References
1. Dewar MJ, Storch DM (1985) Alternative view of enzyme reactions. Proc Natl Acad Sci U S
A 82(8):2225–2229
2. Warshel A, Sharma PK, Kato M, Xiang Y, Liu H (2006) Electrostatic basis for enzyme
catalysis. Chem Rev 106(8):3210–3235. doi:10.1021/cr0503106
3. Albery WJ, Knowles JR (1976) Free-energy profile of the reaction catalyzed by
triosephosphate isomerase. Biochemistry 15(25):5627–5631. doi:10.1021/bi00670a031
4. Rockstr€ om J, Steffen W, Noone K, Persson Å, Chapin FS, Lambin EF, Lenton TM,
Scheffer M, Folke C, Schellnhuber HJ, Nykvist B, de Wit CA, Hughes T, van der
Leeuw S, Rodhe H, S€ orlin S, Snyder PK, Costanza R, Svedin U, Falkenmark M,
Karlberg L, Corell RW, Fabry VJ, Hansen J, Walker B, Liverman D, Richardson K,
Crutzen P, Foley JA (2009) A safe operating space for humanity. Nature 461
(7263):472–475. doi:10.1038/461472a
5. Lubitz W, Ogata H, Ruediger O, Reijerse E (2014) Hydrogenases. Chem Rev
114:4081–4148. doi:10.1021/cr4005814
6. Hiromoto T, Warkentin E, Moll J, Ermler U, Shima S (2009) The crystal structure of an [Fe]hydrogenase-substrate complex reveals the framework for H 2 activation. Angew Chem Int Ed
48:6457–6460. doi:10.1002/anie.200902695
7. Fontecilla-Camps JC, Volbeda A, Cavazza C, Nicolet Y (2007) Structure/function relationships of [NiFe]- and [FeFe]-hydrogenases. Chem Rev 107(10):4273–4303. doi:10.1021/
cr050195z
8. 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. doi:10.1039/b905841a
9. Esselborn J, Lambertz C, Adamska-Venkatesh A, Simmons T, Berggren G, Nothl J, Siebel J,
Hemschemeier A, Artero V, Reijerse E, Fontecave M, Lubitz W, Happe T (2013) Spontaneous activation of [FeFe]-hydrogenases by an inorganic [2Fe] active site mimic. Nat Chem
Biol 9:607–609. doi:10.1038/nchembio.1311
10. Liu T, DuBois DL, Bullock RM (2013) An iron complex with pendent amines as a molecular
electrocatalyst for oxidation of hydrogen. Nat Chem 5:228–233. doi:10.1038/nchem.1571
11. Wilson AD, Newell RH, McNevin MJ, Muckerman JT, DuBois MR, DuBois DL (2006)
Hydrogen oxidation and production using nickel-based molecular catalysts with positioned
proton relays. J Am Chem Soc 128:358–366. doi:10.1021/ja056442y
12. Nicolet Y, Lemon BJ, Fontecilla-Camps JC, Peters JW (2000) A novel [FeS] cluster in Fe-only
hydrogenases. Trends Biochem Sci 25:138–143. doi:10.1016/s0968-0004(99)01536-4
13. Schilter D, Rauchfuss TB, Stein M (2012) Connecting [NiFe]- and [FeFe]-hydrogenases:
mixed-valence nickel-iron dithiolates with rotated structures. Inorg Chem 51:8931–8941.
doi:10.1021/ic300910r
14. Hexter SV, Grey F, Happe T, Climent V, Armstrong FA (2012) Electrocatalytic mechanism
of reversible hydrogen cycling by enzymes and distinctions between the major classes of
hydrogenases. Proc Natl Acad Sci U S A 109:11516–11521. doi:10.1073/pnas.1204770109
15. Hajj V, Baffert C, Sybirna K, Meynial-Salles I, Soucaille P, Bottin H, Fourmond V, Le ´ger C
(2014) [FeFe]-hydrogenase reductive inactivation and implication for catalysis. Energy
Environ Sci 7:715–719. doi:10.1039/c3ee42075b
16. Adamska A, Silakov A, Lambertz C, Rudiger O, Happe T, Reijerse E, Lubitz W (2012)
Identification and characterization of the “super-reduced” state of the H-cluster in [FeFe]hydrogenase: a new building block for the catalytic cycle? Angew Chem Int Ed
51:11458–11462. doi:10.1002/anie.201204800
17. Mulder DW, Ratzloff MW, Shepard EM, Byer AS, Noone SM, Peters JW, Broderick JB,
King PW (2013) EPR and FTIR analysis of the mechanism of H 2 activation by [FeFe]262
