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Are Clusters Important in Understanding the Mechanisms in Atmospheric Pressure Ionization? Part 1: Reagent Ion Generation and Chemical Control of Ion Populations

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Journal of The American Society for Mass Spectrometry

Abstract

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

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Notes

  1. At first sight this appears to be the ultimate success of alchemy: deuteron/proton transmutation.

  2. This is the answer Deep Thought, a mighty super-computer replied (after 7.5 million years of computation time) to the question about “Life, the universe, and everything” [21]. And for sure generations of students have pulled that answer to get at least partial credit for working through tough PChem exam questions. And many instructors have done exactly that: award partial credit. But only if the student did in fact not know what the question really was: “I’m afraid that the Question and the Answer are mutually exclusive. Knowledge of one logically precludes knowledge of the other. It is impossible that both can ever be known about the same universe. Except if it happened, it seems that the Question and the Answer would just cancel each other out and take the Universe with them, which would then be replaced by something even more bizarrely inexplicable. It is possible that this has already happened" [22].

  3. HeM represents the lowest electronically excited 23S1 state of He and lies 19.82 eV above the 11S0 ground state, which is the greatest amount of energy that can be stored in any atomic or molecular system. The 23S1 ← 11S0 transition is dipole and spin forbidden but can well occur upon collision of ground state He with fast electrons as they are present in LTPs. The lifetime of He 23S1 is about 8000 s [26].

  4. In comparison to the extremely light and swiftly moving electron, HeM is more like a Death Star loaded with an enormous amount of energy ready to be released when slowly coming about; recall the fate of Alderaan [27]. In a very nice article on HeM Baldwin writes: “They behave like nano-hand grenades …” [26]

  5. “Space … is big. Really big. You just won't believe how vastly, hugely, mind-bogglingly big it is. I mean, you may think it's a long way down the road to the chemist's, but that's just peanuts to space” [43].

  6. It appears as if this N2 is not as ultra-pure: microscopic ice crystals are speculated to be transported with the N2 gas stream, leading to quite high H2O mixing ratios upon reaching warmer regions (Private communication 2013. Sascha Albrecht, IEK-7, Research Center Jülich, Jülich, Germany).

  7. Based on a saturation mass of water in air at T = 20°C of 9 g m−3 [45].

  8. This compilation covers more than 2300 references from the years 1936 to 2003 [47].

  9. OK, they are not that simple. It sounds better though—every PChem instructor uses such a wording one day or the other. Thermodynamics lectures provide ample opportunities to do so, as do quantum chemistry classes …

  10. From the IUPAC Compendium of Chemical Terminology [50]: “The number of reactant molecular entities that are involved in the 'microscopic chemical event' constituting an elementary reaction …”

  11. This approach is known as the Lindemann Mechanism. A rigorous modern treatment of such reaction systems builds on RRKM Theory [51]. This theory incorporates transition state geometries, quantum statistics, internal energies of the reactants, internal energy redistributions, and much more, and is thus much more accurate …

  12. In other words, the collision rate of A+…B* with M is larger than the unimolecular decay rate of A+…B*. This is due to the fact that (a) the complex is “sticky” and (b) the collision cross section of an association complex is considerably larger than of a bound ion [52].

  13. Or we could search the literature and will certainly find this piece of text form the early 1980s: “The basic difference between API and EI or CI mass spectra is that API spectra normally show relative concentrations of ions under conditions of chemical and thermal equilibration, while EI and CI reflect relative rates of ionization reactions” [48].

  14. Deep Thought’s reply in Douglas Adams Hitchhikers Guide to the Galaxy to the request of telling the answer to Life, the Universe, Everything [54].

  15. In Thermodynamics reactions reaching completion cannot exist [41]. Rather, the equilibrium positions are “far to the left” or “far to the right”, e.g., with 99.999 % product formation. The point though is that even much longer reaction times would not affect at all the ion concentrations present.

  16. The conclusion from such observations could be: “… ‘Oh, that was easy,’ says Man, and for an encore goes on to prove that black is white …” [56]

  17. You may recall this approach from your General Chemistry textbook when setting up ICE (initial, change, equilibrium) tables for the calculation of equilibrium concentrations of weak acids and bases …

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Authors and Affiliations

  1. Institute for Pure and Applied Mass Spectrometry, Physical and Theoretical Chemistry, University of Wuppertal, 42119, Wuppertal, Germany

    Sonja Klee, Valerie Derpmann, Walter Wißdorf, Sebastian Klopotowski, Hendrik Kersten, Klaus J. Brockmann & Thorsten Benter

  2. Forschungszentrum Juelich GmbH, Institute for Energy and Climate Research–Stratosphere, (IEK-7), 52425, Juelich, Germany

    Sascha Albrecht

  3. Mass Spectrometry Core Facility, University of Groningen, 9713 AV, Groningen, The Netherlands

    Andries P. Bruins

  4. Department of Chemistry, The University of British Columbia, Kelowna, BC, V1V 1V7, Canada

    Faezeh Dousty

  5. Division of Pharmaceutical Chemistry and Technology, Faculty of Pharmacy, University of Helsinki, Helsinki, Finland

    Tiina J. Kauppila & Risto Kostiainen

  6. Supra Research and Development, Kelowna, BC, V1W 4C2, Canada

    Rob O’Brien

  7. Department of Chemistry, University of British Columbia, Vancouver, Canada

    Damon B. Robb

  8. Morpho Detection, Inc., Santa Ana, CA, 92705, USA

    Jack A. Syage

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  1. Sonja Klee
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  2. Valerie Derpmann
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  3. Walter Wißdorf
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  4. Sebastian Klopotowski
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  7. Thorsten Benter
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Correspondence to Thorsten Benter.

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Klee, S., Derpmann, V., Wißdorf, W. et al. Are Clusters Important in Understanding the Mechanisms in Atmospheric Pressure Ionization? Part 1: Reagent Ion Generation and Chemical Control of Ion Populations. J. Am. Soc. Mass Spectrom. 25, 1310–1321 (2014). https://doi.org/10.1007/s13361-014-0891-2

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