Tandem mass spectrometry of laser-reduced anthraquinones for painted works and dyed cultural artifacts

Michael P. Napolitano, Ping-Chung Kuo, Jodie V. Johnson, Julie Arslanoglu, Richard A. Yost

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The peculiar ionization of anthraquinones, including the artistic dyes alizarin and purpurin, is examined. When alizarin (MW = 240) is ionized by either LDI or MALDI it exhibits a dominant ion of m/z 242 [M + 2H][rad]+ with a far greater abundance than expected from the 13C isotopic contribution from the [M + H]+ ion at m/z 241. For the first time, MS/MS analysis of these anomalous [M + 2H][rad]+ ions is presented, which indicates that they arise from a laser-induced photoreduction of one of the anthraquinone's carbonyl groups. MS/MS daughter ions produced from neutral losses of either water or ammonia from the [M + 2H][rad]+ ions exhibit different relative abundances, depending upon their respective functional groups’ proximity to the reduced carbonyl. LDI-MS/MS was used for the in situ detection of alizarin in a painting cross section and a swatch of dyed silk.

Original languageEnglish
Pages (from-to)14-24
Number of pages11
JournalInternational Journal of Mass Spectrometry
Volume421
DOIs
Publication statusPublished - 2017 Oct 1

Fingerprint

Anthraquinones
anthraquinones
Mass spectrometry
artifacts
Alizarin
mass spectroscopy
Ions
Lasers
lasers
ions
silk
Silk
Painting
Ammonia
photochemical reactions
Functional groups
Ionization
proximity
ammonia
Coloring Agents

All Science Journal Classification (ASJC) codes

  • Instrumentation
  • Condensed Matter Physics
  • Spectroscopy
  • Physical and Theoretical Chemistry

Cite this

Napolitano, Michael P. ; Kuo, Ping-Chung ; Johnson, Jodie V. ; Arslanoglu, Julie ; Yost, Richard A. / Tandem mass spectrometry of laser-reduced anthraquinones for painted works and dyed cultural artifacts. In: International Journal of Mass Spectrometry. 2017 ; Vol. 421. pp. 14-24.
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abstract = "The peculiar ionization of anthraquinones, including the artistic dyes alizarin and purpurin, is examined. When alizarin (MW = 240) is ionized by either LDI or MALDI it exhibits a dominant ion of m/z 242 [M + 2H][rad]+ with a far greater abundance than expected from the 13C isotopic contribution from the [M + H]+ ion at m/z 241. For the first time, MS/MS analysis of these anomalous [M + 2H][rad]+ ions is presented, which indicates that they arise from a laser-induced photoreduction of one of the anthraquinone's carbonyl groups. MS/MS daughter ions produced from neutral losses of either water or ammonia from the [M + 2H][rad]+ ions exhibit different relative abundances, depending upon their respective functional groups’ proximity to the reduced carbonyl. LDI-MS/MS was used for the in situ detection of alizarin in a painting cross section and a swatch of dyed silk.",
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Tandem mass spectrometry of laser-reduced anthraquinones for painted works and dyed cultural artifacts. / Napolitano, Michael P.; Kuo, Ping-Chung; Johnson, Jodie V.; Arslanoglu, Julie; Yost, Richard A.

In: International Journal of Mass Spectrometry, Vol. 421, 01.10.2017, p. 14-24.

Research output: Contribution to journalArticle

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T1 - Tandem mass spectrometry of laser-reduced anthraquinones for painted works and dyed cultural artifacts

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AU - Kuo, Ping-Chung

AU - Johnson, Jodie V.

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AU - Yost, Richard A.

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AB - The peculiar ionization of anthraquinones, including the artistic dyes alizarin and purpurin, is examined. When alizarin (MW = 240) is ionized by either LDI or MALDI it exhibits a dominant ion of m/z 242 [M + 2H][rad]+ with a far greater abundance than expected from the 13C isotopic contribution from the [M + H]+ ion at m/z 241. For the first time, MS/MS analysis of these anomalous [M + 2H][rad]+ ions is presented, which indicates that they arise from a laser-induced photoreduction of one of the anthraquinone's carbonyl groups. MS/MS daughter ions produced from neutral losses of either water or ammonia from the [M + 2H][rad]+ ions exhibit different relative abundances, depending upon their respective functional groups’ proximity to the reduced carbonyl. LDI-MS/MS was used for the in situ detection of alizarin in a painting cross section and a swatch of dyed silk.

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