transfer process leading to two product ions, C12H18O+ (resulting from non-dissociative charge transfer) and C11H15O+ that results from the elimination of one of the methyl groups from C12H18O+. This dissociative pathway is more pronounced for O2+• than for NO+ throughout the E/N range investigated (approximately 60–210 Td), which reflects the higher recombination energy of O2+• (12.07 eV) compared to that of NO+ (9.3 eV), and hence the higher internal energy deposited into the singly charged propofol. Of the four reagent ions investigated, only H3O+ and H3O+.H2O react with 2,6-diisopropyl-1,4-benzoquinone, resulting in only the protonated parent at all E/N values investigated. The fundamental ion-molecule studies reported here provide underpinning information that is of use for the development of soft chemical ionisation mass spectrometric analytical techniques to monitor propofol and its major metabolite in the breath. The detection of propofol in breath has potential applications for determining propofol blood concentrations during surgery and for elucidating metabolic processes in real time

Incomplete synchrony of inflorescence scent emissions and thermogenesis in Arum maculatum L

International audienc

Compendium of the Reactions of H3O+ with Selected Ketones of Relevance to Breath Analysis Using Proton Transfer Reaction Mass Spectrometry

Soft chemical ionization mass spectrometric techniques, such as proton transfer reaction mass spectrometry (PTR-MS), are often used in breath analysis, being particularly powerful for real-time measurements. To ascertain the type and concentration of volatiles in exhaled breath clearly assignable product ions resulting from these volatiles need to be determined. This is difficult for compounds where isomers are common, and one important class of breath volatiles where this occurs are ketones. Here we present a series of extensive measurements on the reactions of H3O+ with a selection of ketones using PTR-MS. Of particular interest is to determine if ketone isomers can be distinguished without the need for pre-separation by manipulating the ion chemistry through changes in the reduced electric field. An additional issue for breath analysis is that the product ion distributions for these breath volatiles are usually determined from direct PTR-MS measurements of the compounds under the normal operating conditions of the instruments. Generally, no account is made for the effects on the ion-molecule reactions by the introduction of humid air samples or increased CO2 concentrations into the drift tubes of these analytical devices resulting from breath. Therefore, another motivation of this study is to determine the effects, if any, on the product ion distributions under the humid conditions associated with breath sampling. However, the ultimate objective for this study is to provide a valuable database of use to other researchers in the field of breath analysis to aid in analysis and quantification of trace amounts of ketones in human breath. Here we present a comprehensive compendium of the product ion distributions as a function of the reduced electric field for the reactions of H3O+. (H2O)n (n = 0 and 1) with nineteen ketones under normal and humid (100% relative humidity for 37 C) PTR-MS conditions. The ketones selected for inclusion in this compendium are (in order of increasing molecular weight): 2-butanone; 2-pentanone; 3-pentanone; 2-hexanone; 3-hexanone; 2-heptanone; 3-heptanone; 4-heptanone; 3-octanone; 2-nonanone; 3-nonanone; 2-decanone; 3-decanone; cyclohexanone; 3-methyl-2-butanone; 3-methyl-2-pentanone; 2-methyl-3-pentanone; 2-methyl-3-hexanone; and 2-methyl-3-heptanone.(VLID)4826166Version of recor

Distinguishing two isomeric mephedrone substitutes with selective reagent ionisation mass spectrometry (SRI-MS).

The isomers 4-methylethcathinone and N-ethylbuphedrone are substitutes for the recently banned drug mephedrone. We find that with conventional proton transfer reaction mass spectrometry (PTR-MS), it is not possible to distinguish between these two isomers, because essentially for both substances, only the protonated molecules are observed at a mass-to-charge ratio of 192 (C12 H18 NO(+) ). However, when utilising an advanced PTR-MS instrument that allows us to switch the reagent ions (selective reagent ionisation) from H3 O(+) (which is commonly used in PTR-MS) to NO(+) , O2 (+) and Kr(+) , characteristic product (fragment) ions are detected: C4 H10 N(+) (72 Da) for 4-methylethcathinone and C5 H12 N(+) (86 Da) for N-ethylbuphedrone; thus, selective reagent ionisation MS proves to be a powerful tool for fast detection and identification of these compounds