Table 1. Cu–Ligand Bond Lengths (Å) for the Active Site of LPMO.
state | Cun | (spin) | Cu–NHis86ε | Cu–NHisl | Cu–NHis1δ | Cu–OTyr175 | Cu–OW229 | Cu–OW230 |
---|---|---|---|---|---|---|---|---|
1fixed | CuII | S = 1/2 | 2.02 | 2.07 | 1.98 | 2.80 | 2.28 | 2.11 |
1free | CuII | S = 1/2 | 2.03 | 2.03 | 1.99 | 2.34 | 2.83 | 2.03 |
1free,a | CuII | S = 1/2 | 2.02 | 2.02 | 1.97 | 2.48 | 3.00 | 2.06 |
1free,b | CuII | S = 1/2 | 2.04 | 1.98 | 2.02 | 2.47 | 2.96 | 2.07 |
1(42) | CuII | S = 1/2 | 1.99 | 2.08 | 1.99 | 3.08 | 2.33 | |
1(31),c | CuI | S = 1/2 | 1.99 | 2.07 | 1.98 | 2.22 | 2.12 | |
2fixed | CuI | S = 0 | 1.97 | 2.11 | 1.99 | 2.87 | 2.30 | 3.01 |
2free | CuI | S = 0 | 1.95 | 2.08 | 1.96 | 3.03 | 2.28 | 3.02 |
2free,a | CuI | S = 0 | 1.93 | 2.09 | 1.93 | 3.05 | 2.54 | 3.03 |
2free,b | CuI | S = 0 | 1.97 | 1.97 | 1.95 | 2.90 | 2.74 | 3.04 |
2(42) | CuI | S = 0 | 1.93 | 2.14 | 1.93 | 4.37 | 2.19 | |
2(41) | CuI | S = 0 | 1.91 | 2.27 | 1.91 | 3.23 | 3.32 | 3.11 |
2(31),c | CuI | S = 0 | 1.98 | 2.18 | 1.98 | |||
2YET(8) | CuI/II | S = 0, 1/2 | 2.32 | 2.10 | 2.43 | 2.80 | 2.65 | 2.23 |
3ZUD(8) | CuI/II | S = 0, 1/2 | 2.03 | 2.20 | 1.91 | 2.92 | 2.89 | |
4EIR(27) | CuI/II | S = 0, 1/2 | 1.99 | 2.25 | 1.92 | 2.76 | 1.84 | |
5ACF(56) | CuI/II | S = 0, 1/2 | 2.06 | 1.88 | 2.16 | 2.47 | ||
4ALC(31),c | CuII | S = 1/2 | 1.97 | 2.12 | 1.99 | 2.21 | 2.19 | |
4ALT(31),c | CuI | S = 0 | 1.91 | 2.19 | 1.94 |
Optimized with TPSS-D3/def2-TZVPD.
Optimized with B3LYP-D3/def2-TZVPD.
This is from an AA10 LPMO enzyme, whose reduction in the X-ray beam has been carefully followed.