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The Biochemistry of Nitrogenase: Mechanism, Diversity, and Regulation

At a Glance

Title: The Biochemistry of Nitrogenase: Mechanism, Diversity, and Regulation

Total Categories: 7

Category Stats

  • Nitrogen Fixation Fundamentals: 5 flashcards, 10 questions
  • MoFe Nitrogenase Structure: 7 flashcards, 14 questions
  • Nitrogenase Reaction Mechanism: 13 flashcards, 26 questions
  • Alternative Nitrogenases: 7 flashcards, 14 questions
  • Regulation and Inhibition: 3 flashcards, 6 questions
  • Nitrogenase Evolution and Diversity: 9 flashcards, 18 questions
  • Assay Methods: 2 flashcards, 4 questions

Total Stats

  • Total Flashcards: 46
  • True/False Questions: 46
  • Multiple Choice Questions: 46
  • Total Questions: 92

Instructions

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Study Guide: The Biochemistry of Nitrogenase: Mechanism, Diversity, and Regulation

Study Guide: The Biochemistry of Nitrogenase: Mechanism, Diversity, and Regulation

Nitrogen Fixation Fundamentals

Nitrogenases are a class of enzymes produced by certain bacteria, such as cyanobacteria and rhizobacteria, that catalyze the reduction of atmospheric nitrogen to ammonia.

Answer: True

Nitrogenases are enzymes synthesized by specific bacteria, including cyanobacteria and rhizobacteria, which are responsible for catalyzing the reduction of atmospheric nitrogen (N₂) into ammonia (NH₃).

Related Concepts:

  • What are nitrogenases and what is their primary biological function?: Nitrogenases are a class of enzymes produced by certain bacteria, including cyanobacteria and rhizobacteria. Their primary biological function is to catalyze the reduction of atmospheric nitrogen (N₂) to ammonia (NH₃), a crucial step in the process of nitrogen fixation, which is essential for the biosynthesis of molecules like nucleotides and amino acids in all forms of life.

Nitrogen fixation is a vital process for all forms of life because nitrogen is an essential element for the biosynthesis of nucleotides and amino acids.

Answer: True

Nitrogen fixation is indispensable for all life forms, as nitrogen is a fundamental component required for the biosynthesis of critical biological macromolecules like nucleotides and amino acids.

Related Concepts:

  • What is the significance of nitrogen fixation for living organisms?: Nitrogen fixation is a vital process for all forms of life because nitrogen is an essential element required for the biosynthesis of fundamental biological molecules, such as nucleotides (the building blocks of DNA and RNA) and amino acids (the building blocks of proteins), which are necessary for the creation of plants, animals, and other organisms.

Nitrogenase acts as a catalyst to significantly reduce the high activation energy required for the thermodynamically favorable formation of ammonia from nitrogen and hydrogen.

Answer: True

Nitrogenase functions as a catalyst, effectively lowering the substantial activation energy barrier for the synthesis of ammonia from nitrogen and hydrogen, a reaction that is thermodynamically favorable but kinetically slow.

Related Concepts:

  • How do nitrogenases overcome the high activation energy of ammonia formation from nitrogen and hydrogen?: Although the formation of ammonia from molecular hydrogen and nitrogen is thermodynamically favorable (exothermic), it has a very high activation energy. Nitrogenase acts as a catalyst, significantly reducing this energy barrier, thereby allowing the reaction to occur efficiently at ambient biological temperatures.

*Azospirillum* and *Frankia* are examples of free-living bacteria that synthesize nitrogenase.

Answer: False

*Azospirillum* and *Frankia* are examples of *mutualistic, symbiotic* bacteria that synthesize nitrogenase, not free-living ones. Free-living examples include cyanobacteria and *Azotobacter*.

Related Concepts:

  • Name some examples of mutualistic bacteria that synthesize nitrogenase and their associated plants.: Examples of mutualistic, symbiotic bacteria that synthesize nitrogenase include *Rhizobium*, which is associated with legumes; *Azospirillum*, associated with grasses; and *Frankia*, which forms symbiotic relationships with actinorhizal plants.
  • Name some examples of free-living bacteria that synthesize nitrogenase.: Examples of free-living, non-symbiotic bacteria that synthesize nitrogenase include cyanobacteria (also known as blue-green algae), green sulfur bacteria, and species of *Azotobacter*.

*Rhizobium* is a mutualistic bacterium that synthesizes nitrogenase and forms symbiotic relationships with legumes.

Answer: True

*Rhizobium* is a well-known mutualistic bacterium that produces nitrogenase and establishes symbiotic associations with leguminous plants, facilitating nitrogen fixation.

Related Concepts:

  • Name some examples of mutualistic bacteria that synthesize nitrogenase and their associated plants.: Examples of mutualistic, symbiotic bacteria that synthesize nitrogenase include *Rhizobium*, which is associated with legumes; *Azospirillum*, associated with grasses; and *Frankia*, which forms symbiotic relationships with actinorhizal plants.

What is the primary biological function of nitrogenases?

Answer: To catalyze the reduction of atmospheric nitrogen (N₂) to ammonia (NH₃).

The fundamental biological role of nitrogenases is to catalyze the reduction of atmospheric dinitrogen (N₂) into ammonia (NH₃), making nitrogen available for biological processes.

Related Concepts:

  • What are nitrogenases and what is their primary biological function?: Nitrogenases are a class of enzymes produced by certain bacteria, including cyanobacteria and rhizobacteria. Their primary biological function is to catalyze the reduction of atmospheric nitrogen (N₂) to ammonia (NH₃), a crucial step in the process of nitrogen fixation, which is essential for the biosynthesis of molecules like nucleotides and amino acids in all forms of life.

Why is nitrogen fixation considered a vital process for all forms of life?

Answer: It is essential for the biosynthesis of fundamental biological molecules like nucleotides and amino acids.

Nitrogen fixation is crucial because it converts atmospheric nitrogen into a usable form, which is then incorporated into essential biological molecules such as nucleotides and amino acids, vital for all life.

Related Concepts:

  • What is the significance of nitrogen fixation for living organisms?: Nitrogen fixation is a vital process for all forms of life because nitrogen is an essential element required for the biosynthesis of fundamental biological molecules, such as nucleotides (the building blocks of DNA and RNA) and amino acids (the building blocks of proteins), which are necessary for the creation of plants, animals, and other organisms.

How do nitrogenases facilitate the formation of ammonia from nitrogen and hydrogen?

Answer: By acting as a catalyst to significantly reduce the high activation energy barrier.

Nitrogenases function as catalysts, effectively lowering the substantial activation energy barrier for the thermodynamically favorable, but kinetically slow, reaction of ammonia formation from nitrogen and hydrogen.

Related Concepts:

  • How do nitrogenases overcome the high activation energy of ammonia formation from nitrogen and hydrogen?: Although the formation of ammonia from molecular hydrogen and nitrogen is thermodynamically favorable (exothermic), it has a very high activation energy. Nitrogenase acts as a catalyst, significantly reducing this energy barrier, thereby allowing the reaction to occur efficiently at ambient biological temperatures.

Which of the following is an example of a free-living bacterium that synthesizes nitrogenase?

Answer: Azotobacter

*Azotobacter* is an example of a free-living, non-symbiotic bacterium capable of synthesizing nitrogenase for atmospheric nitrogen fixation.

Related Concepts:

  • Name some examples of free-living bacteria that synthesize nitrogenase.: Examples of free-living, non-symbiotic bacteria that synthesize nitrogenase include cyanobacteria (also known as blue-green algae), green sulfur bacteria, and species of *Azotobacter*.

