Abstract
The fragmentation behavior of radical anions M−· derived by electron capture of organic molecules was studied extensively in the 1970s and early 1980s. The characteristic cleavages of most functional groups have been documented: This area of ion chemistry has been reviewed over the years.(1–4) More recently, the introduction of such techniques as negative ion chemical ionization,(5) secondary ion mass spectrometry,(6) laser-induced mass spectrometry,(7) 252Cf plasma spectrometry,(8) and fast atom bombardment mass spectrometry(9) has allowed the formation of deprotonated organic molecules (M-H)−. While such ions have been used primarily to provide molecular weight information,(4) on occasions, their fragmentations either in the ion source or under collisional activation conditions have been determined and they have yielded useful structural information. The examples shown in Figure 1 illustrate this point: (1) Nucleotides form (M-H)− ions using a variety of techniques,(10–12) and these ions undergo ready P-O bond cleavage, e.g., N.A.D. (Formula I);(10) (2) C-O bond cleavage is also facile, e.g., glycoside II, undergoes four successive losses of glycose from the (M-H)− ion,(3 while the (M-H)− ion of avilamycin undergoes the cleavage shown in III;(14) (3) collisional activation of peptide (M-H)− ions yield sequence information, e.g., peptide IV,(15) and β-lactam V [negative ion cleavages (—), positive ion cleavages of the corresponding molecular radical cations (~)];(16) and finally (4) the collision-induced dissociations of carboxylate ion VI.(17)
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Bowie, J.H. (1994). The Fragmentations of (M-H)− Ions Derived from Organic Compounds. In: Russell, D.H. (eds) Experimental Mass Spectrometry. Topics in Mass Spectrometry, vol 1. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2569-5_1
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