Supporting Information: Unified Picture for the Conformation and Stabilization of The

Supporting information: Unified picture for the conformation and stabilization of the O-glycosidic linkage in glycopeptide model structures

Pál D. Mezei,1 Gábor I. Csonka,1

1 Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Hungary

Table S1aEquilibrium single point energies, relative energies, the number of hydrogen bonds and torsion angles of the α-GalNAc-Ser model structures (We calculated eight new geometries compared to the reoptimized geometries.)

(hartree) / (kcal mol-1) / H-bonds / φ / ψ / χ1 / χ2 / χ3 / τ2 / τ3 / τ4 / τ5 / τ6
01 / -1314.692287 / 3.8 / 6 / -83.31 / 67.29 / 41.00 / -166.12 / -176.42 / 167.43 / -149.71 / -161.23 / 65.95 / -42.98
02 / -1314.698278 / 0.0 / 7 / -77.25 / 83.19 / 43.36 / 154.32 / -159.16 / 168.16 / -150.33 / -161.17 / 176.74 / -57.15
04 / -1314.689037 / 5.8 / 5 / -83.68 / 66.66 / 42.22 / -168.30 / -179.04 / 168.52 / -152.45 / -159.74 / 164.67 / -154.71
06 / -1314.697100 / 0.7 / 7 / -78.95 / 83.77 / 44.56 / 156.60 / -162.58 / 173.28 / -155.74 / -160.69 / -39.94 / 71.61
09 / -1314.693942 / 2.7 / 6 / -82.84 / 69.95 / -55.14 / 153.62 / -164.21 / 24.97 / -40.26 / 19.72 / 70.06 / 53.81
10 / -1314.695660 / 1.6 / 6 / 73.08 / -44.67 / -175.71 / 89.90 / -162.74 / 160.96 / -143.25 / -160.98 / 68.18 / -44.08
12 / -1314.683527 / 9.3 / 5 / 56.19 / 40.87 / 24.61 / 157.41 / -175.27 / 167.29 / -150.14 / -160.13 / 68.56 / -43.77
13 / -1314.685726 / 7.9 / 4 / 70.37 / -74.12 / 179.29 / -166.68 / -173.51 / 164.35 / -152.87 / -161.24 / -170.48 / -65.16
15 / -1314.691499 / 4.3 / 7 / -84.88 / 79.20 / 47.05 / 140.40 / -164.19 / 165.02 / -135.03 / 38.65 / 64.34 / 53.52
16 / -1314.692679 / 3.5 / 6 / -77.19 / 83.52 / 43.77 / 157.64 / -161.65 / 170.98 / -153.11 / -160.64 / -171.96 / 68.30
n1 / -1314.690276 / 5.0 / 7 / -79.44 / 73.45 / 45.77 / 154.85 / -155.46 / 165.60 / -145.66 / -42.97 / 177.04 / -55.35
n2 / -1314.692748 / 3.5 / 6 / -83.32 / 67.05 / 42.81 / -169.53 / -175.22 / 168.70 / -152.97 / -160.01 / 66.17 / -42.58
n3 / -1314.688071 / 6.4 / 7 / -80.27 / 74.62 / 44.22 / 157.46 / -156.46 / 172.06 / -153.51 / -46.30 / -25.61 / 62.63
n4 / -1314.688585 / 6.1 / 6 / -83.65 / 69.81 / -55.41 / 158.87 / -165.54 / 22.55 / -39.15 / -35.31 / -179.28 / -55.95
n5 / -1314.687563 / 6.7 / 7 / -84.51 / 79.16 / 46.40 / 144.51 / -160.43 / 170.76 / -152.07 / -47.54 / -29.80 / 64.99
n6 / -1314.692085 / 3.9 / 7 / -85.26 / 79.29 / 47.27 / 140.79 / -163.04 / 164.63 / -135.13 / 38.45 / 64.42 / 53.34
n7 / -1314.686345 / 7.5 / 5 / -83.16 / 69.63 / -56.64 / 157.29 / -163.43 / 23.29 / -37.94 / -39.74 / -40.88 / 74.44
n8 / -1314.689462 / 5.5 / 7 / -80.89 / 81.84 / 46.18 / 145.66 / -160.28 / 163.36 / -139.52 / -40.64 / 177.18 / -55.62