Which mutualistic bacterium is associated with legumes and synthesizes nitrogenase?

Answer: Rhizobium

*Rhizobium* is a mutualistic bacterium that forms symbiotic relationships with legumes, residing in root nodules where it synthesizes nitrogenase to fix atmospheric nitrogen.

Related Concepts:

  • Name some examples of mutualistic bacteria that synthesize nitrogenase and their associated plants.: Examples of mutualistic, symbiotic bacteria that synthesize nitrogenase include *Rhizobium*, which is associated with legumes; *Azospirillum*, associated with grasses; and *Frankia*, which forms symbiotic relationships with actinorhizal plants.

MoFe Nitrogenase Structure

The Fe-only protein component of nitrogenase is a heterotetramer, while the MoFe protein is a homodimer.

Answer: False

The Fe-only protein (reductase) is a homodimer, whereas the MoFe protein is a heterotetramer, composed of two alpha and two beta subunits.

Related Concepts:

  • What are the two main components that typically constitute a nitrogenase assembly?: A typical nitrogenase assembly consists of two main components: the homodimeric Fe-only protein, also known as the reductase, which possesses high reducing power and supplies electrons; and the heterotetrameric MoFe protein, which utilizes these electrons to reduce N₂ to NH₃.
  • What are the structural characteristics of the MoFe protein in nitrogenase?: The MoFe protein is a heterotetramer, meaning it is composed of four subunits: two α subunits and two β subunits, with an approximate mass of 240-250 kDa. It contains two P-clusters, located at the interface between the α and β subunits, and two FeMo cofactors, situated within the α subunits.

The FeMo cofactor is a crucial component located within the alpha subunits of the MoFe protein, serving as the active site for nitrogen fixation.

Answer: True

The FeMo cofactor is indeed a vital part of the nitrogenase enzyme, situated within the alpha subunits of the MoFe protein, and functions as the active site where atmospheric nitrogen is reduced to ammonia.

Related Concepts:

  • What is the role of the FeMo cofactor in nitrogenase?: The FeMo cofactor is a crucial component within the nitrogenase enzyme, specifically located within the α subunits of the MoFe protein. It serves as the active site where nitrogen fixation occurs, with the N₂ molecule binding in its central cavity for reduction to ammonia.
  • What are the structural characteristics of the MoFe protein in nitrogenase?: The MoFe protein is a heterotetramer, meaning it is composed of four subunits: two α subunits and two β subunits, with an approximate mass of 240-250 kDa. It contains two P-clusters, located at the interface between the α and β subunits, and two FeMo cofactors, situated within the α subunits.

The reductase (Fe protein) is a monomeric protein containing two [Fe₄S₄] clusters and directly reduces N₂ to NH₃.

Answer: False

The reductase (Fe protein) is a dimer composed of two identical subunits, containing one [Fe₄S₄] cluster, and its role is to transfer electrons from a reducing agent to the MoFe protein, not to directly reduce N₂ to NH₃.

Related Concepts:

  • Describe the structure and function of the reductase, also known as the Fe protein or dinitrogenase reductase (NifH).: The reductase, or Fe protein (NifH), is a dimer composed of two identical subunits, with a mass of approximately 60-64 kDa. It contains one [Fe₄S₄] cluster. Its function is to transfer electrons from a reducing agent, such as ferredoxin or flavodoxin, to the nitrogenase protein (MoFe protein).

The MoFe protein is a homodimer with a mass of approximately 60-64 kDa, containing only P-clusters.

Answer: False

The MoFe protein is a heterotetramer with an approximate mass of 240-250 kDa, and it contains both P-clusters and FeMo cofactors.

Related Concepts:

  • What are the structural characteristics of the MoFe protein in nitrogenase?: The MoFe protein is a heterotetramer, meaning it is composed of four subunits: two α subunits and two β subunits, with an approximate mass of 240-250 kDa. It contains two P-clusters, located at the interface between the α and β subunits, and two FeMo cofactors, situated within the α subunits.

Recent evidence suggests that the oxidation state of Molybdenum (Mo) in MoFe nitrogenases is Mo(III), rather than the previously believed Mo(V).

Answer: True

Recent research indicates that the oxidation state of molybdenum within the MoFe nitrogenase is Mo(III), a revision from the earlier understanding of Mo(V).

Related Concepts:

  • What is the current understanding of the oxidation state of Molybdenum (Mo) in MoFe nitrogenases?: The oxidation state of Molybdenum (Mo) in MoFe nitrogenases was previously believed to be Mo(V), but more recent evidence suggests it is Mo(III). This is notable because molybdenum in many other enzymes is typically found as fully oxidized Mo(VI) bound to molybdopterin.

The P-cluster within the MoFe protein has a core structure of (Fe₆S₆) and is linked to the protein by four histidine residues.

Answer: False

The P-cluster in the MoFe protein has a core structure of (Fe₈S₇) and is linked to the protein by six cysteine residues, not four histidine residues.

Related Concepts:

  • Detail the structure of the P-cluster within the MoFe protein.: The P-cluster within the MoFe protein has a core structure of (Fe₈S₇), which is formed by two [Fe₄S₃] cubes. These two cubes are interconnected by a central sulfur atom, and each P-cluster is further linked to the MoFe protein itself by six cysteine residues.

Each FeMo cofactor has the chemical formula (Fe₇MoS₉C) and is covalently attached to the alpha subunit through one cysteine and one histidine residue.

Answer: True

The FeMo cofactor is accurately described by the chemical formula (Fe₇MoS₉C) and is covalently linked to the alpha subunit of the MoFe protein via one cysteine and one histidine residue.

Related Concepts:

  • Describe the composition and attachment of the FeMo cofactor.: Each FeMo cofactor, with the chemical formula (Fe₇MoS₉C), is composed of two distinct clusters: [Fe₄S₃] and [MoFe₃S₃]. These two sub-clusters are linked together by three sulfide ions. The entire FeMo cofactor is covalently attached to the α subunit of the protein through one cysteine residue and one histidine residue.

Which two main components typically form a nitrogenase assembly?

Answer: The homodimeric Fe-only protein and the heterotetrameric MoFe protein.

A typical nitrogenase enzyme complex is composed of two primary components: the homodimeric Fe-only protein (reductase) and the heterotetrameric MoFe protein.

Related Concepts:

  • What are the two main components that typically constitute a nitrogenase assembly?: A typical nitrogenase assembly consists of two main components: the homodimeric Fe-only protein, also known as the reductase, which possesses high reducing power and supplies electrons; and the heterotetrameric MoFe protein, which utilizes these electrons to reduce N₂ to NH₃.

What is the primary role of the FeMo cofactor in the nitrogenase enzyme?

Answer: To serve as the active site where nitrogen fixation occurs, binding the N₂ molecule.

The FeMo cofactor functions as the active site within the MoFe protein where the dinitrogen molecule binds and is subsequently reduced to ammonia.

Related Concepts:

  • What is the role of the FeMo cofactor in nitrogenase?: The FeMo cofactor is a crucial component within the nitrogenase enzyme, specifically located within the α subunits of the MoFe protein. It serves as the active site where nitrogen fixation occurs, with the N₂ molecule binding in its central cavity for reduction to ammonia.

Which of the following accurately describes the reductase (Fe protein) component of nitrogenase?

Answer: It is a dimer composed of two identical subunits, containing one [Fe₄S₄] cluster.

The reductase, or Fe protein, is a homodimer consisting of two identical subunits, each containing a single [Fe₄S₄] cluster, and its role is to transfer electrons from a reducing agent to the MoFe protein.

