title: CN- secondary ions form by recombination as demonstrated using multi-isotope mass spectrometry of 13C- and 15N-labeled polyglycine.
abstract: We have studied the mechanism of formation CN- secondary ions under Cs+ primary ion bombardment. We have synthesized 13C and 15N labeled polyglycine samples with the distance between the two labels and the local atomic environment of the 13C label systematically varied. We have measured four masses in parallel: 12C, 13C, and two of 12C14N, 13C14N, 12C15N, and 13C15N. We have calculated the 13C/12C isotope ratio, and the different combinations of the CN isotope ratios (27CN/26CN, 28CN/27CN, and 28CN/26CN). We have measured a high 13C15N- secondary ion current from the 13C and 15N labeled polyglycines, even when the 13C and 15N labels are separated. By comparing the magnitude of the varied combinations of isotope ratios among the samples with different labeling positions, we conclude the following: CN- formation is in large fraction due to recombination of C and N; the CO double bond decreases the extent of CN- formation compared to the case where carbon is singly bonded to two hydrogen atoms; and double-labeling with 13C and 15N allows us to detect with high sensitivity the molecular ion 13C15N-.
authors.affiliation: National Resource for Imaging Mass Spectrometry, Harvard Medical School and Brigham and Women's Hospital, Cambridge, Massachusetts 02139, USA.
authors.forename: G
authors.initials: G
authors.lastname: McMahon
authors.forename: H Francois
authors.initials: HF
authors.lastname: Saint-Cyr
authors.forename: C
authors.initials: C
authors.lastname: Lechene
authors.forename: C J
authors.initials: CJ
authors.lastname: Unkefer
mesh_terms: D002247:Carbon Isotopes / Q000737:chemistry*; D003486:Cyanides / Q000737:chemistry*; D007477:Ions; D007553:Isotope Labeling / Q000379:methods*; D013058:Mass Spectrometry / Q000379:methods*; D009587:Nitrogen Isotopes / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*
chemical_list: D002247:Carbon Isotopes; D003486:Cyanides; D007477:Ions; D009587:Nitrogen Isotopes; D010455:Peptides; C011080:polyglycine