Cobalt Enzymes/Models

Vitamin B₁₂ and its coenzyme forms are prominent cobalt-containing cofactors and part of the larger class of the natural tetrapyrrolic metal complexes. Such cobalt corrinoids are an important component of human nutrition, and many (other) forms of life also depend upon them. Cobalt-containing corrinoid cofactors play basic roles in carbon fixation and energy metabolism in anaerobes, as well as in the carbon metabolism in a broad range of lower organisms. Microorganisms developed unique B₁₂ biosynthetic means and, indeed, are the only natural sources of the B₁₂ derivatives. Other organisms have evolved intricate strategies for the uptake and transport of the corrinoids.

The cofactor functions of cobalt corrinoids are a result of their extraordinary organometallic chemistry under physiological conditions and their redox chemistry. Coenzyme B₁₂ (a reversible source of a free radical), methylcobalamin (a versatile methylating agent), and reduced (supernucleophilic or radicaloid) corrinoids are cofactors in a range of enzymes. These enzymes channel the specific reactivity of B₁₂ cofactors into biological catalysis of unique reactions, involving radicals and organometallic intermediates. B₁₂-dependent enzymes thus pose still puzzling structural and mechanistic questions, as does the recently discovered interaction of B₁₂ cofactors with RNA.

Bibliography

1 J. J. R. F. da Silva and R. J. P. Williams, The Biological Chemistry of the Elements, Clarendon Press, Oxford, 1991.
Google Scholar
2 B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins. Wiley-VCH, Weinheim, 1998.
10.1002/9783527612192
Google Scholar
3 R. Banerjee, ed., Chemistry and Biochemistry of B₁₂, John Wiley & Sons, New York, 1999.
Google Scholar
4 S. J. Lippard and J. M. Berg, Principles of Bioinorganic Chemistry, University Science Books, Mill Valley, Calif., 1994.
Google Scholar
5 B. A. Brennan, G. Alms, M. J. Nelson, L. T. Durney, and R. C. Scarrow, J. Am. Chem. Soc. 118, 9194–9195 (1996).
10.1021/ja961920d
CAS Web of Science® Google Scholar
6 A. R. Battersby, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 47–61.
10.1002/9783527612192.ch02
Google Scholar
7 M. J. Warren, E. Raux, H. L. Schubert, and J. C. Escalante-Semerena, Nat. Prod. Rep. 19, 390–412 (2002).
10.1039/b108967f
CAS PubMed Web of Science® Google Scholar
8 A. Eschenmoser, Angew. Chem. Int. Ed. 27, 5–39 (1988).
10.1002/anie.198800051
CAS Web of Science® Google Scholar
9 B. Kräutler, in A. Sigel, H. Sigel, and R. K. O. Sigel, eds., Metal–Carbon Bonds in Enzymes and Cofactors, Vol. 6, Royal Society of Chemistry, Cambridge, 2009, pp. 1–51.
10.1039/9781847559333-00001
Google Scholar
10 R. G. Matthews, in A. Sigel, H. Sigel, and R. K. O. Sigel, eds., Metal–Carbon Bonds in Enzymes and Cofactors, Vol. 6, Royal Society of Chemistry, Cambridge, 2009, pp. 53–114.
10.1039/9781847559333-00053
Google Scholar
11 A. Sigel, H. Sigel, and R. K. O. Sigel, eds., Metal–Carbon Bonds in Enzymes and Cofactors, Royal Society of Chemistry, Cambridge, 2009.
10.1039/9781847559333
Google Scholar
12 D. Dolphin, ed., B₁₂, Vol. I, John Wiley & Sons, New York, 1982.
Web of Science® Google Scholar
13 K. L. Brown, Chem. Rev. 105, 2075–2149 (2005).
10.1021/cr030720z
CAS PubMed Web of Science® Google Scholar
14 K. Folkers, in D. Dolphin, ed., B₁₂, Vol. I, John Wiley & Sons, New York, 1982, pp. 1–15.
Google Scholar
15 J. P. Glusker, in D. Dolphin, ed., B_12. Vol. I, John Wiley & Sons, New York, 1982, pp. 23–106.
Google Scholar
16 C. Kratky and B. Kräutler, in R. Banerjee, ed., Chemistry and Biochemistry of B_12. John Wiley & Sons, New York, 1999, pp. 9–41.
