Thermal dissociation of ions limits the degree of the gas‐phase H/D exchange at the atmospheric pressure

Kostyukevich, Yury; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene

doi:10.1002/jms.3917

Cited by 8 publications

(8 citation statements)

References 56 publications

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“…It is also possible to couple the multiplexed ion source to the gas phase H/D exchange reaction. Recently we have presented a simple approach to perform in-ESI source H/D exchange. ,,− Droplet of D 2 O is placed beneath the desolvating capillary. Because of the evaporation, the desolvating capillary becomes saturated with D 2 O vapors, ions interact with D 2 O, and exchange its labile hydrogens for deuterium.…”

Section: Resultsmentioning

confidence: 99%

“…The temperature variation at different capillary positions and over a single experiment was found to be less than 5 °C. More details about the setup can be found elsewhere …”

Section: Methodsmentioning

confidence: 99%

“…More details about the setup can be found elsewhere. 36 In-ESI Source H/D Exchange. To create an atmosphere saturated with the vapors of the D 2 O 600 μL of solvent were placed on a copper plate positioned at approximately 7 mm below the ESI needle.…”

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confidence: 99%

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Ion Source Multiplexing on a Single Mass Spectrometer

Kostyukevich

Nikolaev

2018

Anal. Chem.

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We present the simple approach for the combination of different ion sources on a single mass spectrometer without any interference between them. Each ion source can be positioned as far as 1 m from the mass spectrometer; ions are transported by the means of flexible copper tubes, which are connected, to the separate inlet capillaries. Special valves enable switching channels on and off. Using this approach, we successfully combined native electrospray ionization (ESI), regular ESI, β-electrons ionization, and atmospheric pressure photoionization (APPI) of thermally desorbed vapors of petroleum on a single mass spectrometer. In addition, separate channels allow infusing internal calibration mixture or performing ion molecular reactions in one channel and using the other as a reference. Using this idea, we have developed an original sequential window acquisition of all theoretical mass spectra (SWATH MS) approach in which peptide ions are transported in different channels, one of which is heated to high temperature so that ions are thermally fragmented, and the other channel ensures the presence of nonfragmented ions in the spectrum. Also, we demonstrated the possibility to perform gas phase H/D exchange reaction in one channel and using another as reference. Use of valves makes it possible to exclude any interference between them. Thus, we have demonstrated the possibility to create a multichannel system in which ions would be transported through several inlet tubes in which different ion molecular reactions such as Paternò-Büchi, ozonation, or H/D exchange will occur. Comparison of mass spectra recorded when different channels are open will provide structural and chemical information about unknown species.

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Section: Resultsmentioning

confidence: 99%

“…The temperature variation at different capillary positions and over a single experiment was found to be less than 5 °C. More details about the setup can be found elsewhere …”

Section: Methodsmentioning

confidence: 99%

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Ion Source Multiplexing on a Single Mass Spectrometer

Kostyukevich

Nikolaev

2018

Anal. Chem.

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“…Increasing the reaction time by increasing the length of the desolvating capillary can help to increase the degree of the exchange. 51,52 The determination of the activation energy is shown in the Figure 5B. We can see that for [IO 3 ] − and [I 3 O 13 ] − ions the charts obtained using eq 15 have the form of almost perfect lines.…”

Section: ■ Simulation and Experimentsmentioning

confidence: 92%

“…The effect of back exchange is negligible because the atmosphere in the ESI source is saturated with D 2 O. Increasing the reaction time by increasing the length of the desolvating capillary can help to increase the degree of the exchange. , …”

Section: Simulation and Experimentsmentioning

confidence: 99%

Analytical Description of the H/D Exchange Kinetic of Macromolecule

et al. 2018

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We present the accurate analytical solution obtained for the system of rate equations describing the isotope exchange process for molecules containing an arbitrary number of equivalent labile atoms. The exact solution was obtained using Mathematica 7.0 software, and this solution has the form of the time-dependent Gaussian distribution. For the case when forward exchange considerably overlaps the back exchange, it is possible to estimate the activation energy of the reaction by obtaining a temperature dependence of the reaction degree. Using a previously developed approach for performing H/D exchange directly in the ESI source, we have estimated the activation energies for ions with different functional groups and they were found to be in a range 0.04-0.3 eV. Since the value of the activation energy depends on the type of functional group, the developed approach can have potential analytical applications for determining types of functional groups in complex mixtures, such as petroleum, humic substances, bio-oil, and so on.

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Hydrogen/deuterium exchange in mass spectrometry

Kostyukevich

Acter

Zherebker

et al. 2018

Mass Spectrometry Reviews

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The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies.

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Thermal dissociation of ions limits the degree of the gas‐phase H/D exchange at the atmospheric pressure

Cited by 8 publications

References 56 publications

Ion Source Multiplexing on a Single Mass Spectrometer

Ion Source Multiplexing on a Single Mass Spectrometer

Analytical Description of the H/D Exchange Kinetic of Macromolecule

Hydrogen/deuterium exchange in mass spectrometry

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