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Supplementary information

Serum Glycomics Profiling of Patients with Primary Restless

Legs Syndrome (RLS) using LC-MS/MS

Xue Dong1†, Stefania Mondello2,3†, Firas Kobeissy4, Raffaele Ferri3, and Yehia Mechref1*

1

Department of Chemistry and Biochemistry, Texas Tech University

2

Department of Biomedical and Dental Sciences and Morphofunctional Imaging, University of

Messina, Messina, Italy

3

Sleep Research Centre, Department of Neurology IC, Oasi Research Institute- IRCCS, Troina,

Italy

4

Department of Biochemistry & Molecular Genetics, American University of Beirut, Beirut,

Lebanon

Authors contributed equally to this work

*Corresponding Author

Department of Chemistry and Biochemistry

Texas Tech University

Lubbock, TX 79409-1061

Email: [email protected]

Tel: 806-742-3059

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Table of contents

Tabel S1.

Relative abundances of N-glycans derived from human blood sera in control cohort.

The results were acquired in the C18 column at 55 ºC. Glycans in the table are named

according to the number of HexNAc, Hexose, Fucose and Sialic acid in a structure.

Table S2. Relative abundances of N-glycans derived from human blood sera in RLS cohort. The

results were acquired in the C18 column at 55 ºC.

Table S3. Average relative abundances of N-glycans with significant difference in control cohort

vs

. RLS cohort after applying Benjamini-Hochberg multiple testing correction.

Table S4. Isomeric quantitation results in control cohort

Table S5. Isomeric quantitation results in RLS cohort

Table S6. Average relative abundances of N-glycan isomers with significant difference in control

cohort

vs.

RLS cohort after applying Benjamini-Hochberg multiple testing correction.

The p-values listed in the table were acquired from Mann-Whitney U test. The

p

-values

in red represent structures still show significant differences after applying the

Benjamini-Hochberg multiple testing correction. The isomeric structures that cannot

be confidently assigned are differentiated by their elution order. Symbols: ,

N-acetylglucosamine (GlcNAc);

, Galactose (Gal);

, Fucose (Fuc);

, Mannose

(Man); , Glucose (Glc); , N-acetylneuraminic acid (NeuAc/Sialic Acid).

Figure S1. Bar graphs showing N-glycan isomeric distribution with significant difference (labeled

with asterisk) in control cohort

vs.

RLS cohort after applying Benjamini-Hochberg

multiple testing correction. Symbols: see Table S6.

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Table S-1

Table S1.

Relative abundances of N-glycans derived from human blood sera in control cohort.

The results were acquired in C18 column at 55 ºC. Glycans in the table are named according to the

number of HexNAc, Hexose, Fucose and Sialic acid in a structure. (ND: not detected)

Relative abundance (%) in different individuals Structures F01 F02 F03 F04 F07 F10 F11 F14 F15 F16 AVE (%) SD (%) 4502 47 48 40 41 47 37 39 46 45 40 43 4 4501 16 19 17 17 17 19 21 16 14 20 18 2 4310 7 4 13 11 2 14 6 7 5 2 7 4 5603 5.0 4.2 4.7 3.8 3.6 4.1 5.4 4.3 4.1 5.9 4.5 0.8 4511 2.0 3.1 3.2 2.5 4.8 3.2 2.8 3.0 3.7 3.2 3.1 0.7 2500 1.4 1.0 1.5 1.1 2.2 1.2 1.5 1.7 3.6 1.5 1.7 0.8 2600 1.2 1.7 1.5 2.1 2.9 1.6 1.1 1.7 3.3 1.3 1.8 0.8 5310 3 2 5 6 3 4 4 3 3 3 4 1 4512 2.0 2.1 1.8 2.3 1.9 1.3 2.5 2.5 3.0 4.2 2.4 0.8 4410 2.8 1.9 1.8 2.1 1.4 1.3 3.3 1.6 2.0 3.1 2.1 0.7 3401 0.8 1.1 1.5 1.7 1.2 1.3 1.1 1.3 1.7 1.3 1.3 0.3 4400 2.0 0.4 0.5 0.5 1.4 0.9 0.6 0.6 1.2 2.2 1.0 0.7 5300 1.1 1.5 1.5 1.7 0.9 2.4 3.8 1.7 1.2 1.7 1.8 0.8 4300 1.8 0.3 0.4 0.3 0.6 0.9 0.4 0.5 0.9 1.0 0.7 0.5 3300 ND 0.2 0.5 0.1 1.8 0.4 0.09 0.2 0.9 0.1 0.4 0.5

