Supplemental Figure S1. MALDI-TOF/TOF MS analysis of mouse serum glycans. MS/MS spectra were annotated using GlycoWorkbench
software which calculates the percentage of experimental fragments that match with the theoretical fragments generated in silico. For each m/z
value, the shown structure is the one which presented the largest number of fragments that match with the theoretical fragments. Only the B-, C-, Y-
and Z-type ions are shown. The B- and C-type ions resulting from terminal reductive fragmentation are not systematically illustrated by the
software. Most of the observed ions were sodiated. However, the sodiated ion with m/z 428 (NeuGc) has given rise to the ion with m/z 406, which is
a desodiated and protonated form of the ion with m/z 428, and to the ion with m/z 374, which is a decarboxylated form of the ion with m/z 406. The
ions with m/z 374 and 406 were frequently observed on the MS/MS spectra.
Supplemental Figure S1
1580Parent ion with m/z
1784
* The methodology for the extraction of N-glycans can introduce free O-glycans from serum. Therefore, ions 428, 877 and 953 likely are fragments of the parent ion 1807 that
matches with a O-glycan ( ).
Ions 472 and 1389 are fragments of the parent ion 1795.
Parent ion with m/z
*877
472
*428
1389
*953
1795
*1807
1795
* Ions 428 and 877 are fragments of the parent ion 1807.
Ions 1506 and 1565 are fragments of the parent ion 1784.
Parent ion with m/z
*8771506
1565
1784
*1807
*428
1836
* Ions 877 and 953 are fragments of the parent ion 1807 wich is likely a O-Glycan (see parent ion 1784).
Remark: more fragments match with a structure showing a fucose on the terminal GlcNAc rather than a structure with a fucose on the reductive terminal GlcNAc.
Parent ion with m/z
*877 *1807*953
1988
* Ions 374, 406, 472, 877, 1606 and 1795 are fragments of the parent ion 2012.
Ions 1576 and 1593 are fragments of the parent ion 1999.
Parent ion with m/z
1999
*2012
*1795
*1606
1593
1576
*877
*472*406
*374
1999
* Ions 877 and 1606 are fragments of the parent ion 2012
Parent ion with m/z
*877
*1606
*2012
2012
* Ion 1592 is a fragment of ion 1999.
Parent ion with m/z
*1999
*1592
2040
*428
*877
*1157
*2012
* Ions 428, 877 and 1157 are fragments of the parent ion 2012
Parent ion with m/z
2192
* 374, 406, 428, 472, 877, 1780 and 1998 are fragments of the parent ion 2186, a monoantennary fucosylated and sialylated (NeuGc) glycan.
Parent ion with m/z
*2186
*374
*406
*428
*472
*877
*1780
*1998
2216
* 1317, 1781 and 1837 are fragments of the parent ion 2244.
Parent ion with m/z
*2244*1837
*1781
*1317406
374
2244
* 374, 406, 650, 877, 1852, 1980 and 1999 are fragments of the parent ion 2257.
1361 can be attributed to the protonated Z-type ion that comes from ion 2257 (see parent ion with m/z 2257).
Parent ion with m/z
*406*374
*877
*650
*1852
*1980
*1999
*2257
1361
2257
*2244
1361
*1837
406
374
* Ion 1837 is a fragment of the parent ion 2244.
Ion 1361 can be attributed to the protonated Z-type ion:
Parent ion with m/z
2396
*877
*472*428
*406
*374
1268
*2420
*1565
*1592
*2144
*1984
*1995
*2014
* Ions 374, 406, 428, 472, 877, 1565,1592, 1984, 1995, 2014,2144 are fragments of the parent ion 2420.
Ion 1268 was not able to be attributed.
Parent ion with m/z
2420
*2448
*2042
* Ion 2042 is a fragment of the parent ion 2448.
BY
CZ
406
374
Parent ion with m/z
2448
*2461
*877*650
* Ions 650 and 877 can be attributed to ion 2461.
Remark: more fragments matched with a structure displaying a fucose on antennae with Gal-Gal motif.
Parent ion with m/z
2461
406
374
*2448
*2042
* Ion 2042 is a fragment of the parent ion 2448.
Parent ion with m/z
2607
*2635
*2230
*2173
*374
*406
*472
*877
855
*1081*1317
* Ions 374, 406, 472, 855, 877, 1081, 1317, 2173 and 2230 are fragments of the parent ion 2635.