Table S1bEquilibrium single point energies, relative energies, the number of hydrogen bonds and torsion angles of the α-ManNAc-Ser model structures

(hartree) / (kcal mol-1) / H-bonds / φ / ψ / χ1 / χ2 / χ3 / τ2 / τ3 / τ4 / τ5 / τ6
01 / -1314.688082 / 5.7 / 5 / -82.70 / 62.13 / 47.01 / 130.95 / -169.51 / -168.00 / -108.88 / 160.89 / 177.47 / -54.70
02 / -1314.685663 / 7.2 / 4 / -75.00 / 96.24 / -175.71 / -167.67 / 178.82 / -154.32 / -151.72 / 165.46 / -168.62 / 52.62
03 / -1314.689308 / 4.9 / 6 / -83.69 / 65.74 / 42.88 / 113.17 / -161.01 / -171.25 / -103.49 / 167.43 / -72.24 / 47.33
04 / -1314.680808 / 10.2 / 5 / 74.08 / -48.48 / -171.73 / -152.47 / -169.03 / -166.40 / -110.30 / 161.02 / 177.90 / -49.95
05 / -1314.683577 / 8.5 / 6 / -77.10 / 38.41 / 73.59 / -141.72 / -159.19 / -167.53 / -111.21 / 161.03 / -178.39 / -61.75
06 / -1314.686850 / 6.4 / 5 / -83.18 / 65.00 / 48.14 / 129.81 / -178.80 / -163.85 / -132.47 / 168.29 / 64.95 / 55.99
07 / -1314.681382 / 9.9 / 4 / -80.60 / 49.24 / 71.23 / -121.65 / -151.62 / -165.68 / -114.40 / 161.48 / -170.60 / -174.77
08 / -1314.687015 / 6.3 / 6 / -125.20 / -7.61 / 65.21 / -86.66 / -147.50 / -166.85 / -110.15 / 161.58 / -171.41 / 179.68
09 / -1314.682786 / 9.0 / 5 / 71.50 / -55.48 / -179.79 / -164.11 / -174.84 / -173.67 / -100.96 / 161.12 / -74.16 / 50.36
10 / -1314.677701 / 12.2 / 4 / 74.37 / -51.89 / 138.30 / -173.63 / 177.56 / -164.38 / -122.24 / 165.74 / -168.97 / 57.82
11 / -1314.684168 / 8.1 / 4 / -83.24 / 63.13 / 46.33 / 127.65 / -166.53 / -169.80 / -106.85 / 159.95 / -167.78 / 179.52
12 / -1314.683297 / 8.7 / 5 / -84.92 / 62.84 / 43.14 / 121.12 / -154.43 / -165.09 / -108.87 / 177.67 / 61.11 / -179.34
13 / -1314.686883 / 6.4 / 4 / -80.63 / 90.64 / -163.44 / -145.94 / -154.03 / -155.04 / -137.56 / 166.17 / -160.13 / -35.59
14 / -1314.688407 / 5.5 / 4 / -86.86 / 64.83 / -53.83 / -90.72 / -160.68 / -166.50 / -108.93 / 166.15 / -177.17 / 61.42
15 / -1314.685652 / 7.2 / 5 / -85.71 / 70.33 / -59.06 / -159.40 / -174.49 / -166.05 / -112.76 / 169.36 / -73.92 / 49.52
16 / -1314.679662 / 10.9 / 3 / -86.09 / -2.96 / 78.52 / -144.85 / -163.00 / -177.18 / -99.24 / 157.26 / -167.58 / -174.44
17 / -1314.687599 / 6.0 / 4 / 71.82 / -52.53 / -58.05 / -65.12 / -150.58 / -178.62 / -96.99 / 157.06 / -165.23 / -169.03

Table S1cEquilibrium single point energies, relative energies, the number of hydrogen bonds and torsion angles of the β-GalNAc-Ser model structures