L. Gan et al.
1. Dewar MJ, Storch DM (1985) Alternative view of enzyme reactions. Proc Natl Acad Sci U S
A 82(8):2225–2229
2. Warshel A, Sharma PK, Kato M, Xiang Y, Liu H (2006) Electrostatic basis for enzyme
catalysis. Chem Rev 106(8):3210–3235. doi:10.1021/cr0503106
3. Albery WJ, Knowles JR (1976) Free-energy profile of the reaction catalyzed by
triosephosphate isomerase. Biochemistry 15(25):5627–5631. doi:10.1021/bi00670a031
4. Rockstr€ om J, Steffen W, Noone K, Persson Å, Chapin FS, Lambin EF, Lenton TM,
Scheffer M, Folke C, Schellnhuber HJ, Nykvist B, de Wit CA, Hughes T, van der
Leeuw S, Rodhe H, S€ orlin S, Snyder PK, Costanza R, Svedin U, Falkenmark M,
Karlberg L, Corell RW, Fabry VJ, Hansen J, Walker B, Liverman D, Richardson K,
Crutzen P, Foley JA (2009) A safe operating space for humanity. Nature 461
(7263):472–475. doi:10.1038/461472a
5. Lubitz W, Ogata H, Ruediger O, Reijerse E (2014) Hydrogenases. Chem Rev
114:4081–4148. doi:10.1021/cr4005814
6. Hiromoto T, Warkentin E, Moll J, Ermler U, Shima S (2009) The crystal structure of an [Fe]hydrogenase-substrate complex reveals the framework for H 2 activation. Angew Chem Int Ed
48:6457–6460. doi:10.1002/anie.200902695
7. Fontecilla-Camps JC, Volbeda A, Cavazza C, Nicolet Y (2007) Structure/function relationships of [NiFe]- and [FeFe]-hydrogenases. Chem Rev 107(10):4273–4303. doi:10.1021/
cr050195z
8. 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. doi:10.1039/b905841a
9. Esselborn J, Lambertz C, Adamska-Venkatesh A, Simmons T, Berggren G, Nothl J, Siebel J,
Hemschemeier A, Artero V, Reijerse E, Fontecave M, Lubitz W, Happe T (2013) Spontaneous activation of [FeFe]-hydrogenases by an inorganic [2Fe] active site mimic. Nat Chem
Biol 9:607–609. doi:10.1038/nchembio.1311
10. Liu T, DuBois DL, Bullock RM (2013) An iron complex with pendent amines as a molecular
electrocatalyst for oxidation of hydrogen. Nat Chem 5:228–233. doi:10.1038/nchem.1571
11. Wilson AD, Newell RH, McNevin MJ, Muckerman JT, DuBois MR, DuBois DL (2006)
Hydrogen oxidation and production using nickel-based molecular catalysts with positioned
proton relays. J Am Chem Soc 128:358–366. doi:10.1021/ja056442y
12. Nicolet Y, Lemon BJ, Fontecilla-Camps JC, Peters JW (2000) A novel [FeS] cluster in Fe-only
hydrogenases. Trends Biochem Sci 25:138–143. doi:10.1016/s0968-0004(99)01536-4
13. Schilter D, Rauchfuss TB, Stein M (2012) Connecting [NiFe]- and [FeFe]-hydrogenases:
mixed-valence nickel-iron dithiolates with rotated structures. Inorg Chem 51:8931–8941.
doi:10.1021/ic300910r
14. Hexter SV, Grey F, Happe T, Climent V, Armstrong FA (2012) Electrocatalytic mechanism
of reversible hydrogen cycling by enzymes and distinctions between the major classes of
hydrogenases. Proc Natl Acad Sci U S A 109:11516–11521. doi:10.1073/pnas.1204770109
15. Hajj V, Baffert C, Sybirna K, Meynial-Salles I, Soucaille P, Bottin H, Fourmond V, Le ´ger C
(2014) [FeFe]-hydrogenase reductive inactivation and implication for catalysis. Energy
Environ Sci 7:715–719. doi:10.1039/c3ee42075b
16. Adamska A, Silakov A, Lambertz C, Rudiger O, Happe T, Reijerse E, Lubitz W (2012)
Identification and characterization of the “super-reduced” state of the H-cluster in [FeFe]hydrogenase: a new building block for the catalytic cycle? Angew Chem Int Ed
51:11458–11462. doi:10.1002/anie.201204800
17. Mulder DW, Ratzloff MW, Shepard EM, Byer AS, Noone SM, Peters JW, Broderick JB,
King PW (2013) EPR and FTIR analysis of the mechanism of H 2 activation by [FeFe]262
L. Gan et al.