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Structural studies of nickel-iron hydrogenase

  1. Albracht, S.P.J. (1985) The use of electron­paramagnetic­resonance spectroscopy to establish the properties of nickel and the iron-sulphur cluster in hydrogenase from Chromatium vinosum. Biochem. Soc. Trans. 13, 582-585.
  2. Asso, M., Guigliarelli, B., Yagi, T. and Bertrand, P. (1992) EPR and redox properties of Desulfovibrio vulgaris Miyazaki hydrogenase: comparison with the Ni-Fe enzyme from Desulfovibrio gigas. Biochim. Biophys. Acta 1122, 50-56.
  3. Bagley, K.A., van Garderen, C.J., Chen, M., Duin, E.C., Albracht, S.P.J. and Woodruff, W.H. (1994) Infrared studies on the interaction of carbon monoxide with divalent nickel in hydrogenase from Chromatium vinosum. Biochemistry 33, 9229-9236.
  4. Bagyinka, C., Szokefalvi­Nagy, Z., Demeter, I. and Kovacs, K.L. (1989) Metal composition analysis of hydrogenase from Thiocapsa roseopersicina by proton induced X­ray emission spectroscopy. Biochem. Biophys. Res. Commun. 162, 422-426.
  5. Bagyinka, C., Whitehead, J.P. and Maroney, M.J.J. (1993) An X­ray absorption spectroscopic study of nickel redox chemistry in hydrogenase. J. Am. Chem. Soc. 115, 3576-3585.
  6. Cammack, R., Patil, D.S., Aguirre, R. and Hatchikian, E.C. (1982) Redox properties of the ESR­detectable nickel in hydrogenase from Desulfovibrio gigas. FEBS Lett. 142, 289-292.
  7. Cammack, R., Rao, K.K., Serra, J. and Llama, M.J. (1986) The redox properties of the iron-sulphur cluster in hydrogenase from Chromatium vinosum, strain D. Biochimie 68, 93-96.
  8. Cammack, R., Bagyinka, C. and Kovacs, K.L. (1989a) Spectroscopic characterization of the nickel and iron-sulphur clusters of hydrogenase from the purple photosynthetic bacterium Thiocapsa roseopersicina. 1. Electron spin resonance spectroscopy. Eur. J. Biochem. 182, 357-362.
  9. Cammack, R., Kovacs, K.L., McCracken, J. and Peisach, J. (1989b) Spectroscopic characterization of the nickel and iron-sulphur clusters of hydrogenase from the purple photosynthetic bacterium Thiocapsa roseopersicina. 2. Electron spin­echo spectroscopy. Eur. J. Biochem. 182, 363-366.
  10. Chapman, A., Cammack, R., Hatchikian, E.C., McCracken, J. and Peisach, J. (1988) A pulsed EPR study of redox­dependent hyperfine interactions for the nickel centre of Desulfovibrio gigas hydrogenase. FEBS Lett. 242, 134-138.
  11. Coremans, J.M.C.C., van Garderen, C.J. and Albracht, S.P.J. (1992) On the redox equilibrium between H2 and hydrogenase. Biochim. Biophys. Acta 1119, 148-156.
  12. Czechowski, M.H., He, S.H., Nacro, M., DerVartanian, D.V., Peck, H.D., Jr. and LeGall, J. (1984) A cytoplasmic nickel-iron hydrogenase with high specific activity from Desulfovibrio multispirans sp. N., a new species of sulfate reducing bacterium. Biochem. Biophys. Res. Commun. 125, 1025-1032.
  13. de Lacey, A.L., Hatchikian, E.C., Volbeda, A., Frey, M., Fontecilla­Camps, J.C. and Fernandez, V.M. (1997) Infrared­spectroelectrochemical characterization of the [NiFe] hydrogenase of Desulfovibrio gigas. J. Am. Chem. Soc. 119, 7181-7189.
