+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Sulfur Pentafluoride is a Preferred Reagent Cation for Negative Electron Transfer Dissociation

Sulfur Pentafluoride is a Preferred Reagent Cation for Negative Electron Transfer Dissociation

Journal of the American Society for Mass Spectrometry 28(7): 1324-1332

Negative mode proteome analysis offers access to unique portions of the proteome and several acidic post-translational modifications; however, traditional collision-based fragmentation methods fail to reliably provide sequence information for peptide anions. Negative electron transfer dissociation (NETD), on the other hand, can sequence precursor anions in a high-throughput manner. Similar to other ion-ion methods, NETD is most efficient with peptides of higher charge state because of the increased electrostatic interaction between reacting molecules. Here we demonstrate that NETD performance for lower charge state precursors can be improved by altering the reagent cation. Specifically, the recombination energy of the NETD reaction-largely dictated by the ionization energy (IE) of the reagent cation-can affect the extent of fragmentation. We compare the NETD reagent cations of C16H10●+ (IE = 7.9 eV) and SF5●+ (IE = 9.6 eV) on a set of standard peptides, concluding that SF5●+ yields greater sequence ion generation. Subsequent proteome-scale nLC-MS/MS experiments comparing C16H10●+ and SF5●+ further supported this outcome: analyses using SF5●+ yielded 4637 peptide spectral matches (PSMs) and 2900 unique peptides, whereas C16H10●+ produced 3563 PSMs and 2231 peptides. The substantive gain in identification power with SF5●+ was largely driven by improved identification of doubly deprotonated precursors, indicating that increased NETD recombination energy can increase product ion yield for low charge density precursors. This work demonstrates that SF5●+ is a viable, if not favorable, reagent cation for NETD, and provides improved fragmentation over the commonly used fluoranthene reagent. Graphical Abstract ᅟ.

Please choose payment method:

(PDF emailed within 0-6 h: $19.90)

Accession: 060294750

Download citation: RISBibTeXText

PMID: 28349437

DOI: 10.1007/s13361-017-1600-8

Related references

Negative electron transfer dissociation of deprotonated phosphopeptide anions: choice of radical cation reagent and competition between electron and proton transfer. Analytical Chemistry 82(7): 2873-2878, 2010

Electron Transfer Dissociation: Effects of Cation Charge State on Product Partitioning in Ion/Ion Electron Transfer to Multiply Protonated Polypeptides. International Journal of Mass Spectrometry 330-332: 174-181, 2012

Structures of Fluoranthene Reagent Anions Used in Electron Transfer Dissociation and Proton Transfer Reaction Tandem Mass Spectrometry. Analytical Chemistry 88(12): 6126-6129, 2016

The Negative Mode Proteome with Activated Ion Negative Electron Transfer Dissociation (AI-NETD). Molecular and Cellular Proteomics 14(10): 2644-2660, 2015

Electron-transfer reagent anion formation via electrospray ionization and collision-induced dissociation. Analytical Chemistry 78(21): 7387-7391, 2006

Activated-ion electron transfer dissociation improves the ability of electron transfer dissociation to identify peptides in a complex mixture. Analytical Chemistry 82(24): 10068-10074, 2010

Negative electron transfer dissociation of glycosaminoglycans. Analytical Chemistry 82(9): 3460-3466, 2010

Coupling capillary zone electrophoresis with electron transfer dissociation and activated ion electron transfer dissociation for top-down proteomics. Analytical Chemistry 87(10): 5422-5429, 2015

Effects of cation charge-site identity and position on electron-transfer dissociation of polypeptide cations. Journal of the American Chemical Society 129(40): 12232-12243, 2007

Novel synthesis of sulfur containing bicyclic beta lactams thiaisoalkanams using sulfur dichloride as a sulfur transfer reagent. Tetrahedron Letters 31(25): 3627-3630, 1990

Combining UV photodissociation action spectroscopy with electron transfer dissociation for structure analysis of gas-phase peptide cation-radicals. Journal of Mass Spectrometry 50(12): 1438-1442, 2015

Full-Featured Search Algorithm for Negative Electron-Transfer Dissociation. Journal of Proteome Research 15(8): 2768-2776, 2016

Cation-modulated electron-transfer channel: H-atom transfer vs proton-coupled electron transfer with a variable electron-transfer channel in acylamide units. Journal of the American Chemical Society 129(31): 9713-9720, 2007

Analysis of the acidic proteome with negative electron-transfer dissociation mass spectrometry. Analytical Chemistry 84(6): 2875-2882, 2012

Activated ion negative electron transfer dissociation of multiply charged peptide anions. Analytical Chemistry 85(9): 4721-4728, 2013