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Relative abundance (%) in different individuals Structures F01 F02 F03 F04 F07 F10 F11 F14 F15 F16 AVE (%) (%)SD 4411 0.4 0.6 0.7 0.5 0.7 0.9 0.7 1.2 0.8 0.4 0.7 0.2 3501 1.0 0.6 0.7 0.7 0.6 0.7 0.5 1.0 0.7 0.7 0.7 0.2 4401 0.8 0.7 1.0 0.6 0.7 0.9 0.7 0.7 0.6 0.7 0.7 0.1 4500 0.6 0.2 0.2 0.3 0.9 0.3 0.3 0.4 0.5 0.8 0.5 0.2 5400 0.5 0.5 0.5 0.6 0.4 0.7 1.2 0.6 0.5 0.8 0.6 0.2 3400 0.05 0.1 0.1 0.1 0.8 0.1 0.1 0.1 0.5 0.1 0.2 0.3 4510 0.45 0.51 0.39 0.57 0.61 0.37 0.56 0.42 0.52 0.51 0.49 0.08 6704 0.5 0.6 0.5 0.4 0.5 0.4 0.6 0.5 0.4 1.0 0.5 0.2 3411 0.10 0.10 0.18 0.20 0.20 0.18 0.08 0.19 0.39 0.24 0.19 0.09 5410 0.23 0.24 0.27 0.31 0.27 0.22 0.30 0.23 0.33 0.19 0.26 0.04 5602 0.7 0.8 0.7 0.6 0.6 1.0 0.6 0.6 0.3 0.9 0.7 0.2 5613 0.5 0.6 0.3 0.6 0.6 0.4 0.3 0.5 0.3 0.6 0.5 0.1 3310 0.08 0.09 0.18 0.17 0.15 0.15 0.10 0.14 0.25 0.12 0.14 0.05 6703 0.2 0.6 0.3 0.3 0.4 0.4 0.6 0.4 0.2 0.8 0.4 0.2 5601 0.05 0.06 0.10 0.10 0.10 0.21 0.24 0.04 0.02 0.16 0.11 0.07 6714 0.07 0.14 0.04 0.07 0.11 0.04 0.04 0.11 0.11 0.09 0.08 0.03 5511 0.07 0.10 0.13 0.09 0.26 0.08 0.13 0.12 0.11 0.12 0.12 0.05 5501 0.05 0.16 0.07 0.12 0.25 0.10 0.19 0.16 0.07 0.06 0.12 0.06

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Relative abundance (%) in different individuals Structures F01 F02 F03 F04 F07 F10 F11 F14 F15 F16 AVE (%) (%)SD 5411 0.03 0.04 0.11 0.16 0.08 0.09 0.08 0.07 0.05 0.07 0.08 0.04 5612 0.03 0.03 0.02 0.02 0.03 0.03 0.04 0.03 0.05 0.05 0.03 0.01 3410 0.01 0.05 0.02 0.01 0.07 ND 0.001 0.05 0.04 0.07 0.03 0.03 5512 0.06 0.15 0.10 0.09 0.10 0.10 0.18 0.11 0.04 0.07 0.10 0.04 6411 0.07 0.07 0.05 0.09 0.13 0.03 0.10 0.06 0.04 0.15 0.08 0.04 4531 0.06 0.07 0.03 0.09 0.05 0.04 0.05 0.06 0.03 0.14 0.06 0.03 6812 0.04 0.06 0.04 0.05 0.06 0.06 0.05 0.04 0.03 0.09 0.05 0.02 6712 ND 0.03 ND 0.01 ND 0.02 ND 0.001 0.02 0.001 0.01 0.01 5500 ND 0.009 0.005 ND 0.016 0.010 0.012 0.009 0.016 0.009 0.010 0.005 5401 ND 0.04 0.03 0.03 0.01 0.03 0.08 0.03 0.01 0.01 0.03 0.02 3510 ND ND ND ND 0.010 ND ND 0.004 0.012 0.008 0.003 0.005 5604 0.02 0.01 0.01 0.02 0.01 0.01 0.004 0.01 0.01 0.01 0.01 0.01 6702 0.03 0.06 0.03 0.03 0.04 0.06 0.06 0.03 0.01 0.05 0.04 0.02 3500 ND ND ND ND 0.04 ND ND ND 0.01 ND 0.01 0.01 2900 ND 0.01 ND ND 0.01 0.02 0.01 0.002 0.01 0.03 0.01 0.01 6501 ND 0.01 ND ND 0.01 ND ND 0.01 0.01 0.02 0.01 0.01 5711 ND ND 0.003 0.006 ND 0.004 ND ND 0.006 0.014 0.003 0.004 6713 ND 0.003 0.002 0.002 0.005 0.001 0.002 0.003 0.002 0.002 0.003 0.001

