Nature 366, 537 - 543 (09 December 1993); doi:10.1038/366537a0

Crystal structure of a bacterial non-haem iron hydroxylase that catalyses the biological oxidation of methane

Amy C. Rosenzweig^{& ast;}, Christin A. Frederick^{& dagger;}, Stephen J. Lippard^{& ast;& Dagger;} & P& auml;r Nordlund^{& sect;& Dagger;}

^{& ast;}Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA
^{& dagger;}Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School and Dana Farber Cancer Institute, Boston, Massachusetts 02115, USA
^{& sect;}Department of Molecular Biology, Stockholm University, S-10691 Stockholm, Sweden
^{& Dagger;}To whom correspondence should be addressed.

The 2.2 & Aring; crystal structure of the 251K ₂₂₂ dimeric hydroxylase protein of methane mono-oxygenase from Methylococcus capsulatus (Bath) reveals the geometry of the catalytic di-iron core. The two iron atoms are bridged by exogenous hydroxide and acetate ligands and further coordinated by four glutamate residues, two histidine residues and a water molecule. The dinuclear iron centre lies in a hydrophobic active-site cavity for binding methane. An extended canyon runs between pairs, which have many long -helices, for possible docking of the reductase and coupling proteins required for catalysis.

References

1.	Higgins, I. J., Best, D. J. & Hammond, R. C. Nature 286, 561−564 (1980). | Article | PubMed | ISI | ChemPort |
2.	Pearman, G. I. & Fraser, P. J. Nature 332, 489−190 (1988). | Article |
3.	Colby, J. & Dalton, H. Biochem. J. 171, 461−468 (1978). | PubMed | ISI | ChemPort |
4.	Woodland, M. P., Patil, D. S., Cammack, R. & Dalton, H. Biochim, biophys. Acta 873, 237−242 (1986). | ChemPort |
5.	Fox, B. G., Surerus, K. K., Münck, E. & Lipscomb, J. D. J. biol. Chem. 263, 10553−10556 (1988). | PubMed | ChemPort |
6.	DeWitt, J. G. et al. J. Am. chem. Soc. 113, 9219−9235 (1991). | Article | ChemPort |
7.	Que, L. Jr & True, A. E. Prog. inorg. Chem. 38, 97−200 (1990). | ChemPort |
8.	Vincent, J. B., Olivier-Lilley, G. L. & Averill, B. A. Chem. Rev. 90, 1447−1467 (1990). | Article | ChemPort |
9.	Kurtz, D. M. Jr & Pickril, B. C. Biochem. biophys. Res. Commun. 181, 337−341 (1991). | PubMed | ISI | ChemPort |
10.	Fox, B. G., Shanklin, J., Somerville, C. & Münck, E. Proc. natn. Acad. Sci. U.S.A. 90, 2486−2490 (1993). | ChemPort |
11.	Lund, J. & Dalton, H. Eur. J. Biochem. 147, 291−296 (1985). | Article | PubMed | ChemPort |
12.	Green, J. & Dalton, H. J. biol. Chem. 260, 15795−15801 (1985). | PubMed | ChemPort |
13.	Colby, J., Stirling, D. I. & Dalton, H. Biochem. J. 165, 395−402 (1977). | PubMed | ISI | ChemPort |
14.	Lindstrom, J. E. et al. Appl. environ. Microbiol. 57, 2514−2522 (1991). | PubMed | ChemPort |
15.	Pritchard, P. H. & Costa, C. F. Environ. Sci. Technol. 25, 372−379 (1991). | Article | ChemPort |
16.	Green, J. & Dalton, H. J. biol. Chem. 264, 17698−17703 (1989). | PubMed | ISI | ChemPort |
17.	Fox, B. G., Borneman, J. G., Wackett, L. P. & Lipscomb, J. D. Biochemistry 29, 6419−6427 (1990). | Article | PubMed | ISI | ChemPort |
18.	Periana, R. A. et al. Science 259, 340−343 (1993). | ChemPort |
19.	Ericson, A. et al. J. Am. chem. Soc. 110, 2330−2332 (1988). | Article | ChemPort |
20.	DeRose, V., Liu, K. E., Lippard, S. J. & Hoffman, B. J. Am. chem. Soc. 115, 6440−6441 (1993). | Article | ChemPort |
21.	Fox, B. G. et al. J. Am. chem. Soc. 115, 3688−3701 (1993). | Article | ChemPort |
22.	Thomann, H. et al. J. Am. chem. Soc. 115, 8881−8882 (1993). | Article | ChemPort |
23.	Stainthorpe, A. C., Lees, V., Salmond, G. P. C., Dalton, H. & Murrell, J. C. Gene 91, 27−34 (1990). | Article | PubMed | ChemPort |