Google Scholar
17 L. Randaccio, S. Geremia, G. Nardin, and J. Würges, Coord. Chem. Rev. 250, 1332–1350 (2006).
10.1016/j.ccr.2005.12.005
CAS Web of Science® Google Scholar
18 B. Kräutler, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂ Proteins, Wiley-VCH, Weinheim, 1998, pp. 3–43.
10.1002/9783527612192
Google Scholar
19 P. A. Butler, M.-O. Ebert, A. Lyskowski, K. Gruber, C. Kratky, and B. Kräutler, Angew. Chem Int. Ed. 45, 989–993 (2006).
10.1002/anie.200502638
CAS PubMed Web of Science® Google Scholar
20 B. Kräutler, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins. Wiley-VCH, Weinheim, 1998, pp. 517–521.
10.1002/9783527612192.ch34
Google Scholar
21 E. Stupperich and H. J. Eisinger, Arch. Microbiol. 151, 372–377 (1989).
10.1007/BF00406567
CAS Web of Science® Google Scholar
22 R. Konrat, M. Tollinger, and B. Kräutler, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 349–368.
10.1002/9783527612192.ch23
Google Scholar
23 M. F. Summers, L. G. Marzilli, and A. Bax, J. Am. Chem. Soc. 108, 4285–4294 (1986).
10.1021/ja00275a008
CAS Web of Science® Google Scholar
24 S. Van Doorslaer, G. Jeschke, B. Epel, D. Goldfarb, R. A. Eichel, B. Kräutler, and A. Schweiger, J. Am. Chem. Soc. 125, 5915–5927 (2003).
10.1021/ja021218j
CAS PubMed Web of Science® Google Scholar
25 B. Kräutler, W. Keller, and C. Kratky, J. Am. Chem. Soc. 111, 8936–8938 (1989).
10.1021/ja00206a037
Web of Science® Google Scholar
26 J. Halpern, Science 227, 869–875 (1985).
10.1126/science.2857503
CAS PubMed Web of Science® Google Scholar
27 G. Kontaxis, D. Riether, R. Hannak, M. Tollinger, and B. Kräutler, Helv. Chim. Acta 82, 848–869 (1999).
10.1002/(SICI)1522-2675(19990609)82:6<848::AID-HLCA848>3.0.CO;2-L
CAS Web of Science® Google Scholar
28 R. G. Finke, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 383–402.
10.1002/9783527612192.ch25
Google Scholar
29 B. Kräutler, in R. Banerjee, ed., Chemistry and Biochemistry of B₁₂, John Wiley & Sons, New York, 1999, pp. 315–339.
Google Scholar
30 J. M. Pratt, Inorganic Chemistry of Vitamin B₁₂, Academic Press, New York, 1972.
Google Scholar
31 B. Kräutler, Helv. Chim. Acta 70, 1268–1278 (1987).
10.1002/hlca.19870700506
Web of Science® Google Scholar
32 B. Kräutler and S. Ostermann, in K. M. Kadish, K. M. Smith, and R. Guilard, eds., The Porphyrin Handbook, Vol. 11, Elsevier Science, Oxford, 2003, pp. 229–276.
10.1016/B978-0-08-092385-7.50013-6
Google Scholar
33 P. J. Craig and F. Glockling, eds., The Biological Alkylation of Heavy Elements, Royal Society of Chemistry, London, 1988.
Google Scholar
34 H. Mosimann and B. Kräutler, Angew. Chem. Int. Ed. 39, 393–200 (2000).
10.1002/(SICI)1521-3773(20000117)39:2<393::AID-ANIE393>3.0.CO;2-M
CAS PubMed Web of Science® Google Scholar
35 R. D. Woodyer, G. Li, H. Zhao, and W. A. van der Donk, Chem. Commun., 359–361 (2007).
10.1039/B614678C
CAS PubMed Web of Science® Google Scholar
36 P. K. Galliker, O. Gräther, M. Rümmler, W. Fitz, and D. Arigoni, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 447–458.
