Table 1. X-ray crystal structures of LPMOs.
The key to the footnote markers is given at the end of the table.
| Crystallization and diffraction data | Active site | Specificity | ||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Family | Organism | Protein name | PDB code | ASU† | Protein concentration and buffer | Crystallization conditions | Space group | Res. (Å) | Element (oxidation)‡ | Residues | Substrates | Site of attack | Comments | Reference |
| AA9 | Lentinus similis | LsAA9_A | 5acf | 1 | 19.2 mg ml−1, 0.02 M sodium acetate pH 5.5 | 3.6 M NaCl, 0.1 M citric acid pH 4.0 (pH 5.5) | P4132 | 1.80 | Copper(II) | MeHis1, His78, Tyr164 | PASC, cellooligosaccharides | C4 | Preincubated with 1 mM copper(II) acetate. Cellotriose bound in the active site. Exogenous ligand (Cl−) mimicking superoxide. | Frandsen et al. (2016 ▸) |
| AA9 | Lentinus similis | LsAA9_A | 5acg | 1 | 19.2 mg ml−1, 0.02 M sodium acetate pH 5.5 | 3.9 M NaCl, 0.1 M citric acid pH 4.0 (pH 5.5) | P4132 | 1.91 | Copper(II) | MeHis1, His78, Tyr164 | PASC, cellooligosaccharides | C4 | Preincubated with 1 mM copper(II) acetate. | Frandsen et al. (2016 ▸) |
| AA9 | Lentinus similis | LsAA9_A | 5ach | 1 | 8.5 mg ml−1, 0.02 M sodium acetate pH 5.5 | 3.0 M NaCl, 0.1 M citric acid pH 3.5 (pH 5.5) | P4132 | 1.28 | Copper(II)/copper(I) 0.9 | MeHis1, His78, Tyr164 | PASC, cellooligosaccharides | C4 | Preincubated with 1 mM copper(II) acetate. | Frandsen et al. (2016 ▸) |
| AA9 | Lentinus similis | LsAA9_A | 5aci | 1 | 19.2 mg ml−1, 0.02 M sodium acetate pH 5.5 | 3.6 M NaCl, 0.1 M citric acid pH 4.0 (pH 5.5) | P4132 | 1.75 | Copper(II)/copper(I) | MeHis1, His78, Tyr164 | PASC, cellooligosaccharides | C4 | Preincubated with 1 mM copper(II) acetate. Cellohexaose bound in the active site. | Frandsen et al. (2016 ▸) |
| AA9 | Lentinus similis | LsAA9_A | 5acj | 1 | 19.2 mg ml−1, 0.02 M sodium acetate pH 5.5 | 3.0 M NaCl, 0.1 M citric acid pH 3.5 (pH 5.5) | P4132 | 1.70 | Copper(I) | MeHis1, His78, Tyr164 | PASC, cellooligosaccharides | C4 | Preincubated with 1 mM copper(II) acetate. Cellotriose bound in the active site. | Frandsen et al. (2016 ▸) |
| AA9 | Neurospora crassa | NcAA9_D, NcLPMO9D, PMO-2, NCU01050, GH61-4 | 4eir | 2 | 0.15 M NaCl, 0.010 M Tris pH 8.5 | PEG 3350 (pH 6.7) | P21 | 1.10 | Copper(II)/copper(I) | MeHis1, His84, Tyr168 | PASC | C4 | Proposed O2 molecule near active-site axial position. | Li et al. (2012 ▸), Phillips et al. (2011 ▸) |
