Dihydroxybenzenes give rise to anion radical adduct ions with 3-nitrobenzyl alcohol in addition to the deprotonated adduct ions under fast atom bombardment. 2-Nitrophenyl octyl ether gives only radical anion adducts, whereas other common matrices give deprotonated adducts. Unimolecular decomposition
Fast atom bombardment mass spectra of dihydroxybenzenes: Formation of radical cation adduct between sample and matrix
β Scribed by K. P. Madhusudanan
- Publisher
- John Wiley and Sons
- Year
- 1995
- Tongue
- English
- Weight
- 572 KB
- Volume
- 30
- Category
- Article
- ISSN
- 1076-5174
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β¦ Synopsis
Abstract
Under fast atom bombardment, dihydroxybenzenes form predominantly the M^+Β·^ and [M + Matrix]^+Β·^ ions. The second fieldβfree region metastable decomposition of the [M + Matrix]^+Β·^ ion involves the loss of a neutral molecule of the matrix. In the case of the hydroquinoneβmatrix adduct ion, elimination of both the matrix and hydroquinone are observed. Surprisingly, alkali metal cationization also leads to the formation of abundant radical cations in which the acidic hydrogens have been replaced with alkali metal. The degree of this exchange varies among the isomeric compounds. The facile formation of radical cations and their adducts appears to be due to various factors such as the ionization potentials, redox potentials and the proton affinities of the dihydroxybenzenes and the analyteβmatrix interactions.
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