Related Concepts:

  • Describe the structure and function of the reductase, also known as the Fe protein or dinitrogenase reductase (NifH).: The reductase, or Fe protein (NifH), is a dimer composed of two identical subunits, with a mass of approximately 60-64 kDa. It contains one [Fe₄S₄] cluster. Its function is to transfer electrons from a reducing agent, such as ferredoxin or flavodoxin, to the nitrogenase protein (MoFe protein).

Which of the following accurately describes the structural characteristics of the MoFe protein?

Answer: It is a heterotetramer composed of two alpha and two beta subunits, with a mass of 240-250 kDa.

The MoFe protein is a heterotetramer, comprising two alpha and two beta subunits, and has an approximate mass of 240-250 kDa.

Related Concepts:

  • What are the structural characteristics of the MoFe protein in nitrogenase?: The MoFe protein is a heterotetramer, meaning it is composed of four subunits: two α subunits and two β subunits, with an approximate mass of 240-250 kDa. It contains two P-clusters, located at the interface between the α and β subunits, and two FeMo cofactors, situated within the α subunits.

What is the currently suggested oxidation state of Molybdenum (Mo) in MoFe nitrogenases?

Answer: Mo(III)

Current evidence indicates that the oxidation state of molybdenum in MoFe nitrogenases is Mo(III), a revision from earlier assumptions.

Related Concepts:

  • What is the current understanding of the oxidation state of Molybdenum (Mo) in MoFe nitrogenases?: The oxidation state of Molybdenum (Mo) in MoFe nitrogenases was previously believed to be Mo(V), but more recent evidence suggests it is Mo(III). This is notable because molybdenum in many other enzymes is typically found as fully oxidized Mo(VI) bound to molybdopterin.

What is the core structure of the P-cluster within the MoFe protein?

Answer: (Fe₈S₇)

The P-cluster within the MoFe protein possesses a core structure of (Fe₈S₇), formed by two interconnected [Fe₄S₃] cubes.

Related Concepts:

  • Detail the structure of the P-cluster within the MoFe protein.: The P-cluster within the MoFe protein has a core structure of (Fe₈S₇), which is formed by two [Fe₄S₃] cubes. These two cubes are interconnected by a central sulfur atom, and each P-cluster is further linked to the MoFe protein itself by six cysteine residues.

How is the FeMo cofactor covalently attached to the alpha subunit of the MoFe protein?

Answer: Through one cysteine residue and one histidine residue.

The FeMo cofactor is covalently linked to the alpha subunit of the MoFe protein via a cysteine residue and a histidine residue.

Related Concepts:

  • Describe the composition and attachment of the FeMo cofactor.: Each FeMo cofactor, with the chemical formula (Fe₇MoS₉C), is composed of two distinct clusters: [Fe₄S₃] and [MoFe₃S₃]. These two sub-clusters are linked together by three sulfide ions. The entire FeMo cofactor is covalently attached to the α subunit of the protein through one cysteine residue and one histidine residue.

Nitrogenase Reaction Mechanism

The transfer of electrons by the Fe protein is powered by the binding and subsequent hydrolysis of adenosine triphosphate (ATP).

Answer: True

The energy required for electron transfer by the Fe protein is supplied through the binding and subsequent hydrolysis of ATP, which also induces conformational changes necessary for the interaction between the Fe and MoFe proteins.

Related Concepts:

  • How is the transfer of electrons by the Fe protein powered?: The transfer of electrons by the Fe protein requires an input of chemical energy, which is derived from the binding and subsequent hydrolysis of adenosine triphosphate (ATP). This ATP hydrolysis also induces a conformational change in the nitrogenase complex, bringing the Fe protein and MoFe protein closer together to facilitate electron transfer.
  • What role does MgATP binding play in the nitrogenase mechanism?: MgATP binding is a central event in the nitrogenase mechanism, as the hydrolysis of its terminal phosphate group provides the necessary energy to transfer electrons from the Fe protein to the MoFe protein, driving the reduction process.

Electrons flow directly from the Fe protein to the FeMo cofactors, bypassing the P-clusters entirely.

Answer: False

Electrons from the Fe protein first enter the MoFe protein at the P-clusters, and then are transferred from the P-clusters to the FeMo cofactors, meaning the P-clusters are not bypassed.

Related Concepts:

  • Trace the path of electrons through the nitrogenase complex.: Electrons originating from the Fe protein first enter the MoFe protein at the P-clusters. From the P-clusters, these electrons are then transferred to the FeMo cofactors, which are the ultimate sites where nitrogen fixation takes place.

The Lowe-Thorneley kinetic model describes the sequential addition of eight proton and electron equivalents during the reduction of nitrogen to ammonia.

Answer: True

The Lowe-Thorneley kinetic model precisely outlines the sequential transfer of eight proton and electron equivalents to the FeMo-cofactor, leading to the reduction of nitrogen to ammonia.

Related Concepts:

  • What is the Lowe-Thorneley kinetic model and what does it describe?: The Lowe-Thorneley (LT) kinetic model describes the sequential addition of proton and electron equivalents from Component II (dinitrogenase reductase) to the FeMo-cofactor of Component I (dinitrogenase) during the reduction of nitrogen to ammonia. Developed from kinetic measurements in the 1970s and 80s, it documents the eight correlated proton and electron transfers required for the reaction.
  • How many equivalents of protons and electrons are required for nitrogen reduction according to the Lowe-Thorneley model, and how does this compare to the balanced chemical reaction?: According to the Lowe-Thorneley model, nitrogen reduction requires 8 equivalents of protons and electrons. This is notably more than the 6 equivalents that would be predicted by the balanced chemical reaction for the conversion of N₂ to 2 NH₃.

The Lowe-Thorneley model requires 6 equivalents of protons and electrons for nitrogen reduction, which is fewer than predicted by the balanced chemical reaction.

Answer: False

The Lowe-Thorneley model specifies that 8 equivalents of protons and electrons are required for nitrogen reduction, which is *more* than the 6 equivalents predicted by the balanced chemical reaction.

Related Concepts:

  • How many equivalents of protons and electrons are required for nitrogen reduction according to the Lowe-Thorneley model, and how does this compare to the balanced chemical reaction?: According to the Lowe-Thorneley model, nitrogen reduction requires 8 equivalents of protons and electrons. This is notably more than the 6 equivalents that would be predicted by the balanced chemical reaction for the conversion of N₂ to 2 NH₃.

The E₀ intermediate in the Lowe-Thorneley model represents the resting state of the nitrogenase enzyme before the catalytic process begins.

Answer: True

The E₀ intermediate is defined as the inactive, resting state of the nitrogenase enzyme prior to the initiation of the nitrogen fixation catalytic cycle.

Related Concepts:

  • Describe the E₀ intermediate in the Lowe-Thorneley kinetic model.: The E₀ intermediate represents the resting state of the nitrogenase enzyme before the catalytic process of nitrogen fixation begins. Electron Paramagnetic Resonance (EPR) characterization indicates that this species has a spin of ³/₂.

The E₂ intermediate is proposed to contain the metal cluster in an oxidized state with two free protons.

Answer: False

The E₂ intermediate is proposed to contain the metal cluster in its *resting oxidation state*, with two added electrons stored as a bridging hydride and a proton bonded to a sulfur atom.

Related Concepts:

  • What is the proposed composition of the E₂ intermediate?: The E₂ intermediate is proposed to contain the metal cluster in its resting oxidation state, with two added electrons stored in a bridging hydride and an additional proton bonded to a sulfur atom. When isolated in mutated enzymes, the FeMo-cofactor in this state exhibits a high spin of ³/₂.