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Relative abundance (%) in different individuals Structures F01 F02 F03 F04 F07 F10 F11 F14 F15 F16 AVE (%) (%)SD 5611 ND ND 0.002 0.002 0.002 ND ND ND 0.001 ND 0.001 0.001 6723 ND 0.002 ND 0.001 0.001 0.001 0.002 0.001 0.001 0.003 0.001 0.001 6613 ND 0.0021 0.0016 0.0011 0.0014 0.0020 0.0021 0.0013 0.0013 0.0024 0.0017 0.0004 7804 ND 0.001 0.001 ND ND 0.001 0.002 0.001 0.001 0.002 0.001 0.001 2310 ND 0.015 0.009 0.007 ND 0.006 ND 0.002 0.001 ND 0.004 0.005 5610 ND 0.003 ND 0.003 0.008 0.002 0.002 ND 0.001 ND 0.002 0.003 7803 ND 0.0010 ND 0.0004 0.0005 0.0010 ND 0.0006 0.0009 ND 0.0004 0.0004 5623 ND 0.002 0.001 0.002 0.003 0.001 0.001 0.001 ND 0.001 0.001 0.001 6724 ND 0.001 ND ND 0.001 ND 0.08 0.001 ND ND 0.01 0.02

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Table S-2

Table S2 Relative abundances of N-glycans derived from human blood sera in RLS cohort. The

results were acquired in C18 column at 55 ºC. Glycans in the table are named according to the

number of HexNAc, Hexose, Fucose and Sialic acid in a structure. (ND: not detected)

