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charge density on the nickel center in hydrogenase from Chromatium vinosum. Biochemistry 34:5527–5535
19. Darensbourg DJ, Reibenspies JH, Lai CH et al (1997) Analysis of an organometallic iron site
model for the heterodimetallic unit of [NiFe] hydrogenase. J Am Chem Soc 119:7903–7904
20. Lai CH, Lee WZ, Miller ML et al (1998) Responses of the Fe (CN) 2 (CO) unit to electronic
changes as related to its role in [NiFe] hydrogenase. J Am Chem Soc 120:10103–10114
21. Ding S, Ghosh P, Lunsford AM et al (2016) Hemilabile bridging thiolates as proton shuttles
in bioinspired H 2 production electrocatalysts. J Am Chem Soc 138:12920–12927
22. Brazzolotto D, Gennari M, Queyriaux N et al (2016) Nickel-centred proton reduction
catalysis in a model of [NiFe] hydrogenase. Nat Chem 8:1054–1060
23. Ogo S, Ichikawa K, Kishima T et al (2013) A functional [NiFe] hydrogenase mimic that
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24. Silakov A, Wenk B, Reijerse E, Lubitz W (2009) (14)N HYSCORE investigation of the
H-cluster of [FeFe]-hydrogenase: evidence for a nitrogen in the dithiol bridge. Phys Chem
Chem Phys 11:6592–6599
25. Winkler M, Senger M, Duan J et al (2017) Accumulating the hydride state in the catalytic
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26. Nicolet Y, Lemon BJ, Fontecilla-Camps JC, Peters JW (2000) A novel FeS cluster in
Fe-only hydrogenases. Trends Biochem Sci 25:138–143
27. Volbeda A, Charon MH, Piras C et al (1995) Crystal structure of the nickel–iron
hydrogenase from Desulfovibrio gigas. Nature 373:580–587
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29. Garcin E, Vernede X, Hatchikian EC et al (1999) The crystal structure of a reduced [NiFeSe]
hydrogenase provides an image of the activated catalytic center. Structure 7:557–566
30. Hiromoto T, Ataka K, Pilak O et al (2009) The crystal structure of C176A mutated [Fe]hydrogenase suggests an acyl-iron ligation in the active site iron complex. FEBS Lett
58:585–590
31. Fontecilla-Camps JC, Volbeda A, Cavazza C, Nicolet Y (2007) Structure/function
relationships of [NiFe]-and [FeFe]-hydrogenases. Chem Rev 107:4273–4303
32. Lubitz W, Ogata H, Rüdiger O, Reijerse E (2014) Hydrogenases. Chem Rev 114:4081–4148
33. Schilter D, Camara JM, Huynh MT et al (2016) Hydrogenase enzymes and their synthetic
models: the role of metal hydrides. Chem Rev 116:8693–8749
34. Thauer RK (2011) Hydrogenases and the global H 2 cycle. Eur J Inorg Chem 2011:919–921
35. De Lacey AL, Fernandez VM, Rousset M, Cammack R (2007) Activation and inactivation
of hydrogenase function and the catalytic cycle: spectroelectrochemical studies. Chem Rev