  14. DerVartanian, M.E., Menon, N.K., Przybyla, A.E., Peck, H.D., Jr. and DerVartanian, D.V. (1996) Electron paramagnetic resonance (EPR) studies on hydrogenase­1 (HYD1) purified from a mutant strain (AP6) of Escherichia coli enhanced in HYD1. Biochem. Biophys. Res. Commun. 227, 211-215.
  15. Dole, F., Medina, M., More, C., Cammack, R., Bertrand, P. and Guigliarelli, B. (1996) Spin-spin interactions between the Ni site and the [4Fe-4S] centers as a probe of light­induced structural changes in active Desulfovibrio gigas hydrogenase. Biochemistry 35, 16399-16406.
  16. Dole, F., Fournel, A., Magro, V., Hatchikian, E.C., Bertrand, P. and Guigliarelli, B. (1997) Nature and electronic structure of the Ni-X dinuclear center of Desulfovibrio gigas hydrogenase. Implications for the enzymatic mechanism. Biochemistry 36, 7847-7854.
  17. Eidsness, M.K., Scott, R.A., Prickril, B.C., DerVartanian, D.V., LeGall, J., Moura, I., Moura, J.J.G. and Peck, H.D., Jr. (1989) Evidence for selenocysteine coordination to the active site nickel in the [NiFeSe] hydrogenases from Desulfovibrio baculatus. Proc. Natl. Acad. Sci. USA 86, 147-151.
  18. Fauque, G., Teixeira, M., Moura, I., Lespinat, P.A., Xavier, A.V., DerVartanian, D.V., Peck, H.D., Jr., LeGall, J. and Moura, J.J.G. (1984) Purification, characterization and redox properties of hydrogenase from Methanosarcina barkeri (DSM 800). Eur. J. Biochem. 142, 21-28.
  19. Fauque, G., Czechowski, M., Berlier, Y.M., Lespinat, P.A., LeGall, J. and Moura, J.J.G. (1992) Partial purification and characterization of the first hydrogenase isolated from a thermophilic sulfate­reducing bacterium. Biochem. Biophys. Res. Commun. 184, 1256-1260.
  20. Fernandez, V.M., Rao, K.K., Fernandez, M.A. and Cammack, R. (1986) Activation and deactivation of the membrane­bound hydrogenase from Desulfovibrio desulfuricans, Norway strain. Biochimie 68, 43-48.
  21. Fernandez, V.M., Rua, M.L., Reyes, P., Cammack, R. and Hatchikian, E.C. (1989) Inhibition of Desulfovibrio gigas hydrogenase with copper salts and other metal ions. Eur. J. Biochem. 185, 449-454.
  22. Franco, R., Moura, I., LeGall, J., Peck, H.D., Jr., Huynh, B.­H. and Moura, J.J.G. (1994) Characterization of D. desulfuricans (ATCC 27774) [NiFe] hydrogenase EPR and redox properties of the native and the dihydrogen reacted states. Biochim. Biophys. Acta 1144, 302-308.
  23. Gessner, C., Trofanchuk, O., Kawagoe, K., Higuchi, Y., Yasuoka, N. and Lubitz, W. (1996) Single crystal EPR study of the Ni center of NiFe hydrogenase. Chem. Phys. Lett. 256, 518-524.
  24. Gu, Z., Dong, J., Allan, C.B., Choudhury, S.B., Franco,R., Moura, J.J.G., Moura, I., LeGall, J., Przybyla, A.E., Roseboom, W., Albracht, S.P.J., Axley, M.J., Scott, R.A. and Maroney, M.J. (1996) Structure of the Ni sites in hydrogenases by X­ray absorption spectroscopy. Species variation and the effects of redox poise. J. Am. Chem. Soc. 118, 11155-11165.
  25. Guigliarelli, B., More, C., Fournel, A., Asso, M., Hatchikian, E.C., Williams, R., Cammack, R. and Bertrand, P. (1995) Structural organization of the Ni and (4Fe-4S) centers in the active form of Desulfovibrio gigas hydrogenase. Analysis of the magnetic interactions by electron paramagnetic resonance spectroscopy. Biochemistry 34, 4781-4790.