Relative abundance (%) in different individuals Glycan R01 R02 R03 R04 R05 R06 R07 R08 R09 R10 R11 R12 AVE (%) SD(%) 4502 20 12 31 14 7 10 15 9 15 28 13 23 16 8 4511 3 10 3 4 7 12 26 6 25 23 20 9 12 9 4310 26 8 17 7 30 20 4 23 2 1 2 8 12 10 4501 8 12 5 19 6 12 2 10 1 1 14 11 8 6 4512 8 8 4 10 6 3 8 6 6 9 4 8 7 2 2500 4 6 3 5 4 1 6 8 5 ND 4 4 5 2 4410 2 0.1 7 5 1 6 2 12 0.2 0.4 3 6 4 4 5613 1 5 1 3 2 2 8 1 8 4 4 1 3 2 5602 2 4 2 2 3 4 5 1 3 6 2 2 3 2 4611 2 4 2 3 2 2 ND 3 ND ND 4 7 3 2 5310 4 3 3 3 5 3 1 2 2 1 2 1 2 1 3401 3.0 2.6 2.3 3.2 2.1 2.1 1.2 2.1 1.7 4.0 1.3 2.2 2.3 0.8 2600 1 3 1 1 2 3 3 1 4 2 4 2 2 1 5603 1 3 4 3 1 2 1 3 1 0.4 4 3 2 1 5300 2 2 3 3 3 3 3 2 1 0.4 1 1 2 1 4411 1 1 2 1 1 3 1 1 4 3 2 1 2 1 4510 1.3 2.4 1.5 1.3 0.7 2.4 1.9 1.2 ND 1.5 1.7 2.7 1.7 0.8 4401 3 1 2 3 0.2 2 0.2 1 0.4 1 2 2 2 1 6703 0.5 2 1 1 1 1 1 1 4 1 1 1 1 1 3310 1 3 1 0.5 1 0.3 0.1 1 5 1 2 0.3 1 1 4400 1 0.5 1 1 3 0.2 ND 0.3 1 ND 0.2 2 1.0 0.9 3501 0.5 0.7 0.5 1.2 0.9 0.9 0.3 0.7 1.0 1.0 0.8 0.8 0.8 0.3 4300 0.7 0.2 1.0 0.2 3.5 0.2 0.1 0.7 0.1 0.3 1.0 0.7 0.7 0.9 5410 0.4 0.3 0.3 0.6 0.8 1.1 1.0 0.3 0.3 0.4 1.0 0.5 0.6 0.3 5400 0.5 0.8 0.4 1.1 0.8 0.7 ND 0.5 0.3 1.1 0.5 0.2 0.6 0.3 5512 0.1 0.3 0.2 0.2 0.4 0.7 2.1 0.1 1.2 0.9 0.4 0.3 0.6 0.6 6714 0.2 0.9 0.3 0.5 0.3 0.1 0.6 0.5 0.6 2.1 0.4 0.1 0.5 0.5 4500 0.5 0.7 0.5 0.6 0.7 0.2 0.8 0.6 ND 0.4 0.5 0.8 0.6 0.2 5612 0.1 0.7 0.1 0.5 0.4 0.1 0.9 0.3 1.5 0.8 0.3 0.2 0.5 0.4 3411 0.1 0.7 0.3 0.2 0.4 0.3 1.2 0.2 0.9 0.5 0.5 0.2 0.4 0.3 6704 0.3 0.4 0.2 0.2 0.1 0.2 0.1 0.3 0.4 0.4 0.4 0.5 0.3 0.1 4531 0.1 0.2 0.1 0.2 0.3 0.1 0.7 0.1 0.4 1.0 0.3 0.03 0.3 0.3 3400 0.1 0.1 0.04 0.2 0.4 0.1 0.3 0.1 0.2 ND 0.5 0.2 0.2 0.1 3300 0.3 0.3 0.1 0.2 0.1 0.05 0.3 0.03 0.2 0.3 0.1 0.1 0.2 0.1 5501 0.02 0.1 0.02 0.3 0.1 0.1 0.3 0.1 0.2 0.2 0.1 0.2 0.1 0.1 3410 ND 0.4 0.03 ND 0.2 0.1 0.1 0.2 0.5 ND 0.2 0.1 0.2 0.2 5511 0.02 0.1 0.1 0.03 0.2 0.1 0.3 0.04 0.2 ND 0.3 0.1 0.1 0.1 6600 ND 0.14 0.14 0.03 0.03 0.13 0.14 0.14 0.18 0.17 0.17 0.10 0.12 0.06 2900 ND 0.1 0.1 0.1 0.1 0.04 0.1 0.1 0.3 0.3 0.04 0.04 0.1 0.1 2300 0.2 0.4 0.003 0.03 0.04 0.1 0.4 0.1 0.03 0.1 0.03 ND 0.1 0.1 5401 0.03 0.002 0.04 0.1 0.1 0.1 0.2 0.1 0.2 0.4 0.02 ND 0.1 0.1 5601 0.02 0.07 0.04 0.07 0.12 0.14 0.19 0.04 0.22 0.15 0.04 0.03 0.09 0.07 7410 ND 0.2 0.02 0.03 ND 0.009 ND ND 0.1 0.5 0.02 ND 0.1 0.1 5411 0.03 0.03 0.04 0.07 0.13 0.04 0.05 0.03 0.14 0.13 0.04 0.01 0.06 0.05

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Glycan Relative abundance (%) in different individuals AVE (%) SD (%) 6702 0.01 0.06 0.01 0.02 0.04 0.03 0.17 0.03 0.14 0.17 0.03 0.04 0.06 0.06 6411 ND 0.17 0.02 0.02 0.03 0.03 0.24 0.04 0.01 ND 0.06 0.01 0.06 0.07 5500 0.01 0.002 0.01 0.14 ND ND 0.09 ND 0.02 0.03 0.04 0.02 0.04 0.04 5604 0.01 0.04 0.01 0.02 0.01 0.00 0.03 0.02 0.09 0.08 0.02 0.01 0.03 0.03 7510 ND 0.06 0.01 ND ND ND 0.05 0.002 0.03 0.10 0.03 ND 0.04 0.03 3510 ND ND ND ND 0.06 ND ND ND ND 0.10 0.06 0.02 0.06 0.03 6713 0.003 0.02 0.01 0.01 0.01 0.004 0.02 0.005 0.04 0.05 0.02 0.004 0.02 0.01 4701 ND ND ND 0.03 ND ND ND ND 0.06 0.003 0.02 ND 0.03 0.02 7803 ND 0.01 0.01 0.01 0.002 0.002 0.02 0.01 0.02 0.02 0.01 0.002 0.01 0.01 7804 ND 0.002 0.003 0.035 0.003 0.003 ND 0.01 0.04 ND 0.003 0.002 0.01 0.01 4520 ND ND ND ND ND ND ND 0.02 0.01 0.02 ND ND 0.02 0.01 7812 ND 0.004 0.005 0.003 0.002 0.002 ND 0.004 0.007 ND 0.005 ND 0.004 0.002 4602 0.002 0.004 ND ND ND ND ND ND 0.005 ND ND ND 0.004 0.002