(hartree) / (kcal mol-1) / H-bonds / φ / ψ / χ1 / χ2 / χ3 / τ2 / τ3 / τ4 / τ5 / τ6
01 / -1314.695693 / 0.9 / 6 / -81.72 / 55.39 / -57.39 / 122.78 / 169.02 / 176.18 / -150.67 / -163.35 / 69.82 / -49.68
02 / -1314.693708 / 2.1 / 7 / -82.83 / 57.66 / 56.74 / -174.52 / -58.65 / -146.58 / 179.73 / -164.88 / 64.89 / -44.70
03 / -1314.696403 / 0.4 / 7 / -81.96 / 56.51 / 38.19 / 68.44 / 162.47 / -167.28 / -169.07 / -161.63 / 73.47 / -49.57
04 / -1314.692794 / 2.7 / 7 / -82.81 / 60.40 / 55.75 / -179.48 / -57.05 / -141.25 / 174.82 / -165.59 / -178.61 / -51.39
05 / -1314.684087 / 8.2 / 6 / 64.28 / -56.16 / 72.87 / -157.85 / 171.32 / 174.45 / -148.51 / -161.22 / 68.07 / -49.41
06 / -1314.693708 / 2.1 / 6 / -81.73 / 73.10 / 177.18 / -157.91 / 157.30 / -175.36 / -162.73 / -160.08 / 64.51 / -40.57
07 / -1314.690259 / 4.3 / 5 / 76.59 / -29.03 / -61.14 / 132.80 / -178.92 / 171.49 / -159.85 / -159.92 / -179.29 / -73.77
08 / -1314.695236 / 1.2 / 7 / -86.22 / 62.78 / 51.13 / 177.88 / -62.18 / -148.29 / 178.53 / -163.83 / -178.16 / -55.32
09 / -1314.690682 / 4.0 / 5 / -83.46 / 56.25 / -61.96 / 133.12 / 163.89 / -155.01 / -179.51 / -163.14 / -176.25 / 173.11
10 / -1314.691359 / 3.6 / 5 / -85.35 / 61.50 / -169.19 / -139.26 / 162.33 / 169.18 / -154.95 / -159.83 / -176.09 / -55.66
11 / -1314.679967 / 10.8 / 6 / 61.74 / -33.67 / 66.42 / -158.77 / 169.14 / -132.10 / 168.21 / -165.82 / -173.61 / -58.13
12 / -1314.688281 / 5.5 / 6 / -84.07 / 50.79 / 62.24 / 172.91 / -44.17 / 169.05 / -146.54 / -162.03 / -164.67 / -170.42
13 / -1314.690406 / 4.2 / 6 / 69.45 / -53.10 / -168.98 / -131.87 / 168.31 / -159.71 / -175.73 / -161.41 / 65.85 / -42.77
14 / -1314.692740 / 2.7 / 7 / -83.86 / 50.77 / 62.57 / 172.19 / -44.69 / 168.52 / -145.01 / -162.20 / -40.53 / 69.98
15 / -1314.692734 / 2.7 / 5 / -114.49 / 10.74 / 44.38 / 107.46 / 171.20 / -170.76 / -170.07 / -162.95 / -165.00 / -52.48
17 / -1314.695465 / 1.0 / 7 / -82.89 / 51.70 / 38.42 / 127.74 / -151.02 / 94.88 / -44.24 / 22.15 / 64.00 / 62.43
18 / -1314.688633 / 5.3 / 7 / -83.76 / 49.12 / 59.02 / -150.26 / 176.57 / -20.99 / -38.87 / 32.39 / 65.41 / 58.36
19 / -1314.684943 / 7.6 / 5 / 64.91 / -40.95 / 80.20 / 119.29 / 174.84 / -147.03 / 178.57 / -163.88 / -179.74 / -70.68
20 / -1314.689119 / 5.0 / 6 / 69.43 / -53.88 / -168.84 / -130.92 / 168.11 / -152.95 / 178.71 / -162.98 / -176.60 / -57.21
21 / -1314.687174 / 6.2 / 4 / 62.62 / 32.61 / -52.66 / 130.50 / -178.33 / -150.04 / 175.76 / -163.06 / 179.86 / -74.18

Table S1dEquilibrium single point energies, relative energies, the number of hydrogen bonds and torsion angles of the β-ManNAc-Ser model structures