10.1002/9783527612192.ch29
Google Scholar
37 J. M. Pratt, in D. Dolphin, ed., B₁₂, Vol. I, John Wiley & Sons, New York, 1982, pp. 325–392.
Google Scholar
38 R. J. Sension, D. A. Harris, and A. G. Cole, J. Phys. Chem. B 109, 21954–21962 (2005).
10.1021/jp053202w
CAS PubMed Web of Science® Google Scholar
39 D. Lexa and J. M. Savéant, Acc. Chem. Res. 16, 235–243 (1983).
10.1021/ar00091a001
CAS Web of Science® Google Scholar
40 L. Auer, C. Weymuth, and R. Scheffold, Helv. Chim. Acta 76, 810–818 (1993).
10.1002/hlca.19930760205
CAS Web of Science® Google Scholar
41 S. Busato and R. Scheffold, Helv. Chim. Acta 77, 92–99 (1994).
10.1002/hlca.19940770112
CAS Web of Science® Google Scholar
42 R. Scheffold, S. Abrecht, R. Orlinski, H. R. Ruf, P. Stamouli, O. Tinembart, L. Walder, and C. Weymuth, Pure Appl. Chem. 59, 363–372 (1987).
10.1351/pac198759030363
CAS Web of Science® Google Scholar
43 B. Steiger, A. Ruhe, and L. Walder, Anal. Chem. 62, 759–766 (1990).
10.1021/ac00206a023
CAS Web of Science® Google Scholar
44 H. Shimakoshi, M. Tokunaga, T. Baba, and Y. Hisaeda, Chem. Commun., 1806–1807 (2004).
10.1039/b406400c
CAS PubMed Web of Science® Google Scholar
45 R. Keese, T. Darbre, U. V. Arx, S. Muller, A. Wolleb Gygi, D. Hirschi, V. Siljegovic, M. Pfammatter, A. Amolins, and T. Otten, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 289–301.
10.1002/9783527612192.ch19
Google Scholar
46 G. N. Schrauzer and E. Deutsch, J. Am. Chem. Soc. 91, 3341–3350 (1969).
10.1021/ja01040a041
CAS PubMed Web of Science® Google Scholar
47 N. Bresciani Pahor, M. Forcolin, L. G. Marzilli, L. Randaccio, M. F. Summers, and P. J. Toscano, Coord. Chem. Rev. 63, 1–125 (1985).
10.1016/0010-8545(85)80021-7
CAS Web of Science® Google Scholar
48 C. L. Drennan, S. Huang, J. T. Drummond, R. G. Matthews, and M. L. Ludwig, Science 266, 1669–1674 (1994).
10.1126/science.7992050
CAS PubMed Web of Science® Google Scholar
49 M. L. Ludwig and R. G. Matthews, Ann. Rev. Biochem. 66, 269–313 (1997).
10.1146/annurev.biochem.66.1.269
CAS PubMed Web of Science® Google Scholar
50 E. N. G. Marsh, D. E. Holloway, and H. P. Chen, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 253–264.
10.1016/S0167-739X(98)80025-3
Web of Science® Google Scholar
51 W. Friedrich, Vitamins, Walter de Gruyter, Berlin, 1988.
Google Scholar
52 E. Nexø, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 461–475.
10.1002/9783527612192.ch30
Google Scholar
53 G. Wohlfahrt and G. Diekert, in R. Banerjee, ed., Chemistry and Biochemistry of B₁₂, John Wiley & Sons, New York, 1999, pp. 871–893.
Google Scholar
54 B. Kräutler, W. Fieber, S. Ostermann, M. Fasching, K. H. Ongania, K. Gruber, C. Kratky, C. Mikl, A. Siebert, and G. Diekert, Helv. Chim. Acta 86, 3698–3716 (2003).
10.1002/hlca.200390313
Web of Science® Google Scholar
55 K. M. McCauley, D. A. Pratt, S. R. Wilson, J. Shey, T. J. Burkey, and W. A. van der Donk, J. Am. Chem. Soc. 127, 1126–1136 (2005).
10.1021/ja048573p
CAS PubMed Web of Science® Google Scholar
56 C. H. Hagemeier, M. Krüer, R. K. Thauer, E. Warkentin, and U. Ermler, Proc. Natl. Acad. Sci. USA 103, 18917–18922 (2006).
10.1073/pnas.0603650103
CAS PubMed Web of Science® Google Scholar
57 K. Sauer and R. K. Thauer, in R. Banerjee. (Ed), Chemistry and Biochemistry of B₁₂, John Wiley & Sons, New York, 1999, pp. 655–679.
