“…[3][4][5] Not surprisingly, different combinations of ionization techniques, ion activation and mass analyzers will yield results of different analytical utility. Examples of such combinations, over the years of research on the MS/MS of glycans, include fast atom bombardment (FAB)-MS, [7][8][9] infrared-laser desorption MS, 10,11 matrixassisted laser desorption/ionization (MALDI)/magnetic sector MS, [12][13][14] electrospray ionization (ESI)-MS, 15,16 MALDI/time-of-flight (TOF)-MS, [17][18][19] ESI ion-trap MS, 20,21 MALDI Fourier transform MS, 22 ESI-or MALDI-based quadrupole/TOF-MS, [23][24][25][26] and, more recently, MALDI-TOF/TOF-MS. [27][28][29][30][31] Extensive CID has particularly been demonstrated through the tandem time-of-flight (TOF/TOF) approach, [27][28][29][30][31] yielding numerous cross-ring product ions of analytical value, such as those distinguishing between different sialic acid linkages as well as their variable attachment to a glycan antenna. 28 Alternatively, a more selective cross-ring fragmentation might be achieved through irradiation with laser light (photofragmentation), as recently demonstrated in our preliminary communication 32 on linear oligosaccharides and glycans derived from human milk.…”