(hartree) / (kcal mol-1) / H-bonds / φ / ψ / χ1 / χ2 / χ3 / τ2 / τ3 / τ4 / τ5 / τ6
02 / -1314.685388 / 7.4 / 7 / 58.95 / 6.50 / 48.00 / 118.06 / 177.73 / 170.90 / -92.82 / 161.67 / -174.49 / -50.14
03 / -1314.686496 / 6.7 / 7 / -78.33 / 28.84 / 47.34 / 136.42 / -179.87 / -168.40 / -113.30 / 167.32 / 175.81 / -64.81
04 / -1314.691409 / 3.6 / 7 / -85.03 / 76.87 / 50.11 / 154.07 / -158.72 / -161.94 / -118.80 / 165.86 / 64.27 / 47.93
05 / -1314.681414 / 9.8 / 5 / -79.28 / 63.83 / 41.60 / -175.95 / 144.98 / -89.10 / 50.14 / -82.80 / 61.13 / 59.84
06 / -1314.687982 / 5.7 / 4 / -85.35 / 56.04 / -53.55 / 114.92 / 157.07 / -167.17 / -114.53 / 165.13 / 179.04 / 164.82
07 / -1314.686697 / 6.5 / 5 / 74.23 / -63.55 / -64.20 / 135.05 / 176.05 / 176.49 / -93.11 / 159.48 / -172.92 / -65.83
09 / -1314.686711 / 6.5 / 4 / -83.86 / 56.32 / -47.92 / 119.10 / 165.49 / -169.36 / -110.82 / 166.31 / 63.73 / -160.30
10 / -1314.679162 / 11.3 / 5 / -75.45 / 63.18 / 42.40 / -167.39 / 128.31 / -97.17 / 171.56 / 177.58 / 67.17 / 63.49
11 / -1314.681903 / 9.5 / 5 / -85.14 / 59.63 / 43.69 / -144.82 / 142.89 / -92.06 / 48.47 / -49.64 / -56.66 / 176.40
12 / -1314.687530 / 6.0 / 6 / 59.17 / -19.93 / 67.13 / 122.12 / -170.39 / 177.13 / -92.80 / 156.94 / 70.98 / 76.98
13 / -1314.680603 / 10.4 / 7 / -79.61 / 37.59 / 38.77 / 129.14 / -169.39 / -85.66 / 49.41 / -72.80 / 170.68 / -65.57
14 / -1314.683613 / 8.5 / 6 / -82.72 / 62.01 / 39.29 / -153.25 / 162.01 / -177.36 / -96.33 / 163.95 / -175.43 / -56.01
15 / -1314.690481 / 4.2 / 5 / -84.13 / 68.06 / -65.99 / 116.34 / 172.68 / -170.38 / -106.37 / 162.36 / 172.36 / 65.73
16 / -1314.678190 / 11.9 / 5 / -76.87 / 47.07 / 56.85 / -177.12 / 101.21 / -90.55 / 171.08 / 171.62 / -177.66 / -51.81
17 / -1314.683782 / 8.4 / 6 / -81.16 / 70.85 / 40.39 / -143.52 / 159.80 / -176.33 / -98.38 / 164.02 / -65.24 / 42.50
18 / -1314.690900 / 3.9 / 6 / 71.00 / -50.93 / 169.68 / 87.47 / -171.99 / -167.66 / -109.47 / 168.00 / 61.99 / 54.51
19 / -1314.687337 / 6.1 / 5 / -102.12 / -7.28 / 58.36 / 127.34 / -168.40 / -169.95 / -106.52 / 164.56 / 70.29 / 75.24
20 / -1314.693207 / 2.4 / 5 / -80.42 / 73.33 / 49.41 / 161.72 / -158.85 / -167.79 / -106.46 / 164.12 / -69.20 / 47.07

Table S2 Torsion angles of the most stable non-hydrated (02)α-GalNAc-Ser model structureand its monohydrated (02w1-3) derivatives

φ / ψ / χ1 / χ2 / χ3 / τ2 / τ3 / τ4 / τ5 / τ6
02 / -77.25 / 83.19 / 43.36 / 154.32 / -159.16 / 168.16 / -150.33 / -161.17 / 176.74 / -57.15
02w1 / -72.32 / 74.65 / 31.48 / -169.60 / -179.17 / 163.81 / -140.04 / -162.78 / -179.40 / -62.06
02w2 / -73.93 / 131.62 / 37.50 / -171.68 / 175.67 / 162.37 / -138.72 / -162.35 / -179.72 / -62.56
02w3 / -129.74 / 170.37 / 62.92 / 148.42 / -167.33 / 93.57 / -43.55 / -40.02 / -179.92 / -57.56