Revealing the Ion Chemistry Occurring in High Kinetic Energy-Ion Mobility Spectrometry: A Proof of Principle Study

Here, we present proof of principle studies to demonstrate how the product ions associated with the ion mobility peaks obtained from a High Kinetic Energy-Ion Mobility Spectrometer (HiKE-IMS) measurement of a volatile can be identified using a Proton Transfer Reaction/Selective Reagent Ion-Time-of-Flight-Mass Spectrometer (PTR/SRI-ToF-MS) when operating both instruments at the same reduced electric field value and similar humidities. This identification of product ions improves our understanding of the ion chemistry occurring in the ion source region of a HiKE-IMS. The combination of the two analytical techniques is needed, because in the HiKE-IMS three reagent ions (NO+, H3O+ and O2+•) are present at the same time in high concentrations in the reaction region of the instrument for reduced electric fields of 100 Td and above. This means that even with a mass spectrometer coupled to the HiKE-IMS, the assignment of the product ions to a given reagent ion to a high level of confidence can be challenging. In this paper, we demonstrate an alternative approach using PTR/SRI-ToF-MS that allows separate investigations of the reactions of the reagent ions NO+, H3O+ and O2+•. In this study, we apply this approach to four nitrile containing organic compounds, namely acetonitrile, 2-furonitrile, benzonitrile and acrylonitrile. Both the HiKE-IMS and the PTR/SRI-ToF-MS instruments were operated at a commonly used reduced electric field strength of 120 Td and with gas flows at the same humidities

High Kinetic Energy Ion Mobility Spectrometry- Mass Spectrometry investigations of four inhalation anaesthetics : isoflurane, enflurane, sevoflurane and desflurane

Here we report the first High Kinetic Energy-Ion Mobility Spectrometry-Mass Spectrometric (HiKE-IMSMS) investigations involving four fluranes; isoflurane, enflurane, sevoflurane and desflurane. Unlike standard (atmospheric pressure) IMS, HiKEIMS can detect these compounds in positive ion mode. This is because its low-pressure environment (similar to 14 mbar) and the associated short ion drift times in the HiKEIMS ensure the reagent ions O-2+(center dot) and H3O+ are present in the reaction region, and these can react with the fluranes by dissociative charge and proton transfer, respectively. However, their ion intensities are very dependent on the value of the reduced electric field (E/N) applied and the humidity of the air in the reaction region of the HiKE-IMS. In this paper we explore the potential use of HiKE-IMS for air quality control and breath analysis of fluranes. To help in the interpretation of the ion mobility spectra, and hence the ion-flurane chemistry occurring in reaction region, a HiKE-IMS was coupled to a Time-of-Flight Mass Spectrometer so that the m/z values of both the reagent and product ions that are contained within the various ion mobility peaks observed could be identified with a high level of confidence. The dependencies of the intensities of these ions as functions of E/N (30-115 Td) and humidity in the reaction region are reported. A number of product ions have been observed only under low humidity conditions (H2O volume-mixing ratio 100 ppm(v)), including CHF(2+)and CHFCl (+) for isoflurane and enflurane, CHF2(+), CF3(+) and C3H2F5O+ for desflurane, and CH3O+, CHF2+, C3H3F4O+, C4H3F6O+ and C4H3F6O+(H2O) for sevoflurane. It is interesting to note that CH3O+, CHF2+, CHFCl+ and CF3+ have shorter drift times than that measured for O-2(+center dot) This is explained by resonant charge transfer reaction processes occurring in the drift region: O-2(+center dot) + O-2 ? O-2+(center dot).O O-2 + O-2 +(center dot) (c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).Peer reviewe

High kinetic energy-ion mobility spectrometry-mass spectrometry investigations of several volatiles and their fully deuterated analogues

The first High Kinetic Energy-Ion Mobility Spectrometry-Mass Spectrometry (HiKE-IMS-MS) studies involving six volatiles (acetone, acetonitrile, methanol, ethanol, 2-propanol, and 1-butanol) and their fully deuterated analogues are reported. The goal is to further our understanding of the ion-molecule chemistry occurring in the HiKE-IMS. This is needed for its full analytical potential to be reached. Product ions are identified as a function of the reduced electric field (30-115 Td) and the influence of sample air humidity in the reaction region on deuterium/hydrogen (D/H) exchange reactions is discussed. Reagent ions include H3O+(H2O)(m), (n = 0, 1, 2 or 3), NO+(H2O)(n) (m = 0 or 1) and O-2(+center dot). Reactions with H3O+(H2O)(m), lead to protonated monomers (through either proton transfer or ligand switching). Reactions with NO+ involve association with acetone and acetonitrile, hydride anion abstraction from ethanol, 2-propanol, and 1-butanol, and hydroxide abstraction from 2-propanol and 1-butanol. With the exception of acetonitrile, O-2(+center dot) predominantly reacts with the volatiles via dissociative charge transfer. A number of sequential secondary ion-volatile processes occur leading to the formation of dimer and trimer-containing ion species, whose intensities depend on a volatile's concentration and the reduced electric field in the reaction region. Deuterium/hydrogen (D/H) exchange does not occur for product ions from acetone-d(6) and acetonitrile-d(3), owing to their inert methyl functional groups. For the deuterated alcohols, rapid D/H-exchange reaction at the hydroxy group is observed, the amount of which increased with the increasing humidity of the sample air and/or lowering of the reduced electric field.Peer reviewe