The E₄ intermediate, known as the Janus intermediate, is significant because it can either revert to the E₀ resting state or proceed with nitrogen binding.

Answer: True

The E₄ intermediate, or Janus intermediate, is a crucial branching point in the catalytic cycle, capable of either returning to the E₀ resting state or advancing to bind nitrogen and continue fixation.

Related Concepts:

  • What is the significance of the E₄ intermediate, also known as the Janus intermediate?: The E₄ intermediate, termed the Janus intermediate, is significant because it occurs after exactly half of the electron and proton transfers have taken place. At this stage, the intermediate can either revert back to the E₀ resting state or proceed with nitrogen binding to complete the catalytic cycle of nitrogen fixation.

The E₄ intermediate was first observed in a wild-type enzyme using X-ray crystallography, showing a single bridging hydride.

Answer: False

The E₄ intermediate was first observed using freeze-quench techniques with a *mutated* protein, not a wild-type enzyme, and ENDOR experiments revealed the presence of *two* bridging hydrides.

Related Concepts:

  • How was the E₄ intermediate first observed and characterized?: The E₄ intermediate was first observed using freeze-quench techniques with a mutated protein where a valine amino acid at residue 70 was replaced with isoleucine, which prevented substrate access to the FeMo-cofactor. EPR characterization of this isolated intermediate showed a new species with a spin of ½, and ENDOR experiments revealed the presence of two bridging hydrides between two iron centers.

The 'distal' and 'alternating' pathways are the two main hypotheses for the mechanism of N₂ fixation after the E₄ complex, differing in hydrogen addition sequence.

Answer: True

Following the E₄ intermediate, the 'distal' and 'alternating' pathways represent the primary mechanistic hypotheses for N₂ reduction, distinguished by their distinct sequences of hydrogen addition to the dinitrogen molecule.

Related Concepts:

  • What are the two main hypotheses for the mechanism of N₂ fixation after the E₄ complex?: After the E₄ complex, there are two main hypotheses for the exact pathway of nitrogen fixation: the 'distal' pathway and the 'alternating' pathway. These pathways differ in the sequence of hydrogen additions to the nitrogen molecule.
  • How do the 'distal' and 'alternating' pathways for N₂ fixation differ?: In the distal pathway, the terminal nitrogen atom of the N₂ molecule is hydrogenated first, leading to the release of ammonia, after which the nitrogen atom directly bound to the metal center is hydrogenated. In contrast, the alternating pathway involves adding one hydrogen to the terminal nitrogen, then one hydrogen to the metal-bound nitrogen, and this alternating pattern continues until ammonia is released.

In the distal pathway, hydrogen additions alternate between the terminal and metal-bound nitrogen atoms until ammonia is released.

Answer: False

In the distal pathway, the terminal nitrogen atom is hydrogenated first, leading to ammonia release, before the metal-bound nitrogen is hydrogenated. The alternating pathway involves alternating hydrogen additions.

Related Concepts:

  • How do the 'distal' and 'alternating' pathways for N₂ fixation differ?: In the distal pathway, the terminal nitrogen atom of the N₂ molecule is hydrogenated first, leading to the release of ammonia, after which the nitrogen atom directly bound to the metal center is hydrogenated. In contrast, the alternating pathway involves adding one hydrogen to the terminal nitrogen, then one hydrogen to the metal-bound nitrogen, and this alternating pattern continues until ammonia is released.

MgATP binding and its subsequent hydrolysis provide the necessary energy for electron transfer from the Fe protein to the MoFe protein.

Answer: True

The energy required for the crucial electron transfer from the Fe protein to the MoFe protein is supplied by the binding and subsequent hydrolysis of MgATP.

Related Concepts:

  • What role does MgATP binding play in the nitrogenase mechanism?: MgATP binding is a central event in the nitrogenase mechanism, as the hydrolysis of its terminal phosphate group provides the necessary energy to transfer electrons from the Fe protein to the MoFe protein, driving the reduction process.
  • How is the transfer of electrons by the Fe protein powered?: The transfer of electrons by the Fe protein requires an input of chemical energy, which is derived from the binding and subsequent hydrolysis of adenosine triphosphate (ATP). This ATP hydrolysis also induces a conformational change in the nitrogenase complex, bringing the Fe protein and MoFe protein closer together to facilitate electron transfer.

Upon MgATP binding to the Fe protein, a salt bridge forms between Lysine 15 and Aspartic acid 125, stabilizing the protein.

Answer: False

In the absence of MgATP, a salt bridge exists between Lysine 15 and Aspartic acid 125; this salt bridge is *interrupted* upon MgATP binding, not formed.

Related Concepts:

  • Which amino acid residues are involved in MgATP binding to the Fe protein, and what happens to the salt bridge upon binding?: Three amino acid residues have significant interactions with the phosphates of MgATP: Lysine 15, Aspartic acid 125, and Serine 16. In the absence of MgATP, a salt bridge exists between Lysine 15 and Aspartic acid 125, which is interrupted upon MgATP binding.

MgATP binding induces a conformational change in the Fe protein, causing the entire protein to contract and decreasing its radius by approximately 2.0 Å.

Answer: True

Binding of MgATP to the Fe protein triggers a significant conformational change, resulting in the contraction of the entire protein and a reduction in its radius by approximately 2.0 Å.

Related Concepts:

  • What conformational change does MgATP binding induce in the Fe protein?: MgATP binding induces significant conformational changes within the Fe protein, causing the entire protein to contract. Studies using X-ray scattering data have shown a decrease in the protein's radius of approximately 2.0 Å upon MgATP binding.

What powers the transfer of electrons by the Fe protein in the nitrogenase complex?

Answer: The binding and hydrolysis of adenosine triphosphate (ATP).

The energy required for the Fe protein to transfer electrons is supplied by the binding and subsequent hydrolysis of ATP.

Related Concepts:

  • How is the transfer of electrons by the Fe protein powered?: The transfer of electrons by the Fe protein requires an input of chemical energy, which is derived from the binding and subsequent hydrolysis of adenosine triphosphate (ATP). This ATP hydrolysis also induces a conformational change in the nitrogenase complex, bringing the Fe protein and MoFe protein closer together to facilitate electron transfer.
  • What role does MgATP binding play in the nitrogenase mechanism?: MgATP binding is a central event in the nitrogenase mechanism, as the hydrolysis of its terminal phosphate group provides the necessary energy to transfer electrons from the Fe protein to the MoFe protein, driving the reduction process.

What is the correct path of electrons through the nitrogenase complex?

Answer: Fe protein -> P-clusters -> FeMo cofactors.

Electrons are transferred sequentially from the Fe protein to the P-clusters within the MoFe protein, and then finally to the FeMo cofactors, where nitrogen reduction occurs.

Related Concepts:

  • Trace the path of electrons through the nitrogenase complex.: Electrons originating from the Fe protein first enter the MoFe protein at the P-clusters. From the P-clusters, these electrons are then transferred to the FeMo cofactors, which are the ultimate sites where nitrogen fixation takes place.

What does the Lowe-Thorneley kinetic model describe in the context of nitrogen fixation?

Answer: The sequential addition of proton and electron equivalents to the FeMo-cofactor during nitrogen reduction.

The Lowe-Thorneley kinetic model elucidates the step-by-step addition of proton and electron equivalents to the FeMo-cofactor, which drives the reduction of nitrogen to ammonia.