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Table S-3

Table S3. Average relative abundances of N-glycans with significant difference in control cohort

vs.

RLS cohort after applying Benjamini-Hochberg multiple testing correction. Glycans in the

table are named according to the number of HexNAc, Hexose, Fucose and Sialic acid in a structure.

(ND: not detected)

Relative abundance (%) ± SD (%)

Structure

Control cohort

RLS cohort

p-value

2300

ND

0.1±0.1

1.07E-04

2900

0.01±0.01

0.1±0.1

6.37E-04

3310

0.14±0.05

1±1

9.74E-04

3401

1.30±0.30

2.3±0.8

1.52E-03

4501

18±2

8±6

7.56E-04

4502

43±4

16±8

7.54E-05

4510

0.49±0.08

1.7±0.8

9.74E-04

4512

2.40±0.80

7±2

1.31E-04

4611

ND

3±2

8.72E-04

5410

0.26±0.04

0.6±0.3

7.66E-04

5602

0.70±0.20

3±2

7.23E-05

5603

4.50±0.80

2±1

2.21E-04

5612

0.03±0.01

0.5±0.4

6.86E-05

5613

0.50±0.10

3±2

7.09E-05

5623

0.001±0.001

ND

2.15E-04

6600

ND

0.12±0.06

1.07E-04

6613

0.0017±0.0004

ND

6.40E-05

6703

0.40±0.20

1±1

3.60E-04

6704

0.50±0.20

0.3±0.1

7.32E-04

6713

0.003±0.001

0.02±0.01

2.04E-04

6714

0.08±0.03

0.5±0.5

1.26E-04

6723

0.001±0.001

ND

2.15E-04

6812

0.05±0.02

ND

1.47E-05

7803

0.0004±0.0004

0.01±0.01

5.62E-04

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Table S-4

Table S4. Isomeric quantitation results in control cohort. Glycans in the table are named according

to the number of HexNAc, Hexose, Fucose and Sialic acid in a structure. (ND: not detected)

Ratio of different isomeric structures in different individuals Structure F01 F02 F03 F04 F07 F10 F11 F14 F15 F16 AVE SD 4502-1 0.02 0.02 0.03 0.04 0.04 0.05 0.12 0.04 0.08 0.04 0.05 0.03 4502-2 0.2 0.2 0.2 0.2 0.1 0.2 0.9 0.3 0.3 0.2 0.3 0.2 4502-3 0.8 0.8 0.7 0.7 0.9 0.7 0.0 0.7 0.6 0.7 0.7 0.2 4501-1 0.07 0.04 0.05 0.07 0.06 0.05 0.07 0.06 0.13 0.08 0.07 0.03 4501-2 0.94 0.96 0.95 0.93 0.94 0.95 0.93 0.94 0.87 0.92 0.93 0.03 3401-1 0.12 0.16 0.09 0.11 0.11 0.11 0.14 0.10 0.15 0.16 0.13 0.03 3401-2 0.06 0.06 0.06 0.03 0.05 0.05 0.10 0.04 0.04 0.08 0.06 0.02 3401-3 0.81 0.78 0.85 0.86 0.85 0.84 0.75 0.86 0.81 0.76 0.82 0.04 4512-1 0.21 0.09 0.07 0.09 0.08 0.02 0.02 0.10 0.07 0.02 0.08 0.06 4512-2 0.52 0.58 0.54 0.58 0.35 0.56 0.63 0.54 0.72 0.65 0.57 0.10 4512-3 0.1 0.1 0.1 0.1 0.4 0.1 0.1 0.1 0.1 0.1 0.1 0.1 4512-4 0.17 0.24 0.28 0.25 0.14 0.33 0.26 0.28 0.12 0.25 0.23 0.07 4511-1 0.04 0.01 0.01 0.02 0.03 0.00 0.00 0.00 0.00 0.00 0.01 0.01 4511-2 0.07 0.04 0.04 0.04 0.02 0.03 0.03 0.04 0.03 0.03 0.04 0.01 4511-3 0.35 0.26 0.21 0.29 0.16 0.25 0.25 0.22 0.32 0.30 0.26 0.06 4511-4 0.55 0.68 0.75 0.65 0.79 0.72 0.72 0.74 0.65 0.67 0.69 0.07 5603-1 0.1 0.1 0.1 0.1 0.5 0.1 0.0 0.1 0.1 0.0 0.1 0.1 5603-2 0.21 0.17 0.16 0.17 0.07 0.14 0.17 0.16 0.20 0.14 0.16 0.04 5603-3 0.09 0.09 0.07 0.07 0.04 0.05 0.05 0.08 0.10 0.07 0.07 0.02 5603-4 0.6 0.7 0.7 0.7 0.4 0.7 0.7 0.7 0.5 0.7 0.6 0.1 5603-5 0.009 0.007 0.000 0.009 0.008 0.007 0.007 0.013 0.008 0.005 0.007 0.003