  26. Hatchikian, E.C., Traore, A.S., Fernandez, V.M. and Cammack, R. (1990) Characterization of the nickel-iron periplasmic hydrogenase from Desulfovibrio fructosovorans. Eur. J. Biochem. 187, 635-643.
  27. Happe, R.P., Roseboom, W. and Albracht, S.P.J. (1999) Pre­steady­state kinetics of the reactions of [NiFe]-hydrogenase from Chromatium vinosum with H2 and CO. Eur. J. Biochem. 259, 602-608.
  28. He, S.H., Woo, S.B., DerVartanian, D.V., Le Gall, J. and Peck, H.D., Jr. (1989) Effects of acetylene on hydrogenases from the sulfate reducing and methanogenic bacteria. Biochem. Biophys. Res. Commun. 161, 127-133.
  29. Higuchi, Y., Yasouka, N., Kakudo, M., Katsube, Y., Yagi, T. and Inokuchi, H. (1987) Single crystals of hydrogenase from Desulfovibrio vulgaris Miyazaki F. J. Biol. Chem. 262, 2823-2825.
  30. Higuchi, Y., Okamoto, T., Fujimoto, K., Misaki, S., Morimoto, Y. and Yasouka, N. (1994) Location of active sites of NiFe hydrogenase determined by the combination of multiple isomorphous replacement and multiwavelength anomalous­diffraction methods. Acta Crystallogr. D50, 781-785.
  31. Higuchi, Y., Okamoto, T. and Yasouka, N. (1996) The heterogeneity in a protein crystal revealed by synchrotron radiation. J. Crystal Growth 168, 99-105.
  32. Higuchi, Y., Yagi, T. and Yasouka, N. (1997) Unusual ligand structure in Ni-Fe active center and an additional Mg site in hydrogenase revealed by high resolution X­ray structure analysis. Structure 5, 1671-1680.
  33. Huyett, J.E., Carepo, M., Pamplona, A., Franco, R., Moura, I., Moura, J.J.G. and Hoffman, B.M. (1997) 57Fe Q­band pulsed ENDOR of the hetero­dinuclear site of nickel hydrogenase: Comparison of the NiA, NiB, and NiC States. J. Am. Chem. Soc. 119, 9291-9292.
  34. Huynh, B.­H., Patil, D.S., Moura, I., Teixeira, M., Moura, J.J.G., DerVartanian, D.V., Czechowski, M.H., Prickril, B.C., Peck, H.D., Jr. and LeGall, J. (1987) On the active sites of the [NiFe] hydrogenase from Desulfovibrio gigas. Mössbauer and redox­titration studies. J. Biol. Chem. 262, 795-800.
  35. Johnson, M.K., Czernuszewicz, R.S., Spiro, T.G., Ramsay, R.R. and Singer, T.P. (1983) Resonance Raman studies of beef heart aconitase and a bacterial hydrogenase. J. Biol. Chem. 258, 12771-12774.
  36. Johnson, M.K., Zambrano, I.C., Czechowski, M.H., Peck, H.D., Jr., DerVartanian, D.V. and LeGall, J. (1985) Low temperature magnetic circular dichroism spectroscopy as a probe for the optical transitions of paramagnetic nickel in hydrogenase. Biochem. Biophys. Res. Commun. 128, 220-225.
  37. Krüger, H.­J., Huynh, B.­H., Ljungdahl, P.O., Xavier, A.V., DerVartanian, D.V., Moura, I., Peck, H.D., Jr., Teixeira, M., Moura, J.J.G. and LeGall, J. (1982) Evidence for nickel and a three­iron center in the hydrogenase of Desulfovibrio desulfuricans. J. Biol. Chem. 257, 14620-14623.
  38. Lalla­Maharajh, W.V., Hall, D.O., Cammack, R., Rao, K.K. and Le Gall, J. (1983) Purification and properties of the membrane­bound hydrogenase from Desulfovibrio desulfuricans. Biochem. J. 209, 445-454.