Related Concepts:

  • What is the Lowe-Thorneley kinetic model and what does it describe?: The Lowe-Thorneley (LT) kinetic model describes the sequential addition of proton and electron equivalents from Component II (dinitrogenase reductase) to the FeMo-cofactor of Component I (dinitrogenase) during the reduction of nitrogen to ammonia. Developed from kinetic measurements in the 1970s and 80s, it documents the eight correlated proton and electron transfers required for the reaction.

According to the Lowe-Thorneley model, how many equivalents of protons and electrons are required for nitrogen reduction, and how does this compare to the balanced chemical reaction?

Answer: 8 equivalents, which is more than predicted by the balanced chemical reaction.

The Lowe-Thorneley model postulates that nitrogen reduction necessitates 8 equivalents of protons and electrons, a quantity exceeding the 6 equivalents predicted by the stoichiometric balanced chemical reaction.

Related Concepts:

  • How many equivalents of protons and electrons are required for nitrogen reduction according to the Lowe-Thorneley model, and how does this compare to the balanced chemical reaction?: According to the Lowe-Thorneley model, nitrogen reduction requires 8 equivalents of protons and electrons. This is notably more than the 6 equivalents that would be predicted by the balanced chemical reaction for the conversion of N₂ to 2 NH₃.

What characterizes the E₀ intermediate in the Lowe-Thorneley kinetic model?

Answer: It represents the resting state of the nitrogenase enzyme before catalysis begins.

The E₀ intermediate signifies the quiescent, resting state of the nitrogenase enzyme prior to the initiation of its catalytic activity in nitrogen fixation.

Related Concepts:

  • Describe the E₀ intermediate in the Lowe-Thorneley kinetic model.: The E₀ intermediate represents the resting state of the nitrogenase enzyme before the catalytic process of nitrogen fixation begins. Electron Paramagnetic Resonance (EPR) characterization indicates that this species has a spin of ³/₂.

What is the proposed composition of the E₂ intermediate in the Lowe-Thorneley model?

Answer: The metal cluster in its resting oxidation state, with two added electrons in a bridging hydride and a proton bonded to sulfur.

The E₂ intermediate is hypothesized to consist of the metal cluster in its resting oxidation state, incorporating two electrons within a bridging hydride and an additional proton bound to a sulfur atom.

Related Concepts:

  • What is the proposed composition of the E₂ intermediate?: The E₂ intermediate is proposed to contain the metal cluster in its resting oxidation state, with two added electrons stored in a bridging hydride and an additional proton bonded to a sulfur atom. When isolated in mutated enzymes, the FeMo-cofactor in this state exhibits a high spin of ³/₂.

Why is the E₄ intermediate, also known as the Janus intermediate, significant in the Lowe-Thorneley model?

Answer: It occurs after half of the electron and proton transfers and can either revert to E₀ or proceed with nitrogen binding.

The E₄ intermediate, or Janus intermediate, is pivotal as it marks the halfway point of electron and proton transfers, offering a bifurcation where the enzyme can either return to its resting state (E₀) or commit to nitrogen binding and further reduction.

Related Concepts:

  • What is the significance of the E₄ intermediate, also known as the Janus intermediate?: The E₄ intermediate, termed the Janus intermediate, is significant because it occurs after exactly half of the electron and proton transfers have taken place. At this stage, the intermediate can either revert back to the E₀ resting state or proceed with nitrogen binding to complete the catalytic cycle of nitrogen fixation.

How was the E₄ intermediate first observed and characterized?

Answer: Using freeze-quench techniques with a mutated protein (Valine 70 to Isoleucine) that prevented substrate access.

The E₄ intermediate was initially detected and characterized using freeze-quench techniques on a mutated nitrogenase protein (Valine 70 to Isoleucine) engineered to restrict substrate access to the FeMo-cofactor.

Related Concepts:

  • How was the E₄ intermediate first observed and characterized?: The E₄ intermediate was first observed using freeze-quench techniques with a mutated protein where a valine amino acid at residue 70 was replaced with isoleucine, which prevented substrate access to the FeMo-cofactor. EPR characterization of this isolated intermediate showed a new species with a spin of ½, and ENDOR experiments revealed the presence of two bridging hydrides between two iron centers.

What are the two main hypotheses for the mechanism of N₂ fixation after the E₄ complex?

Answer: The distal pathway and the alternating pathway.

Following the E₄ complex, the two predominant mechanistic hypotheses for N₂ fixation are the 'distal' pathway and the 'alternating' pathway, which describe different sequences of hydrogen addition.

Related Concepts:

  • What are the two main hypotheses for the mechanism of N₂ fixation after the E₄ complex?: After the E₄ complex, there are two main hypotheses for the exact pathway of nitrogen fixation: the 'distal' pathway and the 'alternating' pathway. These pathways differ in the sequence of hydrogen additions to the nitrogen molecule.

How does the 'distal' pathway for N₂ fixation differ from the 'alternating' pathway?

Answer: The distal pathway hydrogenates the terminal nitrogen first, releases ammonia, then hydrogenates the metal-bound nitrogen.

The distal pathway is characterized by the initial hydrogenation of the terminal nitrogen atom, followed by ammonia release, and then subsequent hydrogenation of the metal-bound nitrogen, contrasting with the alternating pathway's sequential additions.

Related Concepts:

  • How do the 'distal' and 'alternating' pathways for N₂ fixation differ?: In the distal pathway, the terminal nitrogen atom of the N₂ molecule is hydrogenated first, leading to the release of ammonia, after which the nitrogen atom directly bound to the metal center is hydrogenated. In contrast, the alternating pathway involves adding one hydrogen to the terminal nitrogen, then one hydrogen to the metal-bound nitrogen, and this alternating pattern continues until ammonia is released.

What is the primary role of MgATP binding in the nitrogenase mechanism?

Answer: To provide the necessary energy for electron transfer from the Fe protein to the MoFe protein.

MgATP binding and its hydrolysis are crucial for supplying the energetic input required to facilitate electron transfer from the Fe protein to the MoFe protein, a key step in nitrogen fixation.

Related Concepts:

  • What role does MgATP binding play in the nitrogenase mechanism?: MgATP binding is a central event in the nitrogenase mechanism, as the hydrolysis of its terminal phosphate group provides the necessary energy to transfer electrons from the Fe protein to the MoFe protein, driving the reduction process.
  • How is the transfer of electrons by the Fe protein powered?: The transfer of electrons by the Fe protein requires an input of chemical energy, which is derived from the binding and subsequent hydrolysis of adenosine triphosphate (ATP). This ATP hydrolysis also induces a conformational change in the nitrogenase complex, bringing the Fe protein and MoFe protein closer together to facilitate electron transfer.

Which amino acid residues are primarily involved in MgATP binding to the Fe protein, and what happens to the salt bridge between Lysine 15 and Aspartic acid 125 upon binding?

Answer: Lysine 15, Aspartic acid 125, and Serine 16; the salt bridge is interrupted.

Lysine 15, Aspartic acid 125, and Serine 16 are key residues in MgATP binding to the Fe protein, and this binding event leads to the interruption of the salt bridge between Lysine 15 and Aspartic acid 125.

Related Concepts:

  • Which amino acid residues are involved in MgATP binding to the Fe protein, and what happens to the salt bridge upon binding?: Three amino acid residues have significant interactions with the phosphates of MgATP: Lysine 15, Aspartic acid 125, and Serine 16. In the absence of MgATP, a salt bridge exists between Lysine 15 and Aspartic acid 125, which is interrupted upon MgATP binding.

What conformational change does MgATP binding induce in the Fe protein?

Answer: It causes the entire protein to contract, decreasing its radius by approximately 2.0 Å.