| AA9 | Neurospora crassa | NcAA9_F, NcLPMO9F, PMO-03328, NCU03328, GH61-6 | 4qi8 | 2 | — | 0.2 M NH4NO3, 20%(w/v) PEG 3350 pH 7.0 | P21212 | 1.10 | Copper(II) | His1, His72, Tyr157 | PASC | C1 | Regiospecificity in Vu, Beeson, Phillips et al. (2014 ▸). | Tan et al. (2015 ▸), Phillips et al. (2011 ▸) |
| AA9 | Neurospora crassa | NcAA9_M, NcLPMO9M, NcPMO-3, PMO-3, NCU07898, GH61-13 | 4eis | 2 | 104 mg ml−1, 0.010 M Tris pH 8.5 | 0.1 M NaCl, 0.010 M Tris pH 8.5 | P21 | 1.37 | Copper(I) | MeHis1, His82, Tyr171 | PASC | C1/C4 | Proposed peroxide ion near active site. Tyr24 oxidation. | Li et al. (2012 ▸), Phillips et al. (2011 ▸) |
| AA9 | Neurospora crassa | NcAA9_C, NcLPMO9C, NCU02916, PMO-02916, GH61-3 | 4d7u | 2 | 1.4 mg ml−1 | 0.2 M NH4 citrate, 20%(w/v) PEG 3350 pH 5.1 | P21 | 1.56 | Copper(I) | His1, His83, Tyr166 | PASC, cellooligosaccharides, xyloglucan, glucomannan, β-glucan | C4 | — | Borisova et al. (2015 ▸) |
| AA9 | Neurospora crassa | NcAA9_C, NcLPMO9C, NCU02916, PMO-02916, GH61-3 | 4d7v | 2 | 1.4 mg ml−1 | 0.2 M zinc(II) acetate, 17.5/20.0%(w/v) PEG 3350 pH 8.0 | P21 | 1.90 | Zinc(II) | His1, His83, Tyr166 | PASC, cellooligosaccharides, xyloglucan, glucomannan, β-glucan | C4 | — | Borisova et al. (2015 ▸) |
| AA9 | Phanerochaete chrysosporium | PcAA9_D, PcLPMO9D, PcGH61D, GH61D | 4b5q | 2 | 12 mg ml−1, 0.01 M sodium acetate pH 5.0 | 2.1 M malic acid (racemic) pH 7.0 | C2 | 1.75 | Copper(I) | His1, His76, Tyr160 | PASC, Avicel | C1 | — | Wu et al. (2013 ▸) |
| AA9 | Thermoascus aurantiacus | TaAA9_A, TaAA9A, TaGH61, TaGH61A, TaLPMO9A | 3zud | 1 | 15 mg ml−1, 0.02 M sodium acetate pH 5.5 | 0.2 M NaCl, 0.1 M HEPES pH 7.5, 25%(w/v) PEG 3350 | P21 | 1.25 | Copper(II)/copper(I); A, 0.6; B, 0.15 | MeHis1, His86, Tyr175 | PASC, PCS | C1/C4 | Crystal soaked in 10 mM copper(II) nitrate. | Quinlan et al. (2011 ▸) |
| AA9 | Thermoascus aurantiacus | TaAA9_A, TaAA9A, TaGH61, TaGH61A, TaLPMO9A | 2yet | 2 | 15 mg ml−1, 0.02 M sodium acetate pH 5.5 | 0.2 M NaCl, 0.1 M HEPES pH 8.0, 25%(w/v) PEG 3350 | P21 | 1.50 | Copper 0.2 | MeHis1, His86, Tyr175 | PASC, PCS | C1/C4 | Quinlan et al. (2011 ▸) | |
| AA9 | Thielavia terrestris | TtAA9_E, TtGH61E, GH61E, 131562 | 3eii | 4 | 3.1 mg ml−1 (pH 7.6–5.0) | 1.6 M MgSO4, 0.1 M MES pH 6.5 | F23 | 2.25 | Zinc(II) | His1, His68, Tyr153 | PASC, Avicel | C1 | Crystal soaked in 1.8 M ZnSO4, cacodylate pH 6.5. Regiospecificity inferred from Cannella et al. (2016 ▸). | Harris et al. (2010 ▸) |
| AA9 | Thielavia terrestris | TtAA9_E, TtGH61E, GH61E, 131562 | 3eja | 4 | 3.1 mg ml−1 (pH 7.6–5.0) | 1.6 M MgSO4, 0.1 M MES pH 6.5 | F23 | 1.90 | Magnesium(II) | His1, His68, Tyr153 | PASC, Avicel | C1 | — | Harris et al. (2010 ▸) |