  39. LeGall, J., Ljungdahl, P.O., Moura, I., Peck, H.D., Jr., Xavier, A.V., Moura, J.J.G., Teixeira, M., Huynh, B.­H. and DerVartanian, D.V. (1982) The presence of redox­sensitive nickel in the periplasmic hydrogenase from Desulfovibrio gigas. Biochem. Biophys. Res. Commun. 106, 610-616.
  40. Medina, M., Williams, R., Hatchikian, E.C. and Cammack, R. (1994) Studies of light­induced nickel EPR signals in Desulfovibrio gigas hydrogenase. J. Chem. Soc., Faraday Trans. 90, 2921-2924.
  41. Medina, M., Hatchikian, E.C. and Cammack, R. (1996) Studies of light­induced nickel EPR signals in hydrogenase: Comparison of enzymes with and without selenium. Biochim. Biophys. Acta . 1275, 227-236.
  42. Montet, Y., Amara, P., Volbeda, A., Vernede, X., Hatchikian, E.C., Field, M.J., Frey, M. and Fontecilla­Camps, J.C. (1997) Gas access to the active site of Ni-Fe hydrogenases probed by X­ray crystallography and molecular dynamics. Nature Struct. Biol. 4, 523-526.
  43. Montet, Y., Garcin, E., Volbeda, A., Hatchikian, E.C., Frey, M. and Fontecilla­Camps, J.C. (1998) Structural bases for the catalytic mechanism of NiFe hydrogenase. Pure Appl. Chem. 70, 25-31.
  44. Moura, J.J.G., Moura, I., Huynh, B.­H., Krüger, H.­J., Teixeira, M., DuVarney, R.C., DerVartanian, D.V., Xavier, A.V., Peck, H.D., Jr. and LeGall, J. (1982) Unambiguous identification of the nickel EPR signal in 61Ni­enriched Desulfovibrio gigas hydrogenase. Biochem. Biophys. Res. Commun. 108, 1388-1393.
  45. Nivière, V., Forget, N., Gayda, J.P. and Hatchikian, E.C. (1986) Characterization of the soluble hydrogenase from Desulfovibrio africanus. Biochem. Biophys. Res. Commun. 139, 658-665.
  46. Nivière, V., Hatchikian, E.C., Cambillau, C. and Frey, M. (1987) Crystallization, preliminary X­ray study and crystal activity of the hydrogenase from Desulfovibrio gigas. J. Mol. Biol. 195, 969-971.
  47. Pereira, I.A.C., Romão, C.V., Xavier, A.V., LeGall, J. and Teixeira, M. (1998) Electron transfer between hydrogenases and mono­ and multiheme cytochromes in Desulfovibrio ssp. J. Biol. Inorg. Chem. 3, 494-498.
  48. Pierik, A.J., Schmelz, M., Lenz, O., Friedrich, B. and Albracht, S.P.J. (1998) Characterization of the active site of a hydrogen sensor from Alcaligenes eutrophus. FEBS Lett. 438, 231-235.
  49. Pierik, A.J., Roseboom, W., Happe, R.P., Bagley, K.A. and Albracht, S.P.J. (1999) Carbon monoxide and cyanide as intrinsic ligands to iron in the active site of [NiFe]­hydrogenases. NiFe(CN)2CO, biology's way to activate H2. J. Biol. Chem. 274, 3331-3337.
  50. Przybyla, A.E., Robbins, J., Menon, N. and Peck, H.D., Jr. (1992) Structure­function relationships among the nickel­containing hydrogenases. FEMS Microbiol. Rev. 8, 109-135.
  51. Rieder, R., Cammack, R. and Hall, D.O. (1984) Purification and properties of the soluble hydrogenase from Desulfovibrio desulfuricans (strain Norway 4). Eur. J. Biochem. 145, 637-643.