The binding of MgATP to the Fe protein triggers a conformational shift that causes the entire protein to contract, resulting in an approximate 2.0 Å decrease in its radius.

Related Concepts:

  • What conformational change does MgATP binding induce in the Fe protein?: MgATP binding induces significant conformational changes within the Fe protein, causing the entire protein to contract. Studies using X-ray scattering data have shown a decrease in the protein's radius of approximately 2.0 Å upon MgATP binding.

Alternative Nitrogenases

Alternative nitrogenases become active in environments where there is a low availability of the molybdenum (Mo) cofactor.

Answer: True

Alternative nitrogenases are expressed and become active under conditions where molybdenum, a key component of the standard MoFe nitrogenase, is scarce.

Related Concepts:

  • Under what environmental conditions do alternative nitrogenases become active?: Alternative nitrogenases become active in environments where there is a low availability of the molybdenum (Mo) cofactor, which is typically required for the standard MoFe nitrogenase.

The two known types of alternative nitrogenases are the nickel-iron (NiFe) type and the copper-iron (CuFe) type.

Answer: False

The two recognized types of alternative nitrogenases are the vanadium-iron (VFe) type and the iron-iron (FeFe) type, not nickel-iron or copper-iron.

Related Concepts:

  • What are the two known types of alternative nitrogenases?: The two known types of alternative nitrogenases are the vanadium-iron (VFe) type, often referred to as Vnf, and the iron-iron (FeFe) type, known as Anf.

Alternative nitrogenases share homologous alpha and beta subunits with the MoFe nitrogenase, indicating a shared evolutionary origin.

Answer: True

Alternative nitrogenases possess alpha and beta subunits that are homologous to those found in the MoFe nitrogenase, suggesting a common evolutionary lineage.

Related Concepts:

  • How do the structures of alternative nitrogenases compare to the MoFe nitrogenase?: Alternative nitrogenases, whether VFe or FeFe type, form an assembly consisting of two α subunits, two β subunits, and two δ (sometimes γ, like VnfG/AnfG) subunits. The delta subunits are homologous to each other, and the alpha and beta subunits are homologous to those found in the MoFe nitrogenase, indicating a shared evolutionary origin.

All nitrogenases, including alternative types, utilize molybdenum (Mo) as the central metal in their cofactors.

Answer: False

While standard nitrogenase uses molybdenum, alternative nitrogenases utilize vanadium or only iron as the central metal in their cofactors, not molybdenum.

Related Concepts:

  • What is a key difference in the metal cofactors between the standard and alternative nitrogenases?: All nitrogenases share a similar iron-sulfur (Fe-S) core cluster, but the key difference lies in the cofactor metal. The standard nitrogenase uses molybdenum (Mo), while alternative nitrogenases utilize vanadium (V) or only iron (Fe) in their cofactors.

In the FeFe nitrogenase, the δ/γ subunit plays a role in helping to bind the cofactor, assisting in adaptation to new metals.

Answer: True

The δ/γ subunit in FeFe nitrogenase is involved in cofactor binding, a function believed to have facilitated the enzyme's adaptation to different metal cofactors during evolution.

Related Concepts:

  • What is the role of the δ/γ subunit in alternative nitrogenases, particularly in the FeFe type?: In the FeFe nitrogenase, the δ/γ subunit plays a role in helping to bind the cofactor. Its evolution is believed to have assisted the prototypical alternative nitrogenase in adapting to new metals.

Organisms generally prefer alternative nitrogenases when molybdenum is available because they are more efficient in ATP usage than MoFe nitrogenase.

Answer: False

Organisms prefer the MoFe nitrogenase when molybdenum is available because it is the most efficient type, consuming less ATP for proton reduction compared to alternative nitrogenases.

Related Concepts:

  • Why is the MoFe nitrogenase generally preferred by organisms when molybdenum is available?: The MoFe nitrogenase is generally preferred because it is the most efficient type, wasting less ATP on the reduction of protons (H⁺) into dihydrogen (H₂) compared to the alternative nitrogenases. When molybdenum is present, the expression of alternative nitrogenases is repressed, ensuring the use of the more efficient enzyme.

Vanadium nitrogenases uniquely catalyze the conversion of carbon monoxide into alkanes, a reaction comparable to Fischer-Tropsch synthesis.

Answer: True

Vanadium nitrogenases exhibit a unique catalytic capability, converting carbon monoxide into alkanes, a process mechanistically similar to the industrial Fischer-Tropsch synthesis.

Related Concepts:

  • What unique reaction can vanadium nitrogenases catalyze involving carbon monoxide?: Vanadium nitrogenases have been shown to uniquely catalyze the conversion of carbon monoxide (CO) into alkanes through a reaction that is comparable to the Fischer-Tropsch synthesis, a process typically used in industrial chemistry to produce liquid hydrocarbons from CO and H₂.

Under what environmental conditions do alternative nitrogenases typically become active?

Answer: Low availability of the molybdenum (Mo) cofactor.

Alternative nitrogenases are typically activated in environments characterized by a limited supply of molybdenum, which is essential for the standard MoFe nitrogenase.

Related Concepts:

  • Under what environmental conditions do alternative nitrogenases become active?: Alternative nitrogenases become active in environments where there is a low availability of the molybdenum (Mo) cofactor, which is typically required for the standard MoFe nitrogenase.

What are the two known types of alternative nitrogenases?

Answer: Vanadium-iron (VFe) and Iron-iron (FeFe).

The two identified types of alternative nitrogenases are the vanadium-iron (VFe) type and the iron-iron (FeFe) type.

Related Concepts:

  • What are the two known types of alternative nitrogenases?: The two known types of alternative nitrogenases are the vanadium-iron (VFe) type, often referred to as Vnf, and the iron-iron (FeFe) type, known as Anf.

How do the structures of alternative nitrogenases compare to the MoFe nitrogenase?

Answer: They consist of two alpha, two beta, and two delta (or gamma) subunits, with alpha and beta homologous to MoFe nitrogenase.

Alternative nitrogenases are composed of two alpha, two beta, and two delta (or gamma) subunits, where the alpha and beta subunits share homology with those found in the MoFe nitrogenase.

Related Concepts:

  • How do the structures of alternative nitrogenases compare to the MoFe nitrogenase?: Alternative nitrogenases, whether VFe or FeFe type, form an assembly consisting of two α subunits, two β subunits, and two δ (sometimes γ, like VnfG/AnfG) subunits. The delta subunits are homologous to each other, and the alpha and beta subunits are homologous to those found in the MoFe nitrogenase, indicating a shared evolutionary origin.

What is the key difference in the metal cofactors between standard and alternative nitrogenases?

Answer: Standard nitrogenase uses molybdenum, while alternative types use vanadium or only iron.

The primary distinction in metal cofactors is that standard nitrogenase incorporates molybdenum, whereas alternative nitrogenases utilize either vanadium or solely iron.

Related Concepts:

  • What is a key difference in the metal cofactors between the standard and alternative nitrogenases?: All nitrogenases share a similar iron-sulfur (Fe-S) core cluster, but the key difference lies in the cofactor metal. The standard nitrogenase uses molybdenum (Mo), while alternative nitrogenases utilize vanadium (V) or only iron (Fe) in their cofactors.

What is the primary role attributed to the δ/γ subunit in alternative nitrogenases, especially in the FeFe type?

Answer: Helping to bind the cofactor.

The δ/γ subunit in alternative nitrogenases, particularly the FeFe type, is primarily involved in facilitating the binding of the cofactor, a role that likely contributed to the enzyme's adaptation to various metals.