| AA9 | Trichoderma reesei | HjAA9_B, HjGH61B, GH61B, Cel61B, EG7, TrAA9_B | 2vtc | 2 | 2.2 mg ml−1, 0.02 M sodium phosphate pH 6.8 | 15–20%(w/v) PEG 2000, 0.1 M Tris pH 8.4, 0.010 M NiCl2 | P65 | 1.60 | Nickel(II) | His1, His89, Tyr176 | Cellulose | N/D | — | Karkehabadi et al. (2008 ▸) |
| AA10 | Bacillus amyloliquefaciens | BaAA10_A, BaCBM33, ChbB, Rbam17540 | 2yow | 2 | 7.0 mg ml−1, 0.02 M sodium acetate pH 5.0, 0.25 M NaCl | 0.1 M MMT pH 4.0, 25%(w/v) PEG 1500 | P21212 | 1.80 | — | His28, His125, Phe196 | N/D | N/D | Likely to be active on chitin. | Hemsworth, Davies et al. (2013 ▸) |
| AA10 | Bacillus amyloliquefaciens | BaAA10_A, BaCBM33, ChbB, Rbam17540 | 2yox | 2 | 7.0 mg ml−1, 0.02 M sodium acetate pH 5.0, 0.25 M NaCl | 0.1 M MMT pH 4.0, 25%(w/v) PEG 1500 | P21 | 1.90 | Copper(I) | His28, His125, Phe196 | N/D | N/D | 1 mM copper(II) nitrate added to sample. | Hemsworth, Davies et al. (2013 ▸) |
| AA10 | Bacillus amyloliquefaciens | BaAA10_A, BaCBM33, ChbB, Rbam17540 | 2yoy | 2 | 7.0 mg ml−1, 0.02 M sodium acetate pH 5.0, 0.25 M NaCl | 0.1 M MMT pH 4.0, 25%(w/v) PEG 1500 | P21212 | 1.70 | Copper(I) | His28, His125, Phe196 | N/D | N/D | — | Hemsworth, Davies et al. (2013 ▸) |
| AA10 | Burkholderia pseudomallei | BpAA10_A | 3uam | 6 | 21 mg ml−1 | 0.1 M bis-tris propane pH 6.77, 0.2 M NaNO3, 20.54%(w/v) PEG 3500 | P1 | 2.00 | — | His19, His122, Phe205 | N/D | N/D | Mentioned in Book et al. (2014 ▸). | To be published |
| AA10 | Cellvibrio japonicus | CjAA10_A CjLPMO10A, CJA_2191, Cbp33A, Lpmo10A | 5fjq | 3 | 9 mg ml−1, 0.02 M Tris pH 8.0 | 0.1 M sodium acetate pH 5.2, 22%(w/v) PEG 4000 | C2 | 1.85 | Copper(I) [copper(II) in chain B] | His37, His136, Phe205 | α-Chitin, β-chitin | C1 | Copper(II)-saturated sample. | Forsberg et al. (2016 ▸) |
| AA10 | Enterococcus faecalis | EfAA10_A, EfCBM33A, EfaCBM33, EF0362 | 4a02 | 1 | 25 mg ml−1, 0.02 M Tris pH 8.0 | 1.0 M K/Na tartrate, 0.1 M imidazole pH 8.0, 0.2 M NaCl | P32 | 0.95 | — | His29, His114, Phe185 | α-Chitin, β-chitin | C1 | — | Vaaje-Kolstad et al. (2012 ▸) |
| AA10 | Enterococcus faecalis | EfAA10_A, EfCBM33A, EfaCBM33, EF0362 | 4alc | 1 | 25 mg ml−1, 0.02 M Tris pH 8.0 | 0.1 M HEPES pH 7.5, 20%(w/v) PEG 8000 | P21212 | 1.49 | Copper(II) | His29, His114, Phe185 | α-Chitin, β-chitin | C1 | Preincubated with 1 mM CuSO4. | Gudmundsson (et al., 2014 ▸) |
| AA10 | Enterococcus faecalis | EfAA10_A, EfCBM33A, EfaCBM33, EF0362 | 4ale | 1 | 25 mg ml−1, 0.02 M Tris pH 8.0 | 0.1 M HEPES pH 7.5, 20%(w/v) PEG 8000 | P21212 | 1.48 | Copper(II)/copper(I) | His29, His114, Phe185 | α-Chitin, β-chitin | C1 | Preincubated with 1 mM CuSO4. | Gudmundsson (et al., 2014 ▸) |