  52. Roberts, L.M. and Lindahl, P.A. (1994) Analysis of oxidative titrations of Desulfovibrio gigas hydrogenase: implications for the catalytic mechanism. Biochemistry 33, 14339-14350.
  53. Romão, C.V., Pereira, I.A.C., Xavier, A.V., LeGall, J. and Teixeira, M. (1997) Characterization of the [NiFe] hydrogenase from the sulfate reducer Desulfovibrio vulgaris Hildenborough. Biochem. Biophys. Res. Commun. 240, 75-79.
  54. Rousset, M., Montet, Y., Guigliarelli, B., Forget, N., Asso, M., Bertrand, P., Fontecilla­Camps, J.C. and Hatchikian, E.C. (1998) [3Fe-4S] to [4Fe-4S] cluster conversion in Desulfovibrio fructosovorans [NiFe] hydrogenase by site­directed mutagenesis. Proc. Natl. Acad. Sci. USA 95, 11625-11630.
  55. Schneider, K., Cammack, R. and Schlegel, H.G. (1984) Content and localization of FMN, Fe-S clusters and nickel in the NAD­linked hydrogenase of Nocardia opaca 1b. Eur. J. Biochem. 142, 75-84.
  56. Serebryakova, L.T., Medina, M., Zorin, N.A., Gogotov, I.N. and Cammack, R. (1996) Reversible hydrogenase of Anabaena variabilis ATCC 29413: Catalytic properties and characterization of redox centres. FEBS Lett. 383, 79-82.
  57. Sorgenfrei, O., Duin, E.C., Klein, A. and Albracht, S.P.J. (1997) Changes in the electronic structure around Ni in oxidized and reduced selenium­containing hydrogenases from Methanococcus voltae. Eur. J. Biochem. 247, 681-687.
  58. Strekas, T., Antanaitis, B.C. and Krasna, A.I. (1980) Characterization and stability of hydrogenase from Chromatium. Biochim. Biophys. Acta 616, 1-9.
  59. Surerus, K.K., Chen, M., van der Zwaan, J.W., Rusnak, F.M., Kolk, M., Duin, E.C., Albracht, S.P. and Münck, E. (1994) Further characterization of the spin coupling observed in oxidized hydrogenase from Chromatium vinosum. A Mössbauer and multifrequency EPR study. Biochemistry 33, 4980-4993.
  60. Szokefalvi­Nagy, Z., Bagyinka, C., Demeter, I., Kovacs, K.L. and Quynh, L.H. (1990) Location and quantification of metal ions in enzymes combining polyacrylamide gel electrophoresis and particle­induced X­ray emission. Biol. Trace Elem. Res. 26-27, 93-101.
  61. Teixeira, M., Moura, I., Xavier, A.V., DerVartanian, D.V., LeGall, J., Peck, H.D., Jr., Huynh, B.­H. and Moura, J.J.G. (1983) Desulfovibrio gigas hydrogenase: redox properties of the nickel and iron-sulfur centers. Eur. J. Biochem. 130, 481-484.
  62. Teixeira, M., Moura, I., Xavier, A.V., Huynh, B.­H., DerVartanian, D.V., Peck, H.D., Jr., LeGall, J. and Moura, J.J.G. (1985) Electron paramagnetic resonance studies on the mechanism of activation and the catalytic cycle of the nickel­containing hydrogenase from Desulfovibrio gigas. J. Biol. Chem. 260, 8942-8950.
  63. Teixeira, M., Moura, I., Fauque, G., Czechowski, M., Berlier, Y., Lespinat, P.A., LeGall, J., Xavier, A.V. and Moura, J.J.G. (1986) Redox properties and activity studies on a nickel­containing hydrogenase isolated from a halophilic sulfate reducer Desulfovibrio salexigens. Biochimie 68, 75-84.
  64. Teixeira, M., Fauque, G., Moura, I., Lespinat, P.A., Berlier, Y., Prickril, B., Peck, H.D., Jr., Xavier, A.V., LeGall, J. and Moura, J.J.G. (1987) Nickel-[iron-sulfur]-selenium­containing hydrogenases from Desulfovibrio baculatus (DSM 1743). Redox centers and catalytic properties. Eur. J. Biochem. 167, 47-58.
