Table S1. Chemical shift assignment of de-O-acetylated 11F PS

Residue / 1 / 2 / 3 / 4 / 5 / 6 / 6' / CH3
αGal / 5.18 / 3.94 / 4.03 / 4.07 / 4.25 / 3.71 / 3.69
96.35 / 69.06 / 69.58 / 78.73 / 72.19 / 60.77
αGlcNAc / 4.92 / 3.95 / 3.78 / 3.62 / 4.31 / 4.14 / 3.9 / 2.07
98.91 / 54.68 / 71.19 / 70.44 / 71.88 / 69.01 / 69.01 / 22.65 / 174.89
βGlc / 4.52 / 3.4 / 3.67 / 3.67 / 3.6 / 3.99
103.2 / 73.55 / 75.05 / 79.47 / 75.4 / 60.96
βGal / 4.51 / 3.68 / 3.78 / 3.73 / 4.17 / 3.81 / 3.78
103.61 / 70.37 / 78.43 / 75.71 / 65.7 / 61.7
Ribitol / 3.67/65 / 3.85 / 3.89 / 3.74 / 3.81/79
63.17 / 72.81 / 71.49 / 72.54 / 63.15
PO4 / [-0.28]

Chemical shifts (1H/13C[31P]) are in ppm and are referenced to DSS-d6 and DMSO-d6.

Table S2. Chemical shift assignment of native 11F PS

Residue / 1 / 2 / 3 / 4 / 5 / 6 / 6' / CH3 / CH3
αGal / 5.14 / 3.97 / 3.97 / 4.1 / 4.19 / 3.73
95.46 / 68.42 / 69.45 / 78.57 / 71.89 / 60.29
αGlcNAc / 4.95 / 4.23 / 5.25 / 4.42 / 4.5 / 4.18 / 3.94 / 2.02 / H2 / 2.13 / H3
98.78 / 52.6 / 72.88 / 72.35 / 70.65 / 68.56 / 68.61 / 22.51 / 174.9 / 21.33 / 174.4
βGlc / 4.57 / 3.4 / 3.69 / 3.67 / 3.61 / ND
102.97 / 73.7 / 75.03 / 80.19 / 75.27 / ND
βGal / 4.62 / 3.72 / 3.99 / 5.59 / 4.12 / 4.25/4.16 / 2.19 / H4 / 2.12 / H6
103.7 / 70.37 / 75.09 / 66.98 / 71.56 / 63.3 / 20.98 / 173.9 / 20.98 / 174.4
Ribitol / 4.02/3.94 / 3.89 / 3.84 / 3.71 / 3.79/3.66
67.6 / 71.92 / 72.74 / 72.65 / 63.2
PO4 / [-0.51]

Chemical shifts (1H/13C[31P]) are in ppm and are referenced to DSS-d6 and DMSO-d6. ND, not determined.

Table S3. Chemical shift assignment of de-O-acetylated 11C PS

Residue / 1 / 2 / 3 / 4 / 5 / 6 / 6' / CH3
αGal / 5.18 / 3.94 / 4.03 / 4.07 / 4.25 / ND
96.35 / 68.96 / 69.61 / 78.67 / 72.18 / ND
αGlcNAc / 4.92 / 3.94 / 3.78 / 3.62 / 4.32 / 4.14 / 3.9 / 2.07
98.84 / 54.69 / 71.2 / 70.43 / 71.9 / 69 / 69 / 22.64 / 175
βGlc / 4.55 / 3.4 / 3.67 / 3.66 / 3.6 / 3.69
103.14 / 73.57 / 75.11 / 79.47 / 75.39 / 60.77
βGal / 4.51 / 3.68 / 3.77 / 3.72 / 4.17 / 3.81 / 3.78
103.56 / 70.26 / 78.43 / 75.7 / 65.73 / 61.65 / 61.66
Glycerol / 3.67/3.60 / 3.9 / 3.98/3.91
62.87 / 71.47 / 67.35
PO4 / [-0.12]

Chemical shifts (1H/13C[31P]) are in ppm and are referenced to DSS-d6 and DMSO-d6. ND, not determined.

