Transition-metal cationization of laser desorbed perfluorinated polyethers with FTICR mass spectrometry

Cromwell, Evan F.; Reihs, Karsten; Vries, Mattanjah S. de; Ghaderi, Sahba.; Wendt, Hartmut; Hunziker, H. E.

doi:10.1021/j100120a027

Cited by 19 publications

(7 citation statements)

References 15 publications

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“…An essentially identical pattern has been reported previously in an experiment in which Demnum-S was desorbed from a metal surface with one laser, while a second laser was applied to generate low-energy photoelectrons from the metal substrate, and the resulting ions were examined by an ion cyclotron mass spectrometer . The similarity of the cited pattern to that presently observed strongly supports the contention that the negative ion TOF-SIMS spectra of PFPEs are dominated by anions produced by dissociative capture of low-energy electrons.…”

Section: Resultssupporting

confidence: 83%

Perfluoropolyethers: Analysis by TOF-SIMS

Spool¹,

Kasai

1996

Macromolecules

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TOF-SIMS spectra of the following perfluoropolyethers (PFPEs) were analyzed: Demnum-S, Krytox, Fomblin-Z, perfluoropoly(dioxolane), perfluoropoly(tetramethylene oxide), and perfluoropoly(ethylene oxide). In each case, the PFPE produced an intense negative ion spectrum with simple patterns persisting into the high-mass region surpassing the mean MW of the polymer. In contrast, the positive ion spectra are much more complex and compressed toward the low-mass end. Totally unrelated formation mechanisms for the positive and negative ions are thus indicated. It is proposed and substantiated that the negative ion spectra are dominated by anions resulting from one-step dissociative electron capture at ether oxygens, R−O−R‘ + e- → R−O- + •R‘. The Demnum molecule, having locally symmetric ether oxygens, produces two major peaks in each repetitive fragmentation packet, equal in intensity but displaced by the mass difference of the two end groups. PFPEs with asymmetric ether oxygens produce negative ion spectra resulting from asymmetric cleavage. The negative ion pattern of Fomblin-Z can be accurately modeled with the dissociative electron capture at ether oxygens linking randomly distributed methylene and ethylene units. Other less intense peaks in the negative ion spectra of PFPEs result from multiple electron capture events and from polymer chains with anomalous end groups or intrachain units.

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Section: Resultssupporting

confidence: 83%

Perfluoropolyethers: Analysis by TOF-SIMS

Spool¹,

Kasai

1996

Macromolecules

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“…Lignins, the cell wall constituents of wood, produced negative ions up to mlz 3000, and spectra confirmed the existence of stable trimer building blocks. Cromwell et al (1993) examined perfluorinated polyether (PFPE) films on metal substrates using a dual-pulsed laser system. A low fluence laser was used for sample desorption, and a second higher power laser ablated the underlying metal substrate to promote cationization in the gas phase.…”

Section: Polymer Studiesmentioning

confidence: 99%

Fourier transform mass spectrometry—advancing years (1992-mid. 1996)

Dienes

Pastor

Schürch

et al. 1996

Mass Spectrom. Rev.

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This article is one of a series of Fourier transform mass spectrometry (FTMS) reviews that has appeared in this journal at ca. 3–4 year intervals. A comprehensive review of the recent theoretical developments, instrumental developments, electrospray ionization (ESI), and MALDI is given. Ion dissociation techniques are also discussed because of their contributions to gaining insight into chemical structure. Special sections have been devoted to discussing the emerging fields of surface analysis, polymer analysis, Buckminsterfullerenes (buckyballs), and hydrogen/deuterium exchange studies. This review, although not all‐inclusive, is intended to be a starting point for those wishing to learn more about the current status of FTMS, and also as a representative cross‐section of the literature for those familiar with the technique. © 1997 John Wiley & Sons, Inc.

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“…Substrates ranging from glass, graphite, stainless steel, to other metals can be used in laser desorption to decrease the internal energy of analyte molecules, thereby reducing their fragmentation by an order of magnitude − It has recently been reported that noble transition metal ions produced in the gas phase by laser ablation of a metal probe tip or a metal-substituted zeolite can act as chemical ionization (CI) reagents for analyte molecules, with minimal fragmentation. , …”

mentioning

confidence: 99%

Surface Plasmon Resonance-Laser Desorption/Ionization-Time-of-Flight Mass Spectrometry

1998

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The laser desorption/ionization (LDI) process is investigated under surface plasmon resonance (SPR) conditions using time-of-flight mass spectrometry (TOFMS). We demonstrate that LDI-TOFMS at the SPR angle requires a lower minimum laser fluence for the production of silver monomer and cluster cations from ablation of a thin silver film substrate. In the LDI of gramicidin S deposited on a thin silver film substrate, the largest intensity for the molecular cation peak occurs when the laser light is incident on the substrate at a specific SPR angle. These results fully confirm SPR enhancement of the LDI process. The capability to perform SPR-LDI on a larger molecular weight analyte (1141 amu for gramicidin S) represents a new milestone beyond the previous achievement with rhodamine B (479 amu). A better understanding of the SPR mechanism is gained with respect to the substrate metals (silver vs aluminum), desorption (microscopic vs mesoscopic), and ionization (chemical vs multiphoton). These findings may be useful in the future design of SPR-LDI techniques for better TOFMS analysis of higher mass biomolecules.

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Transition-metal cationization of laser desorbed perfluorinated polyethers with FTICR mass spectrometry

Cited by 19 publications

References 15 publications

Perfluoropolyethers: Analysis by TOF-SIMS

Perfluoropolyethers: Analysis by TOF-SIMS

Fourier transform mass spectrometry—advancing years (1992-mid. 1996)

Surface Plasmon Resonance-Laser Desorption/Ionization-Time-of-Flight Mass Spectrometry

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