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Ratio of different isomeric structures in different individuals Structure F01 F02 F03 F04 F07 F10 F11 F14 F15 F16 AVE SD 5603-6 0.008 0.006 0.012 0.021 0.011 0.017 0.015 0.023 0.010 0.020 0.014 0.006 3501-1 0.17 0.24 0.18 0.21 0.24 0.22 0.25 0.22 0.31 0.35 0.24 0.06 3501-2 0.78 0.68 0.79 0.76 0.71 0.66 0.63 0.72 0.66 0.55 0.69 0.07 3501-3 0.05 0.08 0.03 0.03 0.05 0.11 0.12 0.06 0.03 0.10 0.07 0.03 5601-1 0.61 0.65 0.67 0.65 0.49 0.75 0.68 0.56 0.44 0.66 0.62 0.09 5601-2 0.39 0.36 0.33 0.35 0.51 0.25 0.32 0.44 0.56 0.34 0.38 0.09 5400-1 0.94 0.86 0.90 0.92 0.97 0.84 0.68 0.99 0.97 0.87 0.89 0.09 5400-2 0.06 0.14 0.10 0.09 0.03 0.16 0.32 0.01 0.03 0.13 0.11 0.09 6703-1 0.96 0.99 0.94 0.97 0.96 0.97 0.98 0.97 0.88 0.95 0.96 0.03 6703-2 0.04 0.00 0.06 0.04 0.03 0.03 0.02 0.03 0.12 0.05 0.04 0.03 4401-1 0.08 0.07 0.07 0.08 0.08 0.06 0.08 0.08 0.14 0.13 0.09 0.03 4401-2 0.92 0.93 0.93 0.92 0.92 0.94 0.92 0.92 0.87 0.87 0.91 0.03 3400-1 0.7 0.8 0.8 0.8 1.0 0.8 0.6 0.8 1.0 0.8 0.8 0.1 3400-2 0.3 0.2 0.2 0.2 0.0 0.2 0.4 0.2 0.0 0.2 0.2 0.1 6714-1 0.6 0.5 0.4 0.4 0.5 0.3 0.3 0.5 0.4 0.4 0.4 0.1 6714-2 0.15 0.25 0.29 0.27 0.25 0.45 0.41 0.25 0.41 0.35 0.31 0.09 6714-3 0.21 0.25 0.29 0.32 0.23 0.29 0.29 0.22 0.20 0.28 0.26 0.04

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Table S-5

Table S5. Isomeric quantitation results in RLS cohort. Glycans in the table are named according

to the number of HexNAc, Hexose, Fucose and Sialic acid in a structure. (ND: not detected)

