STRUCTURAL-ANALYSIS OF RAPAMYCIN AND RELATED-COMPOUNDS USING [M+LI]+ IONS GENERATED BY LIQUID SECONDARY-ION MASS-SPECTROMETRY

Cationization of the macrocyclic immunosuppressant rapamycin with lithium ion upon liquid secondary ion mass spectrometric ionization yields a number of fragment ions, which are observable in the full-wan spectrum. These are clearly assigned using B/E linked scanning (fragment ion scanning), B2/E linked scanning (precursor ion scanning) and peak matching for accurate mass measurement. Many of the fragments are produced by processes that open the macrocyclic ring, and it is possible to observe several different pieces of the molecule as fragment ions. The diversity of fragments produced facilitates the elucidation of new rapamycin-like structures through mass spectrometry. Three structurally modified rapamycin analogues have been examined hy this technique, and the modifications to the molecule may be located based on the nominal masses of their fragments.