| AA10 | Enterococcus faecalis | EfAA10_A, EfCBM33A, EfaCBM33, EF0362 | 4alq | 1 | 25 mg ml−1, 0.02 M Tris pH 8.0 | 0.1 M HEPES pH 7.5, 20%(w/v) PEG 8000 | P21212 | 1.48 | Copper(II)/copper(I) | His29, His114, Phe185 | α-Chitin, β-chitin | C1 | Preincubated with 1 mM CuSO4. | Gudmundsson (et al., 2014 ▸) |
| AA10 | Enterococcus faecalis | EfAA10_A, EfCBM33A, EfaCBM33, EF0362 | 4alr | 1 | 25 mg ml−1, 0.02 M Tris pH 8.0 | 0.1 M HEPES pH 7.5, 20%(w/v) PEG 8000 | P21212 | 1.49 | Copper(II)/copper(I) | His29, His114, Phe185 | α-Chitin, β-chitin | C1 | Preincubated with 1 mM CuSO4. | Gudmundsson (et al., 2014 ▸) |
| AA10 | Enterococcus faecalis | EfAA10_A, EfCBM33A, EfaCBM33, EF0362 | 4als | 1 | 25 mg ml−1, 0.02 M Tris pH 8.0 | 0.1 M HEPES pH 7.5, 20%(w/v) PEG 8000 | P21212 | 1.47 | Copper(II)/copper(I) | His29, His114, Phe185 | α-Chitin, β-chitin | C1 | Preincubated with 1 mM CuSO4. | Gudmundsson (et al., 2014 ▸) |
| AA10 | Enterococcus faecalis | EfAA10_A, EfCBM33A, EfaCBM33, EF0362 | 4alt | 1 | 25 mg ml−1, 0.02 M Tris pH 8.0 | 0.1 M HEPES pH 7.5, 20%(w/v) PEG 8000 | P21212 | 1.49 | Copper(I) | His29, His114, Phe185 | α-Chitin, β-chitin | C1 | Preincubated with 1 mM CuSO4. | Gudmundsson (et al., 2014 ▸) |
| AA10 | Jonesia denitrificans | JdAA10_A, JdLPMO10A, Jden_1381 | 5aa7 | 2 | 20 mg ml−1, 0.02 M Tris pH 8.0 | 1.9 M DL-malic acid pH 7 | P212121 | 1.55 | Copper(I) | His32, His109, Phe164 | α-Chitin, β-chitin | C1 | — | Mekasha et al. (2016 ▸) |
| AA10 | Serratia marcescens | SmAA10_A, SmLPMO10A, CBP21, Cbp21, Cbp | 2bem | 3 | 20 mg ml−1, 0.05 M Tris pH 8.0 | 1.26 M (NH4)2SO4, 0.1 M HEPES pH 7.5 | P21212 | 1.55 | Na2+ | His28, His114, Phe187 | α-Chitin, β-chitin | C1 | Chain A and B have no active-site metal. | Vaaje-Kolstad, Houston et al., 2005 ▸) |
| AA10 | Serratia marcescens | SmAA10_A, SmLPMO10A, CBP21, Cbp21, Cbp | 2ben | 2 | 17.5 mg ml−1, 0.05 M Tris pH 8.0 | 20%(w/v) PEG 8000, 0.1 M CHAPS, 0.2 M NaCl | P3221 | 1.80 | — | His28, His114, Phe187 | α-Chitin, β-chitin | C1 | Y54A mutant. | Vaaje-Kolstad, Houston et al. (2005 ▸) |
| AA10 | Serratia marcescens | SmAA10_A, SmLPMO10A, CBP21, Cbp21, Cbp | 2lhs | — | 0.8–1.2 mM, 0.02 M K3PO4, 0.01 M NaCl | pH 5.5 | — | — | — | His28, His114, Phe187 | α-Chitin, β-chitin | C1 | NMR structure. | Aachmann et al. (2012 ▸) |
| AA10 | Streptomyces coelicolor | ScAA10_B, ScLPMO10B, SCO0643, SCF91.03c | 4oy6 | 1 | 10.3 mg ml−1, 0.02 M Tris pH 8.0 | 0.2 M zinc acetate, 0.1 M sodium cacodylate pH 6.5, 9%(v/v) 2-propanol | P3121 | 1.29 | Copper(II)/copper(I) 0.95 | His43, His150, Tyr219 | PASC, Avicel, β-chitin | C1/C4 (C1 on chitin) | Soaked in 1–20 mM CuCl2 (zinc acetate reduced to 0.1 M). | Forsberg, Mackenzie et al. (2014 ▸) |
