METAL IONS INBIOLOGICAL SYSTEM S

Astrid SigelHelmut Sigel

VOLUME 39

PREFACE TO THE SERIES

iii

PREFACE TO VOLUME 39

v

IN MEMORIAM OF PROFESSOR ROBERT C . BRAY

vii

CONTRIBUTORS

xxiii

CONTENTS OF PREVIOUS VOLUMES

xxvii

HANDBOOK ON TOXICITY OF INORGANIC COMPOUNDS

lixHANDBOOK ON METALS IN CLINICAL AND ANALYTICAL

CHEMISTRY

lix

HANDBOOK ON METALLOPROTEINS

lix

Chapter 1THE BIOGEOCHEMISTRY OF MOLYBDENUM AN D

TUNGSTEN

1Edward I. Stiefel1. Introduction

2

2. Molybdenum and Tungsten in the Environment

3

3. The Nitrogen Cycle

7

4. Sulfur Metabolism and the Sulfur Cycle

1 1

5. Carbon Metabolism

1 7

6. Arsenic, Selenium, and Chlorine Metabolism

19

7. Conclusion

21

Acknowledgment

21

Abbreviations

22

References

23

Chapter 2

TRANSPORT, HOMEOSTASIS, REGULATION, AND BINDIN G

OF MOLYBDATE AND TUNGSTATE TO PROTEINS

31Richard N. Pau and David M. Lawson1. Introduction

32

2. Competition with Iron(III)

34

3. Transport Systems

39

4. Cytoplasmic Molybdate-Binding Proteins

49

5. Conclusions

65Acknowledgments

67Abbreviations and Definitions

67References

68

Chapter 3MOLYBDENUM NITROGENASES : A CRYSTALLOGRAPHI CAND MECHANISTIC VIEW

75David M. Lawson and Barry E. Smith1. Introduction

762. The Nitrogenases

773. The Molybdenum-Iron Protein

81

4. The Iron Protein

875. Mechanistic Studies

906. The Nitrogenase Complex

947. The Active Site

98

8. Conclusions

109Acknowledgments

110

Abbreviations and Definitions

110References

111

Chapter 4

CHEMICAL DINITROGEN FIXATION BY MOLYBDENU M

AND TUNGSTEN COMPLEXES : INSIGHTS FRO MCOORDINATION CHEMISTRY

121

Masanobu Hidai and Yasushi Mizobe1. Introduction

1222. Preparation and Structures of Dinitrogen Complexes

124

3. Reactions of Coordinated Dinitrogen

130

4. Conclusions

154

Abbreviations

155References

15 5

Chapter 5BIOSYNTHESIS OF THE NITROGENASE IRON-MOLYBDENUM-COFACTOR FROM AZOTOBACTERVINELANDII

16 3

Jeverson Frazzon and Dennis R . Dean1. Introduction

164

2. Biochemical Genetic Analysis of FeMo Cofactor Biosynthesis 167

3. A General Model for FeMo Cofactor Biosynthesis

169

4. Mobilization of Iron and Sulfur

17 0

5. NifB Cofactor

17 1

6. The NifEN Complex

17 5

7. Homocitrate Formation and Molybdenum Insertion

17 6

8. Role of Intermediate Carriers in FeMo Cofactor Biosynthesis 17 9

9. Role of the Iron Protein in Cofactor Assembly

18 1

10. Summary and Future Prospects

18 2

Acknowledgments

18 3

Abbreviations

18 3

References

18 3

Chapter 6MOLYBDENUM ENZYMES CONTAINING TH EPYRANOPTERIN COFACTOR : AN OVERVIEW

18 7

Russ Hille1. Introduction

18 8

2. Classification of the Mononuclear Molybdenum Enzymes

195

3. Consideration of Selected Enzymes Not Covered in Othe rChapters

2054. Mechanistic Considerations

211

5. Concluding Remarks

218

Acknowledgment

219

Abbreviations

219

References

219

Chapter 7THE MOLYBDENUM AND TUNGSTEN COFACTORS :A CRYSTALLOGRAPHIC VIEW

227Holger Dobbek and Robert Hube r

1. Introduction

2282. Structure of the Mo/W Cofactor

2293. Moco-Containing Enzyme Families

2324. Limitations of a Crystallographic Model

256Acknowledgments

258Abbreviations and Definitions

259References

260

Chapter 8MODELS FOR THE PYRANOPTERIN-CONTAININ GMOLYBDENUM AND TUNGSTEN COFACTORS

265Berthold Fischer and Sharon J. Nieter Burgmaye r

1. Introduction

2662. Early Models

2723. Model Complexes of 1,2-Ene-Dithiolates

2784. Metal Complexes of Pterins

2875. Models with All Three Redox Sites

2956. Conclusion

303Acknowledgments

304Abbreviations

304References

305

Chapter 9BIOSYNTHESIS AND MOLECULAR BIOLOGY OF TH EMOLYBDENUM COFACTOR (Moco)

317Ralf R. Mendel and Gunter Schwarz1. Introduction

3182. Genetics of the Molybdenum Cofactor

3223. Biosynthesis of the Molybdenum Cofactor

3244. Regulation of Molybdenum Cofactor Synthesis

3565. Conclusions

358Acknowledgments

359Abbreviations

359

References

359

Chapter 10MOLYBDENUM IN NITRATE REDUCTASE AND NITRIT EOXIDOREDUCTASE

369Peter M. H. Kroneck and Dietmar J. Abt1. Introduction

3702. Bacterial Respiratory Chains, Metalloenzymes, an d

Bioenergetics

3733. Nitrate Reductase

3794. Nitrite Oxidoreductase

3915. Environmental Aspects and Biosensors

394Acknowledgments

395Abbreviations and Definitions

395References

396

Chapter 1 1THE MOLYBDENUM-CONTAINING HYDROXYLASES OFNICOTINATE, ISONICOTINATE, AND NICOTINE

405Jan R. Andreesen and Susanne Fetzner1. Introduction

4062. Hydroxylations of Nicotinate and Derivatives

4073. Catabolism of Isonicotinate and Derivatives

4154. Nicotine Catabolism: Enzymes and Genes Involved in

Aerobic Transformations

4185. Biotechnological Potentials and Medical Implications

4216. Conclusions

423Acknowledgments

423Abbreviations

423References

424

Chapter 1 2THE MOLYBDENUM-CONTAINING XANTHIN EOXIDOREDUCTASES AND PICOLINATEDEHYDROGENASES

431Emil F. Pai and Takeshi Nishino

1. Introduction

4322. Xanthine Dehydrogenase/Xanthine Oxidase

435

3. Picolinate Dehydrogenase

4474. Conclusions

448Acknowledgments

449Abbreviations

449References

449

Chapter 1 3ENZYMES OF THE XANTHINE OXIDASE FAMILY : THEROLE OF MOLYBDENUM

455David J. Lowe1. Introduction

4562. The Reactions Catalyzed

4583. Spectroscopic Investigations

4624. Kinetic Studies

4695. Theoretical Calculations

4706. Discussion

4727. Conclusions

475Acknowledgment

475Abbreviations

475References

476

Chapter 14THE MOLYBDENUM-CONTAINING HYDROXYLASES O FQUINOLINE, ISOQUINOLINE, AND QUINALDINE

481Reinhard Kappl, Jurgen Hüttermann, and Susanne Fetzne r1. Introduction

4822. Biochemical and Genetic Characterization

4833. Structural Features of Related Enzymes

4944. EPR and ENDOR Characterization of Redox Centers

4975. Conclusions

530Acknowledgments

530Abbreviations

530References

531

Chapter 15MOLYBDENUM ENZYMES IN REACTIONS INVOLVINGALDEHYDES AND ACIDS

539Maria Jodo Romdo, Carlos A . Cunha, Carlos D . Brondino, and

Jose J. G. Moura1. Introduction

5402. Enzymes of the Xanthine Oxidase Family

5413. Enzymes of the Aldehyde Oxidoreductase Family

5594. Conclusions

565Acknowledgments

566Abbreviations

566References

567

Chapter 16MOLYBDENUM AND TUNGSTEN ENZYMES IN C 1METABOLISM

57 1Julia A. Vorholt and Rudolf K. Thauer

1. Introduction

5722. Formate Dehydrogenase

5753. Formylmethanofuran Dehydrogenase

5874. Carbon Monoxide Dehydrogenase

5955. Formaldehyde Dehydrogenases

5986. Conclusions

601Acknowledgments

602Abbreviations and Definitions

602References

603

Chapter 17MOLYBDENUM ENZYMES AND SULFUR METABOLISM

621John H. Enemark and Michele Mader Cospe r

1. Introduction

6222. Sulfite Oxidase

6233. Dimethyl Sulfoxide Reductase

6354. Biotin Sulfoxide Reductase

6425. Polysulfide Reductase

6446. Conclusions

645Acknowledgments

645Abbreviations and Definitions

646

References

647

Chapter 18COMPARISON OF SELENIUM-CONTAININGMOLYBDOENZYMES

655Vadim, N. Gladyshe v1. Introduction

6562. Overview of Selenium-Containing Molybdoenzymes

6583. Incorporation of Selenium into Molybdoenzymes

6624. Selenium Versus Sulfur in Catalysis

6645. Evolution of Selenocysteine-Containing Molybdoenzymes

6676. Conclusions

668Acknowledgments

669Abbreviations

669References

670

Chapter 1 9TUNGSTEN-DEPENDENT ALDEHYDE OXIDOREDUCTASE :A NEW FAMILY OF ENZYMES CONTAINING TH EPTERIN COFACTOR

673Roopali Roy and Michael W. W. Adam s1. Introduction

6742. Classification of Tungstoenzymes

6773. Aldehyde Ferredoxin Oxidoreductase

6804. Carboxylic Acid Reductase and Aldehyde Dehydrogenase

6855. Formaldehyde Ferredoxin Oxidoreductase

6876. Glyceraldehyde-3-Phosphate Ferredoxin Oxidoreductase

6907. Hypothetical Tungstoenzymes-WOR4 and WOR5

6918. Tungsten Versus Molybdenum in the AOR Family

6929. Conclusions

693Acknowledgment

694Abbreviations

694References

695

Chapter 20TUNGSTEN-SUBSTITUTED MOLYBDENUM ENZYMES

699C . David Garner and Lisa J. Stewart1 . Introduction

700

2. Molybdenum and Tungsten Chemistry : Similarities andDifferences

7013. Molybdenum and Tungsten Geochemistry and Link t o

Bioavailability

7044. Early Attempts to Substitute Tungsten for Molybdenum

7055. Tungsten-Substituted Molybdenum Enzymes

7076. Molybdenum-Substituted Tungsten Acetylene Hydratase

7197. Conclusions

720Abbreviations

72 1References

722

Chapter 2 1MOLYBDENUM METABOLISM AND REQUIREMENTS I NHUMANS

72 7Judith R. Turnlund1. Introduction

7282. Essentiality of Molybdenum in Humans

7283. Dietary Intake and Bioavailability of Molybdenum

7294. Molybdenum Deficiency and Toxicity

7315. Stable Isotope Studies of Molybdenum Metabolism

7336. Conclusions

736Abbreviations

736References

736

Chapter 22METABOLISM AND TOXICITY OF TUNGSTEN IN HUMAN SAND ANIMALS

741Florence Lagarde and Maurice Leroy

1. Introduction

7422. Metabolism of Tungsten

7423. Toxicity of Tungsten

7524. Conclusions

755Abbreviations and Definitions

755References

756

SUBJECT INDEX

761