Neutral compounds Structure5 Acidic compounds m/z Composition Ion2 Frag.3 %4   m/z Neu5Ac SO3H Ion2 Frag.3 %4 Found Calc. Hex HNAc dHex   Found Calc. -,1372.4 1372.5 4 3 0 a - - 3,4 1565.5 1565.5 1 0 b - 0.23 1518.5 1518.5 4 3 1 a - 1.10 6,7 1711.6 1711.6 1 - b - 0.17 1575.5 1575.5 4 4 0 a   0.11 8,9 - -   - - - - -,1721.4 1721.6 4 4 1 a   - 10,11 1914.6 1914.7 1 0 b - 0.09 1737.5 1737.4 1737.6 5 4 0 a - 0.20 12 -,1719.4 1719.5 0 1 b - - 1930.6 1930.7 1 0 b + 1.56 1004.8 1004.8 1 1 c - 0.41 2221.7 2221.8 2 0 b + 0.57 1110.3 1110.4 2 0 c - 8.82 1778.6 1778.6 4 5 0 a - 0.12 13,14,15 1760.5 1760.6 0 1 b - 0.16 1971.7 1971.7 1 0 b + 0.67 1025.3 1025.3 1 1 c + 0.82 2262.7 2262.8 2 0 b - 0.09 1130.8 1130.9 2 0 c + 3.97 - 1819.6 3 6 0 a - - 16 1045.8 1045.8 1 1 c - 0.14 940.3 940.3 0 2 c - 0.06 1883.5 1883.6 1883.6 5 4 1 a - 0.22 17 -,1865.6 1865.6 0 1 b + - 2076.7 2076.7 1 0 b + 1.35 1077.8 1077.8 1 1 c - 0.39 2367.7 2367.8 1 0 b + 0.14 1183.3 1183.4 2 0 c + 8.61 1924.6 1924.6 4 5 1 a - 0.06 20 2117.7 2117.8 1 0 b + 0.18 1906.6 1906.6 0 1 b + 0.08 1098.3 1098.4 1 1 c - 0.45 1203.9 1203.9 2 0 c - 0.47 1940.6 1940.7 5 5 0 a - 0.11 21 -,1922.6 1922.6 0 1 b -   2133.7 2133.8 1 0 b + 0.67 1211.9 1211.9 2 0 c + 4.03 2424.7 2424.9 2 0 b - 0.07 2086.7 2086.7 5 5 1 a - 0.12 25 2279.7 2279.8 1 0 b + 0.37 1284.9 1284.9 2 0 c + 2.75 2102.7 2102.7 6 5 0 a - 0.05 26 2295.7 2295.8 1 0 b + 0.36 2586.8 2586.8 2 0 b + 0.07 -,1099.8 1099.9 c -   1292.9 1292.9 2 0 c + 8.15 1438.4 1438.5 3 0 c + 5.08 -,2143.7 2143.7 5 6 0 a - - 28,29,30 2336.7 2336.8 1 0 b - 0.08 1207.9 1207.9 1 1 c - 0.53 1313.4 1313.5 2 0 c + 1.68 1458.9 1459.0 3 0 c - 0.60 -,2125.6 2125.7   1 b + - 2248.7 2248.8 6 5 1 a - 0.05 32 2441.6 2441.6 1 0 b + 0.28 1260.4 1260.4 1 1 c - 0.35 1365.9 1366.0 2 0 c + 6.52 1405.9 1406.0 2 1 c - 0.29 1511.5 1511.5 3 0 c + 3.06 -,1172.8 1172.9 c -   -,2230.7 2230.7 0 1 b - - -,2289.7 2289.8 5 6 1 a - - 33,34 2482.9 2482.9 1 0 b - 0.04 1280.9 1280.9 c 1 1 - 0.36 1386.4 1386.5 2 0 c - 0.47 2305.7 2305.8 6 6 0 a - 0.03 35 2498.8 2498.9 1 0 b + 0.16 1394.4 1394.5 2 0 c + 4.74 1540.0 1540.0 3 0 c + 2.61 -,1201.4 1201.4 c - - 2287.6 2287.8 0 1 b - - -,2451.6 2451.9 6 6 1 a - - 37 2644.8 2644.8 1 0 b - 0.07 1467.5 1467.5 2 0 c - 2.47 -,1274.4 1274.4 c - - 1613.0 1613.0 3 0 c + 0.98 -,2467.6 2467.8 7 6 0 a - - 39,40 1475.5 1475.5 2 0 c - 5.10 1621.0 1621.0 3 0 c + 1.05 -,1282.3 1282.4 c - - 1766.6 1766.6 4 0 c - 0.23 -,2613.6 2613.9 7 6 1 a + - 42,43 1548.5 1548.5 2 0 c + 8.44     1588.5 1588.5 2 1 c - 0.16     1694.1 1694.1 3 0 c + 2.84 -,1355.4 1355.4 c - - 1839.6 1839.6 4 0 c - 0.76 -,2670.7 2670.9 7 7 0 a - - 46,47 1577.0 1577.0 2 0 c - 0.07 -,1383.9 1383.9 c - - 1722.6 1722.6 3 0 c - 0.36 -,2816? 2817.0 7 7 1 a + - 48 1650.1 1650.1 2 0 c - 0.73 -,1456.9 1457.0 c - - 1795.6 1795.6 3 0 c + 0.50 - 2833.0 8 7 0 a - - 49 1658.1 1658.1 2 0 c - 0.09 -,1464.9 1465.0 c - - 1803.6 1803.6 3 0 c - 0.13 -,2978.? 2979.1 8 7 1 a - - (50) 1731.0 1731.0 2 0 c - 0.30 1876.7 1876.7 3 0 c - 0.33 -,1538.0 1538.0 c - - 2022.2 2022.2 4 0 c - 0.29 - 3182.1 8 8 1 a - - 51 1832.7 1832.7 2 0 c - 0.05 - 3344.1 9 8 1 a - - (52) Probably tetra-antennary with one fucose and two N-acetyl-lactosamine extensions 2059.2 2059.2 3 0 c - 0.14

Fragmentation spectra obtained under conditions where some desialylation had occurred(1) Compounds are listed in order of increasing mass of the neutral glycans. The masses for residual 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 the acidic ion column. (2) Ions: a = [M+H2PO4]-, b = [M-H]-, c = [M-2H]2-. (3) + = confirmed by fragmentation. (4) % of total identified glycans. T = trace. (5) Structure shown in manuscript Figure 6.

Table 2: Masses and compositions of the intact and Arthrobacter ureafacienssialidase-treated N-glycans found in urinary hFSH1