Google Scholar
58 S. W. Ragsdale, Chem. Rev. 106, 3317–3337 (2006).
10.1021/cr0503153
CAS PubMed Web of Science® Google Scholar
59 B. Jaun, and R. K. Thauer, in A. Sigel, H. Sigel, and R. K. O. Sigel, eds., Metal–Carbon Bonds in Enzymes and Cofactors. Metal Ions in Life Sciences, Vol. 6, Royal Society of Chemistry, Cambridge, 2009, pp. 115–132.
Google Scholar
60 A. Eschenmoser, Ann. N. Y. Acad. Sci. 471, 108–129 (1986).
10.1111/j.1749-6632.1986.tb48030.x
CAS Web of Science® Google Scholar
61 C. L. Drennan, R. G. Matthews, and M. L. Ludwig, Curr. Opin. Struct. Biol. 4, 919–929 (1994).
10.1016/0959-440X(94)90275-5
CAS PubMed Web of Science® Google Scholar
62 W. Buckel and B. T. Golding, Ann. Rev. Microbiol. 60, 27–49 (2006).
10.1146/annurev.micro.60.080805.142216
CAS PubMed Web of Science® Google Scholar
63 P. A. Frey and A. D. Hegeman, Enzymatic Reaction Mechanisms, Oxford University Press, New York, 2007.
10.1093/oso/9780195122589.001.0001
Google Scholar
64 J. Rétey, Angew. Chem. Int. Ed. 29, 355–361 (1990).
10.1002/anie.199003551
Web of Science® Google Scholar
65 J. Stubbe, S. Licht, G. Gerfen, D. Silva, and S. Booker, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim 1998, pp. 321–331.
10.1002/9783527612192.ch21
Google Scholar
66 J. Rétey, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 273–288.
10.1002/9783527612192.ch18
Google Scholar
67 P. R. Evans and F. Mancia, in B. Kräutler, D. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂ Proteins, Wiley-VCH, Weinheim, 1998, pp. 217–226.
10.1002/9783527612192.ch13
Google Scholar
68 F. Mancia, G. A. Smith, and P. R. Evans, Biochemistry 38, 7999–8005 (1999).
10.1021/bi9903852
CAS PubMed Web of Science® Google Scholar
69 R. Reitzer, K. Gruber, G. Jogl, U. G. Wagner, H. Bothe, W. Buckel, and C. Kratky, Structure 7, 891–902 (1999).
10.1016/S0969-2126(99)80116-6
CAS PubMed Web of Science® Google Scholar
70 N. Shibata, J. Masuda, T. Tobimatsu, T. Toraya, K. Suto, Y. Morimoto, and N. Yasuoka, Structure 7, 997–1008 (1999).
10.1016/S0969-2126(99)80126-9
CAS PubMed Web of Science® Google Scholar
71 M. D. Sintchak, G. Arjara, B. A. Kellogg, J. Stubbe, and C. L. Drennan, Nat. Struct. Biol. 9, 293–300 (2002).
10.1038/nsb774
CAS PubMed Web of Science® Google Scholar
72 W. Buckel, C. Kratky, and B. T. Golding, Chem. Eur. J. 12, 352–362 (2006).
10.1002/chem.200501074
CAS Web of Science® Google Scholar
73 S. Gschösser, R. B. Hannak, R. Konrat, K. Gruber, C. Mikl, C. Kratky, and B. Kräutler, Chem. Eur. J. 11, 81–93 (2005).
