Conservation of dimer peak intensity in ion mobility spectrometers with ketone-doped carrier gas

Puton, Jarosław; Augustyniak, Dariusz; Perycz, Urszula; Witkiewicz, Zygfryd

doi:10.1016/j.ijms.2014.09.008

Cited by 12 publications

(13 citation statements)

References 21 publications

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“…It is very interesting that the same analyte ions are obtained for different reaction mechanisms available for ionization by these two kinds of reactant ions. A similar phenomenon has already been observed for DMMP and TEP detected in the presence of ketone dopants [ 20 ]. However, this only concerned the conservation of dimer ions peaks intensities, while the monomer ions peaks were different depending on whether ketone dopants or pure carrier gas were used.…”

Section: Resultssupporting

confidence: 83%

“…Parameters of the IMSD-B detector used for this research and a schematic of its reaction section are presented in [ 20 ]. It is a precise instrument dedicated for laboratory purposes.…”

Section: Methodsmentioning

confidence: 99%

“…Their presence may affect the detection efficiency and LOD. It was stated, however, that in the detection of organophosphorus compounds (OPC) using ketones as dopants, the detection sensitivity does not depend on the presence and concentration of the dopant [ 19 , 20 ].…”

Section: Introductionmentioning

confidence: 99%

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Nitrogen oxides as dopants for the detection of aromatic compounds with ion mobility spectrometry

et al. 2017

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Limits of detection (LODs) in ion mobility spectrometry (IMS) strictly depend on ionization of the analyte. Especially challenging is ionization of compounds with relatively low proton affinity (PA) such as aromatic compounds. To change the course of ion-molecule reactions and enhance the performance of the IMS spectrometer, substances called dopants are introduced into the carrier gas. In this work, we present the results of studies of detection using nitrogen oxides (NOx) dopants. Three aromatic compounds, benzene, toluene, toluene diisocyanate and, for comparison, two compounds with high PA, dimethyl methylphosphonate (DMMP) and triethyl phosphate (TEP), were selected as analytes. The influence of water vapour on these analyses was also studied. Experiments were carried out with a generator of gas mixtures that allowed for the simultaneous introduction of three substances into the carrier gas. The experiments showed that the use of NOx dopants significantly decreases LODs for aromatic compounds and does not affect the detection of compounds with high PA. The water vapour significantly disturbs the detection of aromatic compounds; however, doping with NOx allows to reduce the effect of humidity. Graphical AbstractTwo possible ionization mechanisms of aromatic compounds in ion mobility spectrometry: proton transfer reaction and adduct formation

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Section: Resultssupporting

confidence: 83%

“…Parameters of the IMSD-B detector used for this research and a schematic of its reaction section are presented in [ 20 ]. It is a precise instrument dedicated for laboratory purposes.…”

Section: Methodsmentioning

confidence: 99%

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Nitrogen oxides as dopants for the detection of aromatic compounds with ion mobility spectrometry

et al. 2017

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“…For compounds with high values of PA (e.g., DMMP), the efficiency of dimer ion formation does not depend on the concentration of the dopant. The same results were obtained when the higher ketones were used as dopants [87]. The explanation of the lack of dependence between dimer peak intensity and dopant concentration is not simple due to the fact that, in this case, not only ionization kinetics must be considered but also the ion transport phenomena affecting concentrations of reactant and product ions.…”

Section: Quantitative Aspects Of Using Dopantssupporting

confidence: 64%

Dopants and gas modifiers in ion mobility spectrometry

Waraksa

Perycz

Namieśnik

et al. 2016

TrAC Trends in Analytical Chemistry

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“…There were only a few previous studies of the specific further reactions of the AH + (H 2 O) n ions with polar molecules M in IMS, − yet they are involved in SESI-MS, , for example These reactions produce proton-bound mixed dimers or hydrated protonated M. When the concentration of M is high enough, secondary reactions can occur that replace the H 2 O molecules, and even replace the molecule A, forming the symmetrical dimer. Clearly, in mixtures of polar molecules A and M, whatever their type, ligand switching ion chemistry can become very complicated, and an analysis by SESI-MS and IMS will be difficult. This is even more so if the rate coefficients for the reactions are not known.…”

Section: Introductionmentioning

confidence: 99%

Ligand Switching Ion Chemistry: An SIFDT Case Study of the Primary and Secondary Reactions of Protonated Acetic Acid Hydrates with Acetone

Spesyvyi

Lacko

Dryahina

et al. 2021

J. Am. Soc. Mass Spectrom.

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A study was performed of the reactions of protonated acetic acid hydrates, CH3COOHH+(H2O) n , with acetone molecules, CH3COCH3, using a selected ion flow-drift tube (SIFDT). The rationale for this study is that hydrated protonated organic molecules are major product ions in secondary electrospray ionization mass spectrometry (SESI-MS) and ion mobility spectrometry (IMS). Yet the formation and reactivity of these hydrates are only poorly understood, and kinetics data are only sparse. The existing SIFDT instrument in our laboratory was upgraded to include an octupole ion guide and a separate drift tube by which hydrated protonated ions can be selectively injected into the drift tube reactor and their reactions with molecules studied under controlled conditions. This case study shows that, in these hydrated ion reactions with acetone molecules, the dominant reaction process is ligand switching producing mostly proton-bound dimer ions (CH3COCH3)H+(CH3COOH), with minor branching into (CH3COCH3)H+(H2O). This switching reaction was observed to proceed at the collisional rate, while other studied hydrated ions reacted more slowly. An attempt is made to understand the reaction mechanisms and the structures of the reaction intermediate ions at the molecular level. Secondary switching reactions of the asymmetric proton-bound dimer ions lead to a formation of strongly bound symmetrical dimers (CH3COCH3)2H+, the terminating ion in this ion chemistry. These results strongly suggest that, in SESI-MS and IMS, the presence of a polar compound, like acetone in exhaled breath, can suppress the analyte ions of low concentration compounds like acetic acid thus compromising their quantification.

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Conservation of dimer peak intensity in ion mobility spectrometers with ketone-doped carrier gas

Cited by 12 publications

References 21 publications

Nitrogen oxides as dopants for the detection of aromatic compounds with ion mobility spectrometry

Nitrogen oxides as dopants for the detection of aromatic compounds with ion mobility spectrometry

Dopants and gas modifiers in ion mobility spectrometry

Ligand Switching Ion Chemistry: An SIFDT Case Study of the Primary and Secondary Reactions of Protonated Acetic Acid Hydrates with Acetone

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