  65. Teixeira, M., Moura, I., Xavier, A.V., Moura, J.J.G., LeGall, J., DerVartanian, D.V., Peck, H.D., Jr. and Huynh, B.­H. (1989) Redox intermediates of Desulfovibrio gigas [NiFe] hydrogenase generated under hydrogen. Mössbauer and EPR characterization of the metal centers. J. Biol. Chem. 264, 16435-16450.
  66. Teixeira, M., Moura, I., Fauque, G., DerVartanian, D.V., LeGall, J., Peck, H.D., Jr., Moura, J.J.G. and Huynh, B.­H. (1990) The iron-sulfur centers of the soluble [NiFeSe] hydrogenase from Desulfovibrio baculatus (DSM 1743). EPR and Mössbauer characterization. Eur. J. Biochem. 189, 381-386.
  67. van der Spek, T.M., Arendsen, A.F., Happe, R.P., Yun, S., Bagley, K.A., Stufkens, D.J., Hagen, W.R. and Albracht, S.P.J. (1996) Similarities in the architecture of the active sites of Ni­hydrogenases and Fe­hydrogenases detected by means of infrared spectroscopy. Eur. J. Biochem. 237, 629-634.
  68. van der Zwaan, J.W., Albracht, S.P.J., Fontijn, R.D. and Slater, E.C. (1985) Monovalent nickel in hydrogenase from Chromatium vinosum. Light sensitivity and evidence for direct interaction with hydrogen. FEBS Lett. 179, 271-277.
  69. van der Zwaan, J.W., Albracht, S.P.J., Fontijn, R.D. and Mul, P. (1987) On the anomalous temperature behaviour of the EPR signal of monovalent nickel in hydrogenase. Eur. J. Biochem. 169, 377-384.
  70. van der Zwaan, J.W., Coremans, J.M., Bouwens, E.C. and Albracht, S.P.J. (1990) Effect of 17O2 and 13CO on EPR spectra of nickel in hydrogenase from Chromatium vinosum. Biochim. Biophys. Acta. 1041, 101-110.
  71. van Heerikhuizen, H., Albracht, S.P.J., Slater, E.C. and van Rheenen, P.S. (1981) Purification and some properties of the soluble hydrogenase from Chromatium vinosum. Biochim. Biophys. Acta 657, 26-39.
  72. Volbeda, A., Piras, C., Charon, M.H., Hatchikian, E.C., Frey, M. and Fontecilla­Camps, J.C. (1993) Location of the redox centers in hydrogenase as determined by X­ray crystallography at 5 Å resolution. Jt. CCP4 ESF-EACBM Newsletter Protein Crystallogr. 28, 30-33.
  73. Volbeda, A., Charon, M.H., Piras, C., Hatchikian, E.C., Frey, M. and Fontecilla­Camps, J.C. (1995) Crystal structure of the nickel-iron hydrogenase from Desulfovibrio gigas. Nature 373, 580-587.
  74. Volbeda, A., Garcin, E., Piras, C., de Lacey, A.L., Fernandez, V.M., Hatchikian, E.C., Frey, M. and Fontecilla­Camps, J.C. (1996) Structure of the [NiFe] hydrogenase active site: Evidence for biologically uncommon Fe ligands. J. Am. Chem. Soc. 118, 12989-12996.
  75. Wang, C.P., Franco, R., Moura, J.J.G., Moura, I. and Day, E.P. (1992) The nickel site in active Desulfovibrio baculatus [NiFeSe] hydrogenase is diamagnetic. Multifield saturation magnetization measurement of the spin state of Ni(II). J. Biol. Chem. 267, 7378-7380.
  76. Zorin, N.A. (1986) Redox properties and active center of phototrophic bacteria hydrogenases. Biochimie 68, 97-101.
Reviews on nickel-iron hydrogenase