Ion 855 is a protonated and desodiated form of the ion 877.
Remark: More ions match with a structure showing a substituted LacNAc antennae instead of a polysialylated structure.
Parent ion with m/z
2635
*406
*374
196
*855
1752
1998
* Ions 374, 406 and 855 are fragments of the parent ion 2635.
Ions 196, 1752 and 1998 were not able to be attributed to a parent ion.
Parent ion with m/z
*2809
*877
*650*1720
*1983 *2433
*406
*374
1143
1593
2448
2822§ 819
*855*428
§ 196
2796
* Ions 374, 406, 650, 855, 877, 1720, 1983 and 2433 are fragments of the parent ion 2809.
Ions 1143, 1593, 1998 and 2448 are fragments of the parent ion 2822.
§ Ions196 and 819 were not able to be attributed to a parent ion.
1998
Parent ion with m/z
2809
406
374 *939
*1143
*1592 *1793
*1998
*2244
*2448
*2822
* Ions 939, 1143, 1592, 1793, 2244 and 2448 are fragments of the parent ion 2822.
Ions 374 and 406 are fragments of the parent ion 2809.
Parent ion with m/z
2822
2837
2852
Parent ion with m/z
2837
* Ions 428, 877, 1081, 1143, 1592, 1793, 1998, 2242, 2447 and 2576 are fragments of the parent ion 2852.
*428
*877
*1081*1143 *1592
*1793
*1998
*2242
*2447
*2576
*2852
Parent ion with m/z
2852Parent ion with m/z
2867
*877
*1143
*2852
*1997
*2447
* Ions 877, 1143, 1997 and 2447 are fragments of the parent ion 2852.
Parent ion with m/z
2895
*877
*939
*2056
*2448
*2505
*2910
2852
* Ions 877, 939, 2056, 2448 and 2505 are fragments of the parent ion 2910.
Parent ion with m/z
2910Parent ion with m/z
3026
406
374
Parent ion with m/z
3056
*3026
*2622
*2173
406
374
* Ions 1967, 2173 and 2622 are fragments of the parent ion 3026.
Ion 855 is a protonated and desodiated form of ion 877.
855 *1967
Parent ion with m/z
3228
*3244
*2839
*1998
*1268*877
*650*406
*374
* Ions 374, 406, 650, 877, 1268, 1998 and 2839 are fragments of the parent ion 3244.
Parent ion with m/z
3244Parent ion with m/z
3259
*3244
*2839
*1997
*1793
*1268
406
374
* Ions 1268, 1793, 1997 and 2839 are fragments of the parent ion 3244.
Ions 374 and 406 are fragments of the parent ion 3259.
Parent ion with m/z
3288
*3244
*2839
*1997
*1268
406
374
* Ions 1268, 1997 and 2839 are fragments of the parent ion 3244.
Ions 374 and 406 are fragments of the parent ion 3288.
Parent ion with m/z
3302
*3244
*2839
*1997*1268
* Ions 1268, 1997 and 2839 are fragments of the parent ion 3244.
Parent ion with m/z
3635Parent ion with m/z
*3663
*2839
*877
*650
*428
*406
*374
* Ions 374, 406, 428, 650, 877 and 2839 are fragments of the parent ion 3663.
3663
1
2
* 2839
* 3288
406
374
Two potential structures (1 and 2) were observed, but more fragments matched with the structure 1 than the structure 2.
* Ions 2839 and 3288 are fragments of the parent ion n°2.
Ions 374 and 406 are related to NeuGc sialic acid
Parent ion with m/z
3678
*3693
*3288
*2839
*1983*1268
406
* Ions 1268, 1983, 2839 and 3288 are fragments of the parent ion 3693.
Ion 406 is related to NeuGc sialic acid.
Parent ion with m/z
3693Parent ion with m/z
406
3708
406
374 *1268 *1984
*2433
*3288
*3693
* Ions 1268, 1984, 2433 and 3288 are fragments of the parent ion 3693.
Parent ion with m/z
*406
*374 *650 *877
*2837
*3230
*4128
4084Parent ion with m/z
* Ions 374, 406, 650, 877, 2837, 3230 are fragments of
the parent ion 4128 ( )