| AA10 | Streptomyces coelicolor | ScAA10_B, ScLPMO10B, SCO0643, SCF91.03c | 4oy8 | 1 | 10.3 mg ml−1, 0.02 M Tris pH 8.0 | 0.2 M zinc acetate, 0.1 M sodium cacodylate pH 6.5, 9%(v/v) 2-propanol | P3121 | 1.40 | Zinc(II) 0.8 | His43, His150, Tyr219 | PASC, Avicel, β-chitin | C1/C4 (C1 on chitin) | — | Forsberg, Mackenzie et al. (2014 ▸) |
| AA10 | Streptomyces coelicolor | ScAA10_C, ScLPMO10C, LPMO10C, CelS2, SCO1188, SCG11A.19 | 4oy7 | 8 | 9.2 mg ml−1, 0.02 M Tris pH 8.0 | 9%(w/v) PEG 10 000, 0.1 M sodium citrate, 0.1 M calcium acetate, 5%(v/v) glycerol | P212121 | 1.50 | Copper(II)/copper(I) 0.5 | His35, His144, Phe219 | PASC, Avicel | C1 | — | Forsberg, Mackenzie et al. (2014 ▸) |
| AA10 | Streptomyces lividans | SlAA10_E, SliLPMO10E, SLI_3182 | 5ftz | 1 | 15 mg ml−1, 0.01 M sodium acetate pH 5.0, 0.15 M NaCl | 0.1 M sodium acetate pH 4.6, 25%(w/v) PEG 4000 | C2 | 1.38 | Copper(I) 0.8 | His30, His120, Phe193 | β-Chitin | C1/(C4) | Definite C1 oxidation Indications of C4 oxidation. | Chaplin et al. (2016 ▸) |
| AA10 | Thermobifida fusca | TfAA10_A, TfLPMO10A, E7, Tfu_1268 | 4gbo | 2 | — | 0.1 M HEPES pH 7.5, 4.3 M NaCl | P3221 | 2.00 | Copper(I) 0.5 | His37, His144, Tyr213 | PASC, Avicel, β-chitin | C1/C4 (C1 on chitin) | Regiospecificity in Forsberg, Mackenzie et al. (2014 ▸). | To be published |
| AA10 | Vibrio cholerae | VcAA10_B, VCA0811, VcGbpA, GbpA | 2xwx | 2 | 2 mg ml−1, 0.02 M Tris pH 7.5 | 0.2 M Mg(HCO3)2, 50%(w/v) PEG 3350, 3.33%(w/v) D-sorbitol pH 7.5 | P21 | 1.80 | — | His24, His121, Phe193 | N/D | N/D | — | Wong et al. (2012 ▸) |
| AA10 | Anomala cuprea entomopoxvirus | Fusolin (ACV034) | 4yn1 | 1 | — | In vivo crystallization (pH 7.0) | P41212 | 1.90 | — | His1, His142, Phe225 | N/D | N/D | Intracellular fusolin microcrystals from EPV-infected larvae of A. cuprea moths. | Chiu et al. (2015 ▸) |
| AA10 | Unidentified entomopoxvirus | Fusolin (partial) | 4yn2 | 1 | — | In vivo crystallization (pH 7.0) | P41212 | 2.02 | Zinc(II) | His1, His222 | N/D | N/D | Intracellular fusolin microcrystals from EPV-infected larvae of Wiseana spp. moths. | Chiu et al. (2015 ▸) |
| AA10 | Unidentified entomopoxvirus (Melolontha melolontha entomopoxvirus) | Fusolin | 4ow5 | 1 | — | In vivo crystallization | P41212 | 1.90 | (H2O) | His1, His142, Phe225 | N/D | N/D | Active-site water molecule may be a low-occupied metal ion. Chitin-binding domain. Mutations: G25D, H192N, I351N, I352H, Q353T, D354G. | Chiu et al. (2015 ▸) |
