ABSTRACT
A tandem mass spectrometric method is described which allows the assignment of stereochemistry to fragment ions comprising intact sugar subunits of larger glycosides without chemical degradation and product isolation by chromatography. The approach relies on the mass selection of the 'sugar ion' of interest followed by analysis of stereoselective fragmentation induced by low-energy collisional activation. The daughter ion spectra provide configurational fingerprints of the selected sugar ions which can be matched for identity with reference spectra obtained from suitable precursors of known stereochemistry. Glucose, mannose and galactose furnished the required set of the most important reference ions. By using peracetyl (and perdeuterioacetyl) derivatives, galactose was readily identified as the glycosidic sugar constituent of the (known) antibiotic papulacandin B and a further (unknown) congener.