Ratio of different isomeric structures in different individuals Structure R01 R02 R03 R04 R05 R06 R07 R08 R09 R10 R11 R12 AVE SD 4502-1 0.08 0.07 0.07 0.06 0.04 0.05 0.06 0.05 0.07 0.08 0.05 0.04 0.06 0.01 4502-2 0.35 0.30 0.25 0.31 0.25 0.27 0.32 0.30 0.21 0.32 0.26 0.31 0.29 0.04 4502-3 0.57 0.63 0.68 0.62 0.70 0.68 0.63 0.65 0.71 0.60 0.68 0.65 0.65 0.04 4501-1 0.15 0.13 0.12 0.11 0.09 0.09 0.11 0.10 0.09 0.17 0.10 0.07 0.11 0.03 4501-2 0.85 0.87 0.88 0.89 0.92 0.91 0.88 0.90 0.91 0.83 0.90 0.93 0.89 0.03 3401-1 0.13 0.12 0.10 0.09 0.07 0.06 0.05 0.003 0.11 0.11 0.07 0.09 0.08 0.04 3401-2 0.04 0.03 0.05 0.02 0.03 0.03 0.02 0.001 0.04 0.03 0.03 0.05 0.03 0.01 3401-3 0.83 0.86 0.85 0.90 0.90 0.91 0.93 1.00 0.85 0.86 0.90 0.87 0.89 0.05 4512-1 0.05 0.07 0.03 0.09 0.03 0.02 0.05 0.02 0.02 0.13 0.11 0.02 0.05 0.04 4512-2 0.79 0.76 0.81 0.74 0.74 0.50 0.67 0.76 0.77 0.72 0.66 0.66 0.71 0.08 4512-3 0.09 0.07 0.05 0.06 0.08 0.09 0.09 0.09 0.07 0.07 0.07 0.09 0.08 0.01 4512-4 0.07 0.09 0.11 0.11 0.15 0.39 0.19 0.13 0.14 0.09 0.16 0.23 0.15 0.09 4511-1 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4511-2 0.05 0.08 0.06 0.09 0.04 0.02 0.05 0.06 0.03 0.12 0.06 0.04 0.06 0.03 4511-3 0.4 0.5 0.4 0.5 0.4 0.2 0.3 0.4 0.4 0.5 0.2 0.2 0.4 0.1 4511-4 0.5 0.5 0.5 0.4 0.6 0.7 0.7 0.5 0.6 0.4 0.7 0.8 0.6 0.1 5603-1 0.14 0.12 0.07 0.12 0.07 0.06 0.14 0.04 0.10 0.18 0.16 0.07 0.11 0.04 5603-2 0.25 0.20 0.21 0.19 0.18 0.16 0.18 0.20 0.13 0.19 0.16 0.19 0.19 0.03 5603-3 0.08 0.09 0.00 0.11 0.08 0.08 0.11 0.06 0.07 0.11 0.08 0.07 0.08 0.03 5603-4 0.53 0.56 0.69 0.55 0.65 0.67 0.54 0.68 0.65 0.48 0.55 0.64 0.60 0.07 5603-5 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 5603-6 0.01 0.02 0.02 0.03 0.02 0.02 0.02 0.01 0.03 0.01 0.04 0.02 0.02 0.01 3501-1 0.34 0.43 0.34 0.32 0.28 0.24 0.18 0.36 0.32 0.32 0.32 0.24 0.31 0.07

(13)

