Radical cation/radical reactions: A Fourier transform ion cyclotron resonance study of allyl radical reacting with aromatic radical cations

Russell, Amber L.; Rohrs, Henry W.; Read, David; Giblin, Daryl; Gaspar, Peter P.; Gross, Michael L.

doi:10.1016/j.ijms.2008.11.002

Cited by 11 publications

(12 citation statements)

References 35 publications

(30 reference statements)

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“…Hence, in the case of o -OHMA in the same MS/MS conditions, the m/z 135.0 ion is more intense than the m/z 106.9 ion. Increased collision energy can lead to further elimination of ethylene from the C 9 H 11 O + ion, which involves only a proton transfer and two facile hydride transfers leading to C-C bond cleavage and creation of the C 7 H 7 O + ion 26 . Figure 4 shows the proposed fragmentation pathways for each isomer of OHMA: a) ortho- , b) meta- , and c) para- .…”

Section: Resultsmentioning

confidence: 99%

“…The novel workflow proposed in this study incorporates sample preparation, extensive fractionation, and analysis by liquid chromatography (LC) in which two columns with different characteristics were connected in tandem. We diminished the very high dynamic range of the synthetic media’s concentration of components (from a few to 1000 mM of glucose, amino acids, phenol red, sodium bicarbonate, and sodium pyruvate, from a few to 200 µM of vitamins and antibiotics) and the much lower levels of macrophages’ secreted metabolites (from a few to hundreds of nM typical levels of biomarkers in blood 26 ). This allowed us to perform a comprehensive investigation of macrophages’ secreted metabolome upon exposure to Meth.…”

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confidence: 99%

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Secreted Metabolome of Human Macrophages Exposed to Methamphetamine

et al. 2019

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Macrophages comprise a major component of the human innate immune system that is involved in maintaining homeostasis and responding to infections or other insults. Besides cytokines and chemokines, macrophages presumably influence the surrounding environment by secreting various types of metabolites. Characterization of secreted metabolites under normal and pathological conditions is critical for understanding the complex innate immune system. To investigate the secreted metabolome, we developed a novel workflow consisting of one Reverse Phase (RP) C18 column linked in tandem with a Cogent cholesterol modified RP C18. This system was used to compare the secreted metabolomes of human monocyte derived macrophages (hMDM) under normal conditions to those exposed to methamphetamine (Meth). This new experimental approach allowed us to measure 92 metabolites, identify 11 of them as differentially expressed, separate and identify three hydroxymethamphetamine (OHMA) isomers, and identify a new, yet unknown metabolite with m/z of 192. This study is the first of its kind to address the secreted metabolomic response of hMDM to an insult by Meth. Besides the discovery of novel metabolites secreted by macrophages, we provide a novel methodology to investigate metabolomic profiling.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Secreted Metabolome of Human Macrophages Exposed to Methamphetamine

et al. 2019

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“…[190] Pulspyrolysedüsen wurden auch an Mikrowellen- [191] und Millimeterwellenspektrometer [192] angepasst, ebenso wie an ein Ionenfallen-Massenspektrometer, [193] welches zur Generierung von C 3 H 2 aus 1,3-Dibrompropin [siehe Gl. [194] Phosphornitrid, PN, wurde durch gepulste Pyrolyse von Dimethylphosphoramidat in Ar bei ca. (51)] wurde mittels ICR-Massenspektrometrie verfolgt.…”

Section: Gepulste Pyrolyse (Strahlexpansions-fvp)unclassified

“…(51)] wurde mittels ICR-Massenspektrometrie verfolgt. [194] Phosphornitrid, PN, wurde durch gepulste Pyrolyse von Dimethylphosphoramidat in Ar bei ca. 900 8 8Cg eneriert [Gl.…”

