Neutral compounds Structure5 Acidic compounds m/z([M+H2PO4]-(Ion type a)2 Composition %3/ Frag4 m/z Acidic groups Ion2 Frag.4 %2 Structure6 Found Calc. Hex HexNAc dHex Found Calc. Neu5Ac SO3H 1007.3 1007.3 3 2 0 0.11 1 - - - - - - - - 1153.4 1153.4 3 2 1 0.18 2 - - - - - - - - -,1372.5 1372.5 4 3 0 + 3,4 1565.5 1565.5 1 0 b + 0.76 - - 1413.5 3 4 0 - 5 1606.6 1606.6 1 0 b - 0.21 - -,1518.5 1518.5 4 3 1 - 6,7 1711.6 1711.6 1 0 b + 0.62 53,54 -,1575.6 1575.5 4 4 0 - 8,9 1768.6 1768.6 1 0 b + 0.22 55,56 -,1721.6 1721.6 4 4 1 + 10,11 1914.7 1914.6 1 0 b + 0.26 - -,1737.7 1737.6 5 4 0 + 12 1930.7 1930.7 1 0 b + 0.35 57 1004.8 1004.8 1 1 c - 0.25 - 1110.4 1110.4 2 0 c - 9.25 - 2221.8 2221.7 b - 0.12 - -,1778.7 1778.6 4 5 0 + 13,14,15 1760.6, 1760.7 1760.6 0 1 b - 0.18 -,+ 1971.7 1971.7 1 0 b + 0.48 58 a2→6-Neu5Ac on Gal 1025.3 1025.3 1 - c - 2.05 - 1130.9 1130.9 2 0 c - 6.57 - 2263.7 2262.7     b - 0.05 - - 1819.6 3 6 0 - 16 940.2, 940.3 940.3 0 2 c - 0.23 - 1045.8 1045.8 1 1 c - 0.29 - -,1883.7 1883.6 5 4 1 + 17 2076.7 2076.7 1 0 b + 0.34 59 1183.4 1183.4 2 0 c - 7.66 - -,1924.7 1924.6 4 5 1 + 18,19,20 1906.6, 1906.7 1906.6 0 1 b + T - 1098.3 1098.4 1 1 c - 1.08 - 2117.4 2117.7 1 0 b - T 60 a2→6-Neu5Ac on Gal 1203.9 1203.9 2 0 c - 0.62 - -,1940.7 1940.7 5 5 0 + 21 2133.8 2133.7 1 0 b + 0.19 61 1211.9 1211.9 2 0 c - 4.44 - 2424.9 2424.8 b - 0.04   - 1965.7 3 6 1 - 22 1013.3 1013.3 0 2 c - 0.16 - - 2029.7 5 4 2 - (23,24) 1256.4 1256.4 2 0 c - 0.28 - -,2086.8 2086.7 5 5 1 + 25 2279.8 2279.7 1 0 b + 0.16 62 1284.9 1284.9 2 0 c - 4.72 - -,2102.8 2102.7 6 5 0 + 26 2295.8 2295.8 1 0 b + 0.03 63 1292.9 1292.9 2 0 c - 4.44 - 2586.7 2586.8 b - T - 1438.5 1438.5 3 0 c - 6.48 -

(1) Compounds are listed in order of increasing mass of the neutral glycans. The masses for the acidic glycans that were found in the sample are listed after the neutral structures. Most compounds were not found as neutral structures in the intact glycan sample (as indicated by the dash in Column 1), but were found in the desialylated sample. Ions found in both samples are indicated as bold type. Where found values differed, both are reported. The same convention was followed in column 8. (2) Ions: a = [M+H2PO4]-, b = [M-H]-, c = [M-2H]2-. (3) % of total identified glycans. T = trace. (4) + = confirmed by fragmentation. (5) The number corresponds to structures in Figure 6. (6) As confirmed by fragmentation and shown in Figure 6. (7) Agalactose residue has been replaced by GalNAc.

Table 1: Masses and compositions of the intact and Arthrobacter ureafacienssialidase-treatedN-glycans found in pituitary hFSH1