Ratio of different isomeric structures in different individuals Structure R01 R02 R03 R04 R05 R06 R07 R08 R09 R10 R11 R12 AVE SD 3501-2 0.57 0.48 0.58 0.65 0.63 0.69 0.76 0.60 0.65 0.62 0.64 0.66 0.63 0.07 3501-3 0.09 0.09 0.08 0.02 0.09 0.06 0.06 0.04 0.03 0.06 0.04 0.10 0.06 0.03 5601-1 0.71 0.62 0.70 0.58 0.69 0.72 0.44 0.51 0.58 0.54 0.54 0.55 0.60 0.09 5601-2 0.29 0.38 0.30 0.42 0.31 0.28 0.56 0.49 0.42 0.46 0.46 0.45 0.40 0.09 5400-1 0.96 0.98 0.99 0.99 0.96 0.85 0.86 0.93 0.98 0.84 0.83 0.75 0.91 0.08 5400-2 0.04 0.02 0.01 0.01 0.04 0.15 0.14 0.07 0.03 0.16 0.17 0.25 0.09 0.08 6703-1 0.77 0.83 0.86 0.81 0.89 0.93 0.81 0.91 0.70 0.72 0.71 0.88 0.82 0.08 6703-2 0.24 0.17 0.14 0.18 0.11 0.07 0.19 0.09 0.30 0.28 0.29 0.12 0.18 0.08 4401-1 0.13 0.12 0.09 0.08 0.04 0.03 0.07 0.05 0.06 0.11 0.07 0.07 0.08 0.03 4401-2 0.87 0.88 0.91 0.91 0.95 0.97 0.92 0.95 0.94 0.89 0.93 0.93 0.92 0.03 3400-1 0.79 0.85 0.81 0.70 0.96 0.67 0.76 0.80 0.84 0.79 0.90 0.86 0.81 0.08 3400-2 0.21 0.15 0.19 0.30 0.04 0.33 0.24 0.19 0.16 0.21 0.10 0.15 0.19 0.08 6714-1 0.26 0.46 0.35 0.40 0.23 0.28 0.37 0.40 0.17 0.42 0.41 0.25 0.33 0.09 6714-2 0.59 0.38 0.47 0.45 0.48 0.40 0.56 0.45 0.53 0.44 0.39 0.52 0.47 0.07 6714-3 0.15 0.16 0.18 0.15 0.29 0.32 0.08 0.16 0.30 0.15 0.20 0.24 0.20 0.07

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Table S-6

Table S6. Average relative abundances of N-glycan isomers with significant difference in control

cohort

vs

. RLS cohort after applying Benjamini-Hochberg multiple testing correction. The

p

-values listed in the table were acquired from Mann-Whitney U test. The

p

-values in red represent

structures still show significant differences after applying the Benjamini-Hochberg multiple

testing correction. The isomeric structures that cannot be confidently assigned are differentiated

by their elution order. Symbols: , N-acetylglucosamine (GlcNAc);

, Galactose (Gal);

,

Fucose (Fuc); , Mannose (Man); , Glucose (Glc); , N-acetylneuraminic acid (NeuAc/Sialic

Acid).

Relative abundance ± SD

Structure | Eluting order

Control cohort

RLS cohort

p

-value

1

0.13±0.03

0.08±0.04

9.54E-03

2

0.06±0.02

0.03±0.01

2.27E-03

3

0.82±0.04

0.89±0.05

1.80E-03

1

0.24±0.06

0.31±0.07

1.85E-02

2

0.690±0.07

0.63±0.07

2.92E-02

3

0.07±0.03

0.06±0.03

9.47E-01

1

0.07±0.03

0.11±0.03

1.46E-03

2

0.93±0.03

0.89±0.03

1.48E-03

1

0.05±0.03

0.06±0.01

4.81E-02

2

0.3±0.2

0.29±0.04

1.61E-02

3

0.7±0.2

0.65±0.04

4.52E-02

1

0.01±0.01

0.00±0.00

7.03E-03

2

0.04±0.01

0.06±0.03

2.92E-02

3

0.26±0.06

0.4±0.1

4.25E-02

4

0.69±0.07

0.6±0.1

2.87E-02

1

0.08±0.06

0.05±0.04

3.82E-01

2

0.6±0.1

0.71±0.08

1.70E-03

(15)

Structure | Eluting order

Relative abundance ± SD

p

-value

3

0.1±0.1

0.08±0.01

3.55E-05

4

0.23±0.07

0.15±0.09

1.33E-02

1

0.1±0.1

0.11±0.04

5.20E-01

2

0.16±0.04

0.19±0.03

9.04E-02

3

0.07±0.02

0.08±0.03

2.85E-01

4

0.6±0.1

0.60±0.07

3.77E-02

5

0.007±0.003

0.01±0.01

5.42E-04

6

0.014±0.006

0.02±0.01

1.30E-01

1

0.96±0.03

0.82±0.08

1.89E-04

2

0.04±0.03

0.18±0.08

1.90E-04

1

0.4±0.1

0.33±0.09

4.54E-02

2

0.31±0.09

0.47±0.07

1.20E-03

3

0.26±0.04

0.20±0.07

5.06E-02

(16)

Figure S-1

Figure S-1. Bar graphs showing N-glycan isomeric distribution with significant difference

(labeled with asterisk) in control cohort

vs.

RLS cohort after applying Benjamini-Hochberg

multiple testing correction. Symbols: see Table S6.

References

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