| AA10 | Unidentified entomopoxvirus (Melolontha melolontha entomopoxvirus) | Fusolin | 4x27 | 1 | — | In vivo crystallization | P41212 | 2.40 | Copper(II) 0.79 | His1, His142, Phe225 | N/D | N/D | Soaked with CuSO4. | Chiu et al. (2015 ▸) |
| AA10 | Unidentified entomopoxvirus (Melolontha melolontha entomopoxvirus) | Fusolin | 4x29 | 1 | — | In vivo crystallization | P41212 | 2.41 | Zinc(II) | His1, His142, Phe225 | N/D | N/D | Soaked with ZnSO4. | Chiu et al. (2015 ▸) |
| AA11 | Aspergillus oryzae | AoAA11 Ao(LPMO11) (AO090102000501) | 4mah | 1 | 25 mg ml−1, 0.02 M sodium acetate pH 5.0 | 0.01 M ZnCl2, 0.1 M MES pH 6.0, 20%(w/v) PEG 6000 | P212121 | 1.55 | Zinc(II) | His1, His60, Tyr140 | β-Chitin | C1 | — | Hemsworth et al. (2014 ▸) |
| AA11 | Aspergillus oryzae | AoAA11 Ao(LPMO11) (AO090102000501) | 4mai | 1 | 25 mg ml−1, 0.02 M sodium acetate pH 5.0 | 0.01 M ZnCl2, 0.1 M MES pH 6.0, 20%(w/v) PEG 6000 | P212121 | 1.40 | Copper(I) | His1, His60, Tyr140 | β-Chitin | C1 | Soaked in 2 mM CuCl2. | Hemsworth et al. (2014 ▸) |
| AA13 | Aspergillus oryzae | AoAA13 (AO090701000246) (AOR_1_454114) | 4opb | 1 | 3 mg ml−1, 0.02 M MES pH 6.0, 0.125 M NaCl | 0.14 M CaCl2, 0.07 M sodium acetate pH 4.6, 14%(v/v) 2-propanol, 30%(v/v) glycerol (+ seed stock) | P212121 | 1.55 | Copper(I) | MeHis1, His91, Tyr224 | N/D (starch) | N/D (C1) | Enzymes with 70–72% sequence identity [AnAA13 in Lo Leggio et al. (2015 ▸) and NcAA13 in Vu, Beeson, Phillips et al. (2014 ▸)] release C1-oxidized products from starch-related substrates. | Lo Leggio et al. (2015 ▸) |
†
Number of molecules in the asymmetric unit.
‡
The criteria for assigning a copper(II) or copper(I) state were informed by structures where both states have been characterized (Gudmundsson et al., 2014 ▸). The electron density of the equatorial exogenous ligand to the copper (from weighted 2F obs − F calc) should be more than 2σ with more than 0.5 occupancy and a distance to the copper of less than 2.4 Å, with similar criteria applying to the exogenous axial ligand, although with a distance of 2.8 Å. In structures where a distorted geometry is observed because of significant steric effects (most AA10 members), structures with a single exogenous ligand within 2.5 Å distance are taken as copper(II). The occupancy of the metal is 1.00 if no other value is indicated. If there is significant metal-site disorder with characteristics that could fit both states, the site is described as copper(II)/copper(I). When the copper occupancy was lower than 0.5, no oxidation state was assigned.