107:4304–4330
36. Cammack R, Frey M, Robson R (eds) (2001) Hydrogen as a fuel: learning from nature. CRC
Press
37. Eberle U, Felderhoff M, Schueth F (2009) Chemical and physical solutions for hydrogen
storage. Angew Chem Int Ed 48:6608–6630
38. Reece SY, Hamel JA, Sung K et al (2011) Wireless solar water splitting using silicon-based
semiconductors and earth-abundant catalysts. Science 334:645–648
39. Reich HJ, Hondal RJ (2016) Why nature chose selenium. ACS Chem Biol 11:821–841
40. Baltazar CS, Marques MC, Soares CM et al (2011) Nickel–iron–selenium hydrogenases–an
overview. Eur J Inorg Chem 2011:948–962
41. Wombwell C, Caputo CA, Reisner E (2015) [NiFeSe]-hydrogenase chemistry. Acc Chem
Res 48:2858–2865
296
M. Y. Darensbourg et al.
mechanism of activation and the catalytic cycle of the nickel-containing hydrogenase from
Desulfovibrio gigas. J Biol Chem 260:8942–8950
18. Bagley KA, Duin EC, Roseboom W et al (1995) Infrared-detectable group senses changes in
charge density on the nickel center in hydrogenase from Chromatium vinosum. Biochemistry 34:5527–5535
19. Darensbourg DJ, Reibenspies JH, Lai CH et al (1997) Analysis of an organometallic iron site
model for the heterodimetallic unit of [NiFe] hydrogenase. J Am Chem Soc 119:7903–7904
20. Lai CH, Lee WZ, Miller ML et al (1998) Responses of the Fe (CN) 2 (CO) unit to electronic
changes as related to its role in [NiFe] hydrogenase. J Am Chem Soc 120:10103–10114
21. Ding S, Ghosh P, Lunsford AM et al (2016) Hemilabile bridging thiolates as proton shuttles
in bioinspired H 2 production electrocatalysts. J Am Chem Soc 138:12920–12927
22. Brazzolotto D, Gennari M, Queyriaux N et al (2016) Nickel-centred proton reduction
catalysis in a model of [NiFe] hydrogenase. Nat Chem 8:1054–1060
23. Ogo S, Ichikawa K, Kishima T et al (2013) A functional [NiFe] hydrogenase mimic that
catalyzes electron and hydride transfer from H 2 . Science 339:682–684
24. Silakov A, Wenk B, Reijerse E, Lubitz W (2009) (14)N HYSCORE investigation of the
H-cluster of [FeFe]-hydrogenase: evidence for a nitrogen in the dithiol bridge. Phys Chem
Chem Phys 11:6592–6599
25. Winkler M, Senger M, Duan J et al (2017) Accumulating the hydride state in the catalytic
cycle of [FeFe]-hydrogenases. Nat Commun 8:1–7
26. Nicolet Y, Lemon BJ, Fontecilla-Camps JC, Peters JW (2000) A novel FeS cluster in
Fe-only hydrogenases. Trends Biochem Sci 25:138–143
27. Volbeda A, Charon MH, Piras C et al (1995) Crystal structure of the nickel–iron
hydrogenase from Desulfovibrio gigas. Nature 373:580–587
28. Ogata H, Nishikawa K, Lubitz W (2015) Hydrogens detected by subatomic resolution
protein crystallography in a [NiFe] hydrogenase. Nature 520:571–574
29. Garcin E, Vernede X, Hatchikian EC et al (1999) The crystal structure of a reduced [NiFeSe]
hydrogenase provides an image of the activated catalytic center. Structure 7:557–566
30. Hiromoto T, Ataka K, Pilak O et al (2009) The crystal structure of C176A mutated [Fe]hydrogenase suggests an acyl-iron ligation in the active site iron complex. FEBS Lett
58:585–590
31. Fontecilla-Camps JC, Volbeda A, Cavazza C, Nicolet Y (2007) Structure/function
relationships of [NiFe]-and [FeFe]-hydrogenases. Chem Rev 107:4273–4303
32. Lubitz W, Ogata H, Rüdiger O, Reijerse E (2014) Hydrogenases. Chem Rev 114:4081–4148
33. Schilter D, Camara JM, Huynh MT et al (2016) Hydrogenase enzymes and their synthetic
models: the role of metal hydrides. Chem Rev 116:8693–8749
34. Thauer RK (2011) Hydrogenases and the global H 2 cycle. Eur J Inorg Chem 2011:919–921
35. De Lacey AL, Fernandez VM, Rousset M, Cammack R (2007) Activation and inactivation
of hydrogenase function and the catalytic cycle: spectroelectrochemical studies. Chem Rev
107:4304–4330
36. Cammack R, Frey M, Robson R (eds) (2001) Hydrogen as a fuel: learning from nature. CRC
Press
37. Eberle U, Felderhoff M, Schueth F (2009) Chemical and physical solutions for hydrogen
storage. Angew Chem Int Ed 48:6608–6630
38. Reece SY, Hamel JA, Sung K et al (2011) Wireless solar water splitting using silicon-based
semiconductors and earth-abundant catalysts. Science 334:645–648
39. Reich HJ, Hondal RJ (2016) Why nature chose selenium. ACS Chem Biol 11:821–841
40. Baltazar CS, Marques MC, Soares CM et al (2011) Nickel–iron–selenium hydrogenases–an
overview. Eur J Inorg Chem 2011:948–962
41. Wombwell C, Caputo CA, Reisner E (2015) [NiFeSe]-hydrogenase chemistry. Acc Chem
Res 48:2858–2865
296
M. Y. Darensbourg et al.