Related Concepts:

  • What is the role of the δ/γ subunit in alternative nitrogenases, particularly in the FeFe type?: In the FeFe nitrogenase, the δ/γ subunit plays a role in helping to bind the cofactor. Its evolution is believed to have assisted the prototypical alternative nitrogenase in adapting to new metals.

Why is the MoFe nitrogenase generally preferred by organisms when molybdenum is available?

Answer: It is the most efficient type, wasting less ATP on proton reduction.

The MoFe nitrogenase is favored when molybdenum is accessible because it demonstrates superior efficiency, minimizing ATP expenditure on the unproductive reduction of protons to dihydrogen compared to alternative nitrogenases.

Related Concepts:

  • Why is the MoFe nitrogenase generally preferred by organisms when molybdenum is available?: The MoFe nitrogenase is generally preferred because it is the most efficient type, wasting less ATP on the reduction of protons (H⁺) into dihydrogen (H₂) compared to the alternative nitrogenases. When molybdenum is present, the expression of alternative nitrogenases is repressed, ensuring the use of the more efficient enzyme.

What unique reaction can vanadium nitrogenases catalyze involving carbon monoxide?

Answer: The conversion of carbon monoxide into alkanes, similar to Fischer-Tropsch synthesis.

Vanadium nitrogenases possess the distinct ability to catalyze the conversion of carbon monoxide into alkanes, a reaction mechanistically analogous to the Fischer-Tropsch synthesis.

Related Concepts:

  • What unique reaction can vanadium nitrogenases catalyze involving carbon monoxide?: Vanadium nitrogenases have been shown to uniquely catalyze the conversion of carbon monoxide (CO) into alkanes through a reaction that is comparable to the Fischer-Tropsch synthesis, a process typically used in industrial chemistry to produce liquid hydrocarbons from CO and H₂.

Regulation and Inhibition

Nitrogenases can reduce carbon dioxide to methane, a reaction that is highly specific to the enzyme.

Answer: False

Nitrogenases can reduce carbon dioxide to carbon monoxide and water, but not methane. Furthermore, nitrogenases are known to reduce a variety of non-specific substrates, indicating a lack of high specificity for reactions other than N₂ reduction.

Related Concepts:

  • What are some non-specific reactions catalyzed by nitrogenases?: In addition to reducing dinitrogen, nitrogenases can also reduce protons to dihydrogen, acting as a dehydrogenase. They can also reduce other substrates such as acetylene to ethylene, nitrous oxide to N₂ and water, azide to N₂ and ammonia, cyanide to methane, ammonia, ethane, and ethylene, nitriles to alkanes and ammonia, carbonyl sulfide to carbon monoxide and hydrogen sulfide, carbon dioxide to carbon monoxide and water, thiocyanate to hydrogen sulfide and hydrogen cyanide, and cyanate to water and hydrogen cyanide or carbon monoxide and ammonia.

Dihydrogen (H₂) acts as a competitive inhibitor of nitrogenase, while carbon monoxide (CO) functions as a non-competitive inhibitor.

Answer: True

Dihydrogen (H₂) competitively inhibits nitrogenase, whereas carbon monoxide (CO) acts as a non-competitive inhibitor by preventing the binding of dinitrogen to the active site.

Related Concepts:

  • Which molecules are known to inhibit nitrogenase activity?: Nitrogenase activity can be inhibited by several molecules: dihydrogen (H₂) acts as a competitive inhibitor, carbon monoxide (CO) functions as a non-competitive inhibitor by preventing dinitrogen binding, and carbon disulfide (CS₂) acts as a rapid-equilibrium inhibitor.

Oxygen is generally beneficial for nitrogenase activity, as it helps to remove excess electrons from the active site.

Answer: False

Oxygen is detrimental to most nitrogenases, causing irreversible inhibition by oxidatively degrading their iron-sulfur cofactors, and is not beneficial for enzyme activity.

Related Concepts:

  • Why is oxygen a problem for most nitrogenases, and how do some organisms protect the enzyme?: Oxygen is problematic for most nitrogenases because it irreversibly inhibits them by oxidatively degrading their iron-sulfur (Fe-S) cofactors. Nitrogen-fixing organisms have developed mechanisms to protect nitrogenase from oxygen *in vivo*, such as a high metabolic rate in Azotobacteraceae to reduce oxygen at the cell membrane, or the use of leghemoglobin in leguminous plant nodules to buffer oxygen levels at the active site while still allowing for efficient respiration.

Besides dinitrogen, which of the following is a non-specific substrate that nitrogenase can reduce?

Answer: Acetylene to ethylene.

Beyond its primary function of reducing dinitrogen, nitrogenase can also non-specifically reduce other substrates, such as acetylene to ethylene.

Related Concepts:

  • What are some non-specific reactions catalyzed by nitrogenases?: In addition to reducing dinitrogen, nitrogenases can also reduce protons to dihydrogen, acting as a dehydrogenase. They can also reduce other substrates such as acetylene to ethylene, nitrous oxide to N₂ and water, azide to N₂ and ammonia, cyanide to methane, ammonia, ethane, and ethylene, nitriles to alkanes and ammonia, carbonyl sulfide to carbon monoxide and hydrogen sulfide, carbon dioxide to carbon monoxide and water, thiocyanate to hydrogen sulfide and hydrogen cyanide, and cyanate to water and hydrogen cyanide or carbon monoxide and ammonia.

Which molecule acts as a non-competitive inhibitor of nitrogenase by preventing dinitrogen binding?

Answer: Carbon monoxide (CO)

Carbon monoxide (CO) functions as a non-competitive inhibitor of nitrogenase, impeding the enzyme's activity by preventing the binding of dinitrogen to its active site.

Related Concepts:

  • Which molecules are known to inhibit nitrogenase activity?: Nitrogenase activity can be inhibited by several molecules: dihydrogen (H₂) acts as a competitive inhibitor, carbon monoxide (CO) functions as a non-competitive inhibitor by preventing dinitrogen binding, and carbon disulfide (CS₂) acts as a rapid-equilibrium inhibitor.

How do some nitrogen-fixing organisms, such as Azotobacteraceae, protect nitrogenase from oxygen?

Answer: By maintaining a high metabolic rate to reduce oxygen at the cell membrane.

Certain nitrogen-fixing organisms, such as Azotobacteraceae, employ strategies like maintaining a high metabolic rate to rapidly consume oxygen at the cell membrane, thereby protecting the oxygen-sensitive nitrogenase enzyme.

Related Concepts:

  • Why is oxygen a problem for most nitrogenases, and how do some organisms protect the enzyme?: Oxygen is problematic for most nitrogenases because it irreversibly inhibits them by oxidatively degrading their iron-sulfur (Fe-S) cofactors. Nitrogen-fixing organisms have developed mechanisms to protect nitrogenase from oxygen *in vivo*, such as a high metabolic rate in Azotobacteraceae to reduce oxygen at the cell membrane, or the use of leghemoglobin in leguminous plant nodules to buffer oxygen levels at the active site while still allowing for efficient respiration.

Nitrogenase Evolution and Diversity

Nitrogenases are exclusively encoded by a single, highly conserved gene across all nitrogen-fixing organisms.

Answer: False

Nitrogenases are encoded by *Nif* genes or their homologous counterparts, which are not a single, highly conserved gene but rather a family of genes that can vary across different nitrogen-fixing organisms.

Related Concepts:

  • Which genes are responsible for encoding nitrogenases?: Nitrogenases are encoded by the *Nif* genes or their homologous counterparts, meaning genes that share a common evolutionary origin and similar sequence or structure.

Nitrogenases are divided into two main groups, with alternative nitrogenases found in Class I.