Tool mastering today – an interdisciplinary perspective

Tools have coined human life, living conditions, and culture. Recognizing the cognitive architecture underlying tool use would allow us to comprehend its evolution, development, and physiological basis. However, the cognitive underpinnings of tool mastering remain little understood in spite of long-time research in neuroscientific, psychological, behavioral and technological fields. Moreover, the recent transition of tool use to the digital domain poses new challenges for explaining the underlying processes. In this interdisciplinary review, we propose three building blocks of tool mastering: (A) perceptual and motor abilities integrate to tool manipulation knowledge, (B) perceptual and cognitive abilities to functional tool knowledge, and (C) motor and cognitive abilities to means-end knowledge about tool use. This framework allows for integrating and structuring research findings and theoretical assumptions regarding the functional architecture of tool mastering via behavior in humans and non-human primates, brain networks, as well as computational and robotic models. An interdisciplinary perspective also helps to identify open questions and to inspire innovative research approaches. The framework can be applied to studies on the transition from classical to modern, non-mechanical tools and from analogue to digital user-tool interactions in virtual reality, which come with increased functional opacity and sensorimotor decoupling between tool user, tool, and target. By working towards an integrative theory on the cognitive architecture of the use of tools and technological assistants, this review aims at stimulating future interdisciplinary research avenues

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

Revealing the Ion Chemistry Occurring in High Kinetic Energy-Ion Mobility Spectrometry: A Proof of Principle Study

Here, we present proof of principle studies to demonstrate how the product ions associated with the ion mobility peaks obtained from a High Kinetic Energy-Ion Mobility Spectrometer (HiKE-IMS) measurement of a volatile can be identified using a Proton Transfer Reaction/Selective Reagent Ion-Time-of-Flight-Mass Spectrometer (PTR/SRI-ToF-MS) when operating both instruments at the same reduced electric field value and similar humidities. This identification of product ions improves our understanding of the ion chemistry occurring in the ion source region of a HiKE-IMS. The combination of the two analytical techniques is needed, because in the HiKE-IMS three reagent ions (NO+, H3O+ and O2+•) are present at the same time in high concentrations in the reaction region of the instrument for reduced electric fields of 100 Td and above. This means that even with a mass spectrometer coupled to the HiKE-IMS, the assignment of the product ions to a given reagent ion to a high level of confidence can be challenging. In this paper, we demonstrate an alternative approach using PTR/SRI-ToF-MS that allows separate investigations of the reactions of the reagent ions NO+, H3O+ and O2+•. In this study, we apply this approach to four nitrile containing organic compounds, namely acetonitrile, 2-furonitrile, benzonitrile and acrylonitrile. Both the HiKE-IMS and the PTR/SRI-ToF-MS instruments were operated at a commonly used reduced electric field strength of 120 Td and with gas flows at the same humidities

Tool mastering today – an interdisciplinary perspective

Tools have coined human life, living conditions, and culture. Recognizing thecognitive architecture underlying tool use would allow us to comprehendits evolution, development, and physiological basis. However, the cognitiveunderpinnings of tool mastering remain little understood in spite of long-timeresearch in neuroscientific, psychological, behavioral and technological fields.Moreover, the recent transition of tool use to the digital domain poses newchallenges for explaining the underlying processes. In this interdisciplinary review,we propose three building blocks of tool mastering: (A) perceptual and motorabilities integrate to tool manipulation knowledge, (B) perceptual and cognitiveabilities to functional tool knowledge, and (C) motor and cognitive abilities tomeans-end knowledge about tool use. This framework allows for integratingand structuring research findings and theoretical assumptions regarding thefunctional architecture of tool mastering via behavior in humans and non-humanprimates, brain networks, as well as computational and robotic models. Aninterdisciplinary perspective also helps to identify open questions and to inspireinnovative research approaches. The framework can be applied to studies on thetransition from classical to modern, non-mechanical tools and from analogueto digital user-tool interactions in virtual reality, which come with increasedfunctional opacity and sensorimotor decoupling between tool user, tool, andtarget. By working towards an integrative theory on the cognitive architecture ofthe use of tools and technological assistants, this review aims at stimulating futureinterdisciplinary research avenues