Section: Gepulste Pyrolyse (Strahlexpansions-fvp)unclassified

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Wentrup

2017

Angewandte Chemie

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Die Anfänge der Flash‐Vakuumpyrolyse (FVP) ergaben sich in den 1940er und 1950er Jahren hauptsächlich aus dem massenspektrometrischen Nachweis pyrolytisch entstandener freier Radikale. In den 1960er Jahren begannen Organiker mit der Durchführung von FVP‐Experimenten zum Zweck der Isolierung neuer und interessanter Verbindungen und zum Verständnis pyrolytischer Prozesse. Seitdem wurden viele unterschiedliche Typen von Apparaten und Techniken entwickelt. Zielsetzung dieses Aufsatzes ist es, die wichtigsten Methoden vorzustellen wie auch eine Übersicht über typische Reaktionen und Beobachtungen zu geben, die mit den verschiedenen Techniken erreicht werden können. Dies umfasst unter anderem präparative FVP, chemische Abfangreaktionen, Matrixisolierung sowie Tieftemperatur‐Spektroskopie reaktiver Intermediate und instabiler Moleküle. Darüber hinaus ist die Kombination von FVP mit Matrixisolierung und Photochemie ein wirkungsvolles Instrument für Untersuchungen von Reaktionsmechanismen.

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“…Similarly, product identification, mechanistic insight, and rough determination of rate constants were achieved by the Gross group using a Chen nozzle coupled to a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer for reactions of the benzyl radical cation with a variety of pyrolysis products including the allyl radical. 8 Relatedly, ion-radical reactions have been used in chemical detection schemes. For instance, proton transfer from water-solvated H 3 O + has been investigated as a detection scheme for peroxy radicals, producing the radicals by photolyzation in a flow reactor, with again rough estimates of the reaction rates being determined.…”

Section: ■ Introductionmentioning

confidence: 99%

Kinetics and Product Branching Fractions of Reactions between a Cation and a Radical: Ar⁺ + CH₃ and O₂⁺ + CH₃

et al. 2015

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A novel technique is described for the measurement of rate constants and product branching fractions of thermal reactions between cation and radical species. The technique is a variant of the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, employing a flowing afterglow-Langmuir probe apparatus. A radical species is produced in situ via dissociative electron attachment to a neutral precursor; this allows for a quantitative derivation of the radical concentration and, as a result, a quantitative determination of rate constants. The technique is applied to the reactions of Ar(+) and O2(+) with CH3 at 300 K. The Ar(+) + CH3 reaction proceeds near the collisional rate constant of 1.1 × 10(-9) cm(3) s(-1) and has three product channels: → CH3(+) + Ar (k = 5 ± 2 × 10(-10) cm(3) s(-1)), → CH2(+) + H + Ar (k = 7 ± 2 × 10(-10) cm(3) s(-1)), → CH(+) + H2 + Ar (k = 5 ± 3 × 10(-11) cm(3) s(-1)). The O2(+) + CH3 reaction is also efficient, with direct charge transfer yielding CH3(+) as the primary product channel. Several results needed to support these measurements are reported, including the kinetics of Ar(+) and O2(+) with CH3I, electron attachment to CH3I, and mutual neutralization of CH3(+) and CH2(+) with I(-).

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Radical cation/radical reactions: A Fourier transform ion cyclotron resonance study of allyl radical reacting with aromatic radical cations

Cited by 11 publications

References 35 publications

Secreted Metabolome of Human Macrophages Exposed to Methamphetamine

Secreted Metabolome of Human Macrophages Exposed to Methamphetamine

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Kinetics and Product Branching Fractions of Reactions between a Cation and a Radical: Ar⁺ + CH₃ and O₂⁺ + CH₃

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Radical cation/radical reactions: A Fourier transform ion cyclotron resonance study of allyl radical reacting with aromatic radical cations

Cited by 11 publications

References 35 publications

Secreted Metabolome of Human Macrophages Exposed to Methamphetamine

Secreted Metabolome of Human Macrophages Exposed to Methamphetamine

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

Kinetics and Product Branching Fractions of Reactions between a Cation and a Radical: Ar+ + CH3 and O2+ + CH3

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Kinetics and Product Branching Fractions of Reactions between a Cation and a Radical: Ar⁺ + CH₃ and O₂⁺ + CH₃