10.1002/chem.200400701
CAS Web of Science® Google Scholar
74 M. Fukuoka, Y. Nakanishi, R. B. Hannak, B. Kräutler, and T. Toraya, FEBS J. 272, 4787–4796 (2005).
10.1111/j.1742-4658.2005.04892.x
CAS PubMed Web of Science® Google Scholar
75 K. Gruber and C. Kratky, Curr. Opin. Chem. Biol. 6, 598–603 (2002).
10.1016/S1367-5931(02)00368-X
CAS PubMed Web of Science® Google Scholar
76 T. Toraya, Chem. Rev. 103, 2095–2127 (2003).
10.1021/cr020428b
CAS PubMed Web of Science® Google Scholar
77 R. Banerjee, Chem. Rev. 103, 2083–2094 (2003).
10.1021/cr0204395
CAS PubMed Web of Science® Google Scholar
78 W. Buckel and B. T. Golding, Chem. Soc. Rev. 25, 329–337 (1996).
10.1039/cs9962500329
CAS Web of Science® Google Scholar
79 E. N. G. Marsh, and C. L. Drennan, Curr. Opin. Chem. Biol. 5, 499–505 (2001).
10.1016/S1367-5931(00)00238-6
CAS PubMed Web of Science® Google Scholar
80 K. Gruber, R. Reitzer, and C. Kratky, Angew. Chem. Int. Ed. 40, 3377–3380 (2001).
10.1002/1521-3773(20010917)40:18<3377::AID-ANIE3377>3.0.CO;2-8
CAS PubMed Web of Science® Google Scholar
81 K. Burkhardt, N. Philippon, and J. A. Robinson, in B. Kräutler, A. Arigoni, and B. T. Golding, eds., Vitamin B₁₂ and B₁₂-Proteins, Wiley-VCH, Weinheim, 1998, pp. 265–271.
Web of Science® Google Scholar
82 P. A. Frey, A. D. Hegeman, and G. H. Reed, Chem. Rev. 106, 3302–3316 (2006).
10.1021/cr050292s
CAS PubMed Web of Science® Google Scholar
83 P. A. Frey and O. T. Magnusson, Chem. Rev. 103, 2129–2148 (2003).
10.1021/cr020422m
CAS PubMed Web of Science® Google Scholar
84 A. Abend, R. Nitsche, V. Bandarian, E. Stupperich, and J. Retey, Angew. Chem. Int. Ed. 37, 625–627 (1998).
10.1002/(SICI)1521-3773(19980316)37:5<625::AID-ANIE625>3.0.CO;2-4
CAS Web of Science® Google Scholar
85 C. B. Grissom, Chem. Rev. 95, 3–24 (1995).
10.1021/cr00033a001
CAS Web of Science® Google Scholar
86 J. Stubbe, D. G. Nocera, C. S. Yee, and M. C. Y. Chang, Chem. Rev. 103, 2167–2201 (2003).
10.1021/cr020421u
CAS PubMed Web of Science® Google Scholar
87 J. Stubbe and W. A. van der Donk, Chem. Rev. 98, 705–762 (1998).
10.1021/cr9400875
CAS PubMed Web of Science® Google Scholar
88 A. Nahvi, N. Sudarsan, M. S. Ebert, X. Zou, K. L. Brown, and R. R. Breaker, Chem. Biol. 9, 1043–1049 (2002).
10.1016/S1074-5521(02)00224-7
CAS PubMed Web of Science® Google Scholar
89 A. Nahvi, J. E. Barrick, and R. R. Breaker, Nucl. Acids Res. 32, 143–150 (2004).
10.1093/nar/gkh167
CAS PubMed Web of Science® Google Scholar
90 W. C. Winkler and R. R. Breaker, Ann. Rev. Microbiol. 59, 487–517 (2005).
10.1146/annurev.micro.59.030804.121336
CAS PubMed Web of Science® Google Scholar
91 S. Gschösser, K. Gruber, C. Kratky, C. Eichmüller, and B. Kräutler, Angew. Chem. Int. Ed. 44, 2284–2288 (2005).
10.1002/anie.200462085
CAS PubMed Web of Science® Google Scholar
92 S. Gschösser and B. Kräutler, Chem. Eur. J. 14, 3605–3619 (2008).
10.1002/chem.200701365
CAS PubMed Web of Science® Google Scholar
93 M. Fasching, H. Perschinka, C. Eichmüller, S. Gschösser, and B. Kräutler, Chem. Biodiv. 2, 178–197 (2005).
10.1002/cbdv.200590001
CAS PubMed Web of Science® Google Scholar
94 G. F. Joyce, Nature 418, 214–221 (2002).
10.1038/418214a
CAS PubMed Web of Science® Google Scholar
95 J. Stubbe, Curr. Opin. Struct. Biol. 10, 731–736 (2000).
10.1016/S0959-440X(00)00153-6
CAS PubMed Web of Science® Google Scholar

Forfurther reading

Citing Literature

Encyclopedia of Catalysis

Browse other articles of this reference work: