Nitrogen Fixation at the Millennium

Leigh, G.J.

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Table of contents
  • Cover
  • Contentsvii
  • Forewordv
  • Chapter 1. Nitrogen Fixation– A General Overview1
  • 1. Introduction1
  • 2. N2-fixing organisms4
  • 3. Nitrogenases6
  • 4. Nitrogen-fixation (nif) genes17
  • 5. Chemical systems22
  • 6. Summary and outlook26
  • 7. References27
  • Chapter 2. Nitrogenase Structure35
  • 1. Introduction35
  • 2. The MoFe protein36
  • 3. The Fe protein49
  • 4. Nitrogenase complexes55
  • 5. Future directions67
  • 6. Acknowledgements68
  • 7. References68
  • Chapter 3. Spectroscopy of Nitrogenase73
  • 1. Introduction73
  • 2. Resting state studies75
  • 3. Oxidized and reduced states84
  • 4. Intermediate states89
  • 5. References94
  • Chapter 4. The Gene Products of the nif Regulon101
  • 1. Introduction101
  • 2. Organization of nitrogen fixation (nif) genes in Azotobacter vinelandii and Klebsiella pneumoniae103
  • 3. Structural genes for dinitrogenase and dinitrogenase reductase104
  • 4. Genes products required for the biosynthesis of the iron-molybdenum cofactor (FeMo–co) of nitro108
  • 5. Other nif-gene products121
  • 6. Non-nif protein requirements127
  • 7. Future studies129
  • 8. Acknowledgements129
  • 9. References130
  • Chapter 5. Use of Short-Chain Alkynes to Locate the Nitrogenase Catalytic Site137
  • 1. Introduction137
  • 2. Background137
  • 3. Insight into the effects of amino acid substitutions around the FeMo-cofactor on substrate reduct142
  • 4. Rationale and strategy for isolation of an acetylene-resistant MoFe protein145
  • 5. Expanding the capacity of nitrogenase to reduce longer-chain alkynes148
  • 6. Acetylene interaction with the MoFe protein in the resting state150
  • 7. Summary and outlook151
  • 8. Acknowledgements152
  • 9. References152
  • Chapter 6. Regulation of Mo Nitrogenases155
  • 1. Introduction155
  • 2. Components of the nif-promoter region156
  • 3. Mechanisms of transcriptional activation157
  • 4. Trans-Acting factors influencing nitrogenase expression158
  • 5. Nitrogen-sensing161
  • 6. Involvement of PII in control of NifA activity in other proteobacteria163
  • 7. Concluding remarks164
  • 8. Acknowledgements164
  • 9. References164
  • Chapter 7. Actinorhizal symbioses167
  • 1. Preface167
  • 2. Microsymbionts167
  • 3. Macrosymbionts171
  • 4. Infection process and nodule development171
  • 5. Mature actinorhizal nodules174
  • 6. Nodule physiology178
  • 7. Phylogeny180
  • 8. Outlook183
  • 9. References183
  • Chapter 8. Alternative Nitrogenases191
  • 1. Introduction191
  • 2. Organization of nitrogen fixation genes (nif, vnf and anf genes)193
  • 3. Regulation of alternative nitrogenase systems200
  • 4. Protein size, subunit structure and features deduced from protein sequences of alternative nitrog206
  • 5. Structure and spectroscopic properties of metallosulfur clusters207
  • 6. Biosynthesis of FeVco and FeFeco211
  • 7. Catalytic features of alternative nitrogenases212
  • 8. Relevance of alternative nitrogenases for diazotrophic bacteria under natural conditions216
  • 9. References217
  • Chapter 9. Advances Towards the Mechanism of Nitrogenases223
  • 1. Introduction to biological nitrogen fixation223
  • 2. The mechanism of biological nitrogen fixation224
  • 3. The binding of dinitrogen232
  • 4. The protonation of dinitrogen242
  • 5. Dinitrogen reactivity on Fe–S-clusters252
  • 6. Future challenges257
  • 7. References257
  • Chapter 10. A Novel Nitrogenase Superoxide-Dependent Nitrogen Fixation263
  • 1. Introduction263
  • 2. Superoxide-dependent nitrogen fixation266
  • 3. Components of superoxide-dependent nitrogenase267
  • 4. Reduction of N2 and other reactions catalyzed271
  • 5. Genetics286
  • 6. Conclusions and perspectives292
  • 7. References295
  • Chapter 11. Dinitrogen Chemistry299
  • 1. Introduction299
  • 2. Properties of dinitrogen300
  • 3. Industrial nitrogen fixation304
  • 4. Metals in biological nitrogen fixation307
  • 5. Dinitrogen complexes308
  • 6. Reactions of dinitrogen311
  • 7. The new generations of dinitrogen complexes314
  • 8. Reactions of coordinated dinitrogen319
  • 9. Conclusions326
  • 10. References327
  • Chapter 12. Chemical Models for Nitrogenase333
  • 1. Introduction333
  • 2. The structures of the clusters of nitrogenase336
  • 3. Theoretical studies339
  • 4. Synthesis of models for the single four-iron cluster341
  • 5. Synthesis of models for FeMoco and cofactors of the alternative nitrogenases341
  • 6. Synthesis of structural models for the P-clusters345
  • 7. Reactivity of Fe–S-clusters including FeMoco itself346
  • 8. Metal complexes with sulfur ligands that relate to the function of FeMoco348
  • 9. Conclusions and future prospects350
  • 10. References351
  • Chapter 13. Quantification of Nitrogen Fixation357
  • 1. Introduction357
  • 2. Overview of approaches used in the past357
  • 3. Detailed evaluation of methods for the new millenium363
  • 4. Conclusions385
  • 5. References386
  • Chapter 14. Nitrogen Fixation and Agricultural Practice391
  • 1. Introduction391
  • 2. The macrosymbiont392
  • 3. The microsymbiont399
  • 4. Challenges for research and development408
  • 5. Conclusions410
  • 6. References410
  • Chapter 15. Nitrogen Fixation in Rice421
  • 1. Introduction421
  • 2. Autochthonous (indigenous) BNF systems423
  • 3. Allochthonous (exogenous) BNF systems425
  • 4. in planta (endogenous) BNF systems427
  • 5. Concluding remarks439
  • 6. References439
  • Index447
Book details
  • Vendor Elsevier S & T
  • SKU 9780444509659
  • ISBN-13 9780080537573
  • Author Leigh, G.J.
  • Category Science
  • Subject Botany

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The turn of the millennium from the twentieth to the twenty-first century provides an occasion to review our understanding of a biological process, biological nitrogen fixation, that is of prime importance for the continued survival of mankind. This process has provided a basis for maintaining soil fertility since the beginning of organised agriculture, yet its very existence was confirmed only just over a century ago. In the intervening years, an enormous intellectual effort has dispersed much of the mystery surrounding biological nitrogen fixation. Biological fixation is widely exploited in agriculture, as are nitrogen fertilisers prepared for the last hundred years under extreme conditions of temperature and pressure. However, despite all our efforts, the fundamental nature of the reactions involved at the heart of the biological process remain unknown.


This book aims to describe what we have learned in the last one hundred years or so about biological nitrogen fixation, about what its chemistry appears to be, and how it is applied in agriculture. This ambitious objective has not been attempted recently. It is aimed at students and those who wish to enter these very challenging areas of research, and who need to learn the state of the art at the turn of the millennium.


The authors are all acknowledged world experts in their fields. They have prepared concise, well referenced and authoritative accounts of their subjects. This book provides a unique summary of the current state of knowledge that will be indispensable to all students and researchers, actual and potential, interested in biological nitrogen fixation.