Fast atom bombardment and tandem mass spectrometry for structure determination: remote site fragmentation of steroid conjugates and bile salts.

A series of 35 steroid conjugates (sulfates and glucuronides) and bile salts were investigated by using fast atom bombardment and tandem mass spectrometry. Collisional activation of the [M - H]- anions of sulfate conjugates and bile salts predominantly yields fragment ions arising by reactions occurring remote from the charge site. These reactions are sometimes sensitive to differences in stereochemistry at positions remote from the charge site and are useful for positional isomer differentiation. On the other hand, collisional activation of the [M - H]- anions of the glucouronide conjugates leads primarily to charge-driven fragementations.