Table 1.
Comparison of labile proton chemical shifts for NmHO-PH-OH and NmHO-PH-H2O
|
NmHO-PH-OH
|
NmHO-PH-H2O
|
Comparison
|
||||
|---|---|---|---|---|---|---|
| δDSS(obs)a | δdip(calc)b | δDSS(dia*)c | δDSS(dia*)e | Δδdip(calc)d | ΔδDSS(dia*)f | |
| Peptide NHs | ||||||
| Ala12 | 9.15 | -0.09 | 9.24 | 9.31 | 0.29 | 0.07 |
| Tyr112 | 8.36 | -0.22 | 8.58 | 8.68 | 0.72 | 0.10 |
| Cys113 | 7.75 | -0.40 | 8.15 | 8.40 | 1.35 | 0.25 |
| Ala114 | 8.70 | -0.40 | 9.10 | 9.00 | 1.33 | -0.10 |
| Gln115 | 9.40 | -0.27 | 9.67 | 9.50 | 0.78 | -0.17 |
| Gly138 | 10.30 | 0.05 | 10.25 | 10.28 | -0.18 | 0.03 |
| Ala139 | 7.67 | 0.08 | 7.59 | 7.58 | -0.30 | -0.01 |
| Arg140 | 12.10 | 0.11 | 11.99 | 12.04 | -0.37 | 0.05 |
| His141 | 10.78 | 0.15 | 10.63 | 10.75 | -0.52 | 0.12 |
| Leu142 | 6.82 | 0.27 | 6.55 | 6.68 | -0.92 | 0.13 |
| Asp147 | 10.70 | 0.12 | 10.58 | 10.60 | -0.39 | 0.02 |
| Ala180 | 8.39 | -0.11 | 8.50 | 8.42 | 0.44 | -0.08 |
| Phe181 | 8.04 | -0.12 | 8.16 | 8.03 | 0.57 | -0.13 |
| Ala182 | 7.77 | -0.02 | 7.79 | 7.97 | 0.20 | 0.12 |
| Phe183 | 8.61 | -0.08 | 8.69 | 8.65 | 0.35 | -0.04 |
| Tyr184 | 8.15 | -0.19 | 8.34 | 8.51 | 0.73 | 0.17 |
| Sidechain NHs | ||||||
| Gln49 Nε1H | 9.70 | 0.14 | 9.56 | 9.76 | -0.72 | 0.20 |
| Gln49 Nε2H | 6.97 | 0.17 | 6.80 | 7.04 | -1.00 | 0.26 |
| His53 Nε1H | 12.07 | 0.10 | 11.97 | 11.48 | -0.66 | -0.51 |
| Trp110 NεH | 11.60 | -0.08 | 11.68 | 11.70 | 0.29 | 0.02 |
| His141 Nδ1H | 13.35 | 0.12 | 13.23 | 13.24 | -0.48 | 0.01 |
| Trp153 NεH | 9.40 | -0.36 | 9.76 | 10.54 | 1.25 | 0.82 |
a
δDSS(obs), in ppm, referenced to DSS via the solvent signal, in 1H2O, 100 mM bicarbonate at 25°C and pH 10.2.
b
Dipolar shift predicted by the determined magnetic axes described in Figure 8.
c
The diamagnetic shift that reflects H-bonding differences between OH- and H2O complexes, as given by Eq. (4).
d
Δδdip(calc) = δdip(calc; NmHO-PH-H2O) - δdip(calc; NmHO-PH-OH)
e
As reported previously.50