Table S4. Chemical shift assignment of de-O-acetylated 11B PS

Residue / 1 / 2 / 3 / 4 / 5 / 6 / 6' / CH3
αGal / 5.18 / 3.94 / 4.03 / 4.06 / 4.24 / 3.7
96.46 / 68.99 / 69.64 / 78.73 / 72.25 / 60.81
αGlcNAc / 4.91 / 3.94 / 3.78 / 3.62 / 4.33 / 4.13 / 3.9 / 2.07
99.18 / 54.78 / 71.28 / 70.41 / 71.89 / 69.01 / 69 / 22.81 / 175
βGlc / 4.53 / 3.39 / 3.67 / 3.67 / 3.6 / ND
103.28 / 73.62 / 75.07 / 79.5 / 75.54 / ND
βGal / 4.51 / 3.67 / 3.78 / 3.72 / 4.17 / ND
103.6 / 70.32 / 78.37 / 75.78 / 65.76 / ND
Ribitol / 4.13/4.02 / 3.94 / 3.94 / 3.75 / ND
67.8 / 71.71 / 69.04 / 72.75 / ND
PO4 / [-0.00]

Chemical shifts (1H/13C[31P]) are in ppm and are referenced to DSS-d6 and DMSO-d6. ND, not determined.

Table S5. Chemical shift assignment of native 11C PS

Residue / 1 / 2 / 3 / 4 / 5 / 6 / 6' / CH3 / C'
αGal (2) / 5.4 / 5.06 / 4.29 / 4.19 / ND / ND / 2.17
93.71 / 71.61 / 71.7 / 78.63 / ND / ND / 21.18 / 174.4
αGal (1) / 5.26
96.55
αGlcNAc / 4.99 / 4.24 / 5.3 / 4.49 / 4.26 / ND / NAc:2.02
99.02 / 52.6 / 72.52 / ND / 67.14 / ND / 22.58 / 175.1
αGlcNAc / 4.96 / 4.22 / 5.27 / OAc:2.13
98.92 / 52.6 / 72.95 / 21.26 / 174.5
βGlc / 4.56 / 3.37 / 3.67 / 3.67 / 3.6
102.92 / 73.79 / 75.07 / 79.3 / 75.43
βGal / 4.51 / 3.71 / 3.8 / 3.72
103.54 / 70.24 / 78.71 / 75.75
Glycerol / 3.65/57 / 3.86 / 3.89/79
62.97 / 71.52 / 67.25
PO4 / [-0.79] / 0.14

Chemical shifts (1H/13C[31P]) are in ppm and are referenced to DSS-d6 and DMSO-d6. ND, not determined.

Table S6. Chemical shift assignment of native 11B PS

Residue / 1 / 2 / 3 / 4 / 5 / 6 / 6' / CH3 / C' / CH3 / C'
αGal / 5.4 / 5.05 / 4.28 / 4.19 / ND / 3.71 / 2.17
93.68 / 71.56 / 78.57 / 78.57 / ND / 60.27 / 21.19 / 174.4
αGal / 5.26 / ND / ND / ND / ND / ND
96.52 / ND / ND / ND / ND / ND
αGlcNAc / 4.99 / 4.24 / 5.30/5.28 / 4.52/4.46 / 4.5 / 4.14 / 2.02 / 2.14
98.96 / 52.62 / 72.55/72.82 / 72.25/72.29 / 70.55 / 68.28 / 22.74 / 175.1 / 21.3 / 174.5
βGlc / 4.56 / 3.38 / 3.68 / 3.68 / 3.6 / ND
102.87 / 73.75 / 75.02 / 79.25 / 75.42 / ND
βGal / 4.49 / 3.67 / 3.77 / 3.72 / 4.18 / 3.79 / 3.74
103.46 / 70.1 / 78.35 / 75.76 / 65.82 / 61.68 / 61.66
Ribitol / 4.01/3.94 / 3.89 / 3.84 / 3.71 / 3.79/3.65
67.64 / 71.83 / 72.73 / 72.6 / 63.08
PO4 / [-0.56]

Chemical shifts (1H/13C[31P]) are in ppm and are referenced to DSS-d6 and DMSO-d6. ND, not determined.

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