title: Accurate mass measurement by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry. I. Measurement of positive radical ions using porphyrin standard reference materials.
abstract: A method for the accurate mass measurement of positive radical ions by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is described. Initial use of a conjugated oligomeric calibration material was rejected in favour of a series of meso-tetraalkyl/tetraalkylaryl-functionalised porphyrins, from which the two calibrants required for a particular accurate mass measurement were chosen. While all measurements of monoisotopic species were within +/-5 ppm, and the method was rigorously validated using chemometrics, mean values of five measurements were used for extra confidence in the generation of potential elemental formulae. Potential difficulties encountered when measuring compounds containing multi-isotopic elements are discussed, where the monoisotopic peak is no longer the lowest mass peak, and a simple mass-correction solution can be applied. The method requires no significant expertise to implement, but care and attention is required to obtain valid measurements. The method is operationally simple and will prove useful to the analytical chemistry community.
authors.affiliation: EPSRC National Mass Spectrometry Service Centre (NMSSC), Institute of Mass Spectrometry (IMS), School of Medicine, Swansea University, Singleton Park, Swansea SA2 8PP, UK.
authors.forename: Nia W
authors.initials: NW
authors.lastname: Griffiths
authors.forename: Mark F
authors.initials: MF
authors.lastname: Wyatt
authors.forename: Suzanna D
authors.initials: SD
authors.lastname: Kean
authors.forename: Andrew E
authors.initials: AE
authors.lastname: Graham
authors.forename: Bridget K
authors.initials: BK
authors.lastname: Stein
authors.forename: A Gareth
authors.initials: AG
authors.lastname: Brenton
mesh_terms: D002138:Calibration; D005609:Free Radicals / Q000737:chemistry*; D008970:Molecular Weight; D011166:Porphyrins / Q000737:chemistry*; D012015:Reference Standards; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods* / Q000592:standards
chemical_list: D005609:Free Radicals; D011166:Porphyrins