24.	Nordlund, P., Dalton, H. & Eklund, H. FEBS Lett. 307, 257−262 (1992). | Article | PubMed | ChemPort |
25.	Nordlund, P., Sjöberg, B.-M. & Eklund, H. Nature 345, 593−598 (1990). | Article | PubMed | ISI | ChemPort |
26.	Nordlund, P. & Eklund, H. J. molec. Biol. 232, 123−164 (1993). | Article | PubMed | ISI | ChemPort |
27.	Prior, S. D. & Dalton, H. FEMS Microbiol. Lett. 29, 105−109 (1985). | Article | ISI | ChemPort |
28.	Fox, B. G., Froland, W. A., Dege, J. E. & Lipscomb, J. D. J. biol. Chem. 264, 10023−10033 (1989). | PubMed | ISI | ChemPort |
29.	Atta, M., Fontecave, M., Wilkins, P. C. & Dalton, H. Eur. J. Biochem. 217, 217−223 (1993). | Article | PubMed | ISI | ChemPort |
30.	Hamman, S. et al. Biochem. biophys. Res. Commun. 195, 594−599 (1993). | Article | PubMed | ChemPort |
31.	Andersson, K. K., Elgren, T. E., Que, L. Jr & Lipscomb, J. D. J. Am. chem. Soc. 114, 8711−8713 (1992). | Article | ChemPort |
32.	Priestley, N. D. et al. J. Am. chem. Soc. 114, 7561−7562 (1992). | Article | ChemPort |
33.	Liu, K. E., Johnson, C. C., Newcomb, M. & Lippard, S. J. J. Am. chem. Soc. 115, 939−947 (1993). | Article | ChemPort |
34.	Rardin, R. L., Tolman, W. B. & Lippard, S. J. New. J. Chem. 15, 417−430 (1991). | ChemPort |
35.	Poulos, T. L., Finzel, B. C. & Howard, A. J. J. molec. Biol. 195, 687−700 (1987). | Article | PubMed | ISI | ChemPort |
36.	Raag, R., Martinis, S. A., Sligar, S. G. & Poulos, T. L. Biochemistry 30, 11420−11429 (1991). | Article | PubMed | ISI | ChemPort |
37.	Poulos, T. L., Finzel, B. C., Gunsalus, I. C., Wagner, G. C. & Kraut, J. J. biol. Chem. 260, 16122−16130 (1985). | PubMed | ChemPort |
38.	Liu, K. E. & Lippard, S. J. J. biol. Chem. 266, 12836−12839 (1991). | PubMed | ChemPort |
39.	Fox, B. G., Liu, Y., Dege, J. E. & Lipscomb, J. D. J. biol. Chem. 266, 540−550 (1991). | PubMed | ChemPort |
40.	Froland, W. A., Andersson, K. K., Lee, S.-K., Liu, Y. & Lipscomb, J. D. J. biol. Chem. 267, 17588−17597 (1992). | PubMed | ChemPort |
41.	Liu, K. E., Feig, A. L., Goldberg, D. P., Watton, S. P. & Lippard, S. J. in The Activation of Dioxygen and Homogeneous Catalytic Oxidation (eds Barton, D. H. R., Martell, A. E. & Sawyer, D.) (Plenum, New York, 1993).
42.	Jiang, Y., Wilkins, P. C. & Dalton, H. Biochem. biophys. Acta 1163, 105−112 (1993). | PubMed | ChemPort |
43.	Nordlund, I., Powlowski, J. & Shingler, V. J. Sact. 172, 6826−6833 (1990). | ChemPort |
44.	Yen, K. M. et al. J. Bact. 173, 5315−5327 (1991). | PubMed | ChemPort |
45.	Rosenzweig, A. C., Frederick, C. A. & Lippard, S. J. J. molec. Biol. 227, 283−285 (1992). | PubMed |
46.	Knight, S. thesis, Swedish Univ. Agric. Sci., 1989.
47.	Terwillinger, T. C. & Eisenberg, D. Acta crystallogr. A39, 813−817 (1983). | ChemPort |
48.	Otwinowski, Z. MLPHARE, CCP4 Proc. 80−88 (Daresbury Lab., Warrington, UK, 1991).
49.	Wang, B. C. Meth. Enzym. 115, 90−112 (1985). | PubMed | ChemPort |
50.	Jones, T. A. in Molecular Replacements (eds Dodson, E.J.) 91−105 (SERC, Daresbury, UK, 1992).
51.	Rould, M. A., Perona, J. J. & Steitz, T. A. Acta crystallogr. A48, 751−756 (1992). | ChemPort |
52.	Nordlund, P. thesis, Swedish Univ. Agric. Sci., 1990.
53.	Jones, T. A. & Thirup, S. EMBO J. 5, 829−822 (1985).
54.	Jones, T. A., Bergdoll, M. & Kjeldgaard, M. in Crystallographic Computing and Modeling Methods in Molecular Design (eds Bugg, C. & Ealick, S.) (Springer, New York, 1989).
55.	Stainthorpe, A. C., Murrell, J. C., Salmond, G. P. C., Dalton, H. & Lees, V. Arch. Microbiol. 152, 154−159 (1989). | Article | PubMed | ChemPort |
56.	Brünger, T. A., Kuriyan, J. & Karplus, M. Science 235, 458−460 (1987). | ISI |
57.	Kraulis, P. J. appl. Crystallogr. 24, 946−950 (1991). | Article | ISI |