Answer: False

Nitrogenases are categorized into three main groups or classes (I, II, and III), with alternative nitrogenases specifically nested within Class III.

Related Concepts:

  • Into how many groups or clades are nitrogenases divided, and where are alternative nitrogenases found within this classification?: Nitrogenases are divided into three main groups, clades, or classes, designated by Roman numerals I through III. The alternative nitrogenases are specifically nested within Class III.

Nif-I nitrogenases are primarily found in aerobic or facultatively anaerobic diazotrophs that possess large *Nif* gene families.

Answer: True

Nif-I nitrogenases are predominantly observed in aerobic or facultatively anaerobic diazotrophs, which are characterized by extensive *Nif* gene families.

Related Concepts:

  • What is the general distribution pattern of Nif-I nitrogenases compared to other types?: Nif-I nitrogenases are primarily found in aerobic or facultatively anaerobic diazotrophs that possess large *Nif* gene families. In contrast, the other types of nitrogenases (Groups II and III) are almost exclusively found in anaerobic diazotrophs, which typically have smaller gene networks.

Ancestral sequence reconstruction indicates that early Group I nitrogenases operated more rapidly and with higher ATP efficiency than modern versions.

Answer: False

Ancestral sequence reconstruction studies suggest that early Group I nitrogenases operated more slowly than modern versions, though they maintained a similar efficiency in ATP usage.

Related Concepts:

  • What does ancestral sequence reconstruction reveal about early nitrogenases?: Ancestral sequence reconstruction has been used to reconstruct early Group I nitrogenases, such as Anc2 (representing the ancestor to all sampled nitrogenases in Gammaproteobacteria) and Anc1 (representing a smaller group including *Azotobacter vinelandii*). These reconstructed ancestral enzymes were found to operate more slowly than the modern *A. vinelandii* version but maintained a similar efficiency in ATP usage, with a largely unchanged ratio between formed H₂ and reduced N₂ (around 2.1), except for Anc1B which was more efficient.

The NifEN maturase has a structure quite similar to nitrogenase component I (NifDK) and is involved in assembling P-cluster and M-cluster precursors.

Answer: True

The NifEN maturase exhibits structural homology to nitrogenase component I (NifDK) and plays a critical role in the assembly and transfer of P-cluster and M-cluster precursors.

Related Concepts:

  • How is the NifEN maturase related to nitrogenase component I (NifDK)?: The NifEN maturase, which is responsible for assembling the precursor to the P-cluster (called an O-cluster) and transferring it to NifDK, and also for assembling the M-cluster with NifH before its transfer to NifDK, has a structure quite similar to the nitrogenase component I (NifDK). NifEN typically carries a P-cluster and an L-cluster (the precursor to the M-cluster).

The structural dissimilarity between NifEN and NifDK, along with NifEN's inability to fix nitrogen, supports their independent evolutionary origins.

Answer: False

The structural *similarity* between NifEN and NifDK, coupled with NifEN's nitrogen-fixing ability when expressed in *E. coli*, supports the hypothesis of their evolution from a gene duplication event, not independent origins.

Related Concepts:

  • What evidence supports the idea that NifEN and NifDK evolved from a gene duplication event?: One interpretation of the structural similarity between NifEN and NifDK, along with NifEN's nitrogen-fixing ability when expressed in *E. coli*, suggests that there was an ancestral single nitrogenase with P- and L-clusters. This ancestral gene then underwent duplication, leading to the evolution of NifEN (which gained the M-cluster) and NifDK (which lost the P-cluster), possibly influenced by increased molybdenum availability after the Great Oxidation Event.

Isotopic data suggests that molybdenum-based nitrogen fixation is an ancient process, at least 3.2 gigayears old.

Answer: True

Isotopic evidence indicates that molybdenum-based nitrogen fixation is a very ancient biological process, dating back at least 3.2 gigayears.

Related Concepts:

  • What is the approximate age of Mo-based nitrogen fixation according to isotopic data?: Isotopic data suggests that molybdenum-based nitrogen fixation is at least 3.2 gigayears old, indicating its ancient origin in Earth's history.

Nitrogenase subunits exhibit significant sequence similarity to subunits of the light-dependent version of protochlorophyllide reductase.

Answer: False

Nitrogenase subunits show significant sequence similarity to the subunits of the *light-independent* version of protochlorophyllide reductase (DPOR), not the light-dependent version.

Related Concepts:

  • How are nitrogenase subunits structurally similar to protochlorophyllide reductase?: The three subunits of nitrogenase exhibit significant sequence similarity to three subunits of the light-independent version of protochlorophyllide reductase (DPOR, composed of (ChlNB)₂ + ChlL₂). This structural similarity places nitrogenase in the same superfamily as DPOR, an enzyme that converts protochlorophyllide to chlorophyll in gymnosperms, algae, and photosynthetic bacteria.

'Class IV' *nif* genes in methanogens, such as the CfbC type, are known to produce coenzyme F430, even though they do not fix nitrogen.

Answer: True

'Class IV' *nif* genes, found in methanogens, are homologs of nitrogenase subunits that do not fix nitrogen but are involved in other metabolic pathways, such as the CfbC type producing coenzyme F430.

Related Concepts:

  • What are 'Class IV' *nif* genes, and what are their known functions in methanogens?: 'Class IV' *nif* genes are homologs of nitrogenase subunits (NifD and NifH) found in methanogens, such as *Methanocaldococcus jannaschii*, that do not fix nitrogen. While their full function was unclear as of 2004, they are known to interact and are constitutively expressed. More recent analysis suggests they are monophyletic, with two known functions: the CfbC type produces coenzyme F430, and the Mar type can synthesize methionine, ethylene, and methane.

Which genes are responsible for encoding nitrogenases?

Answer: Nif genes

Nitrogenases are encoded by a specific set of genes known as *Nif* genes or their homologous counterparts.

Related Concepts:

  • Which genes are responsible for encoding nitrogenases?: Nitrogenases are encoded by the *Nif* genes or their homologous counterparts, meaning genes that share a common evolutionary origin and similar sequence or structure.

Into how many main groups or clades are nitrogenases divided, and where are alternative nitrogenases found?

Answer: Three groups; Class III.

Nitrogenases are classified into three primary groups (Classes I, II, and III), with the alternative nitrogenases specifically categorized within Class III.

Related Concepts:

  • Into how many groups or clades are nitrogenases divided, and where are alternative nitrogenases found within this classification?: Nitrogenases are divided into three main groups, clades, or classes, designated by Roman numerals I through III. The alternative nitrogenases are specifically nested within Class III.

What is the general distribution pattern of Nif-I nitrogenases?

Answer: Primarily found in aerobic or facultatively anaerobic diazotrophs with large *Nif* gene families.

Nif-I nitrogenases are predominantly observed in aerobic or facultatively anaerobic diazotrophs, which are characterized by the presence of large *Nif* gene families.

Related Concepts:

  • What is the general distribution pattern of Nif-I nitrogenases compared to other types?: Nif-I nitrogenases are primarily found in aerobic or facultatively anaerobic diazotrophs that possess large *Nif* gene families. In contrast, the other types of nitrogenases (Groups II and III) are almost exclusively found in anaerobic diazotrophs, which typically have smaller gene networks.

What did ancestral sequence reconstruction reveal about early Group I nitrogenases like Anc2 and Anc1?

Answer: They operated more slowly than modern versions but maintained similar ATP usage efficiency.

Ancestral sequence reconstruction studies indicated that early Group I nitrogenases, such as Anc2 and Anc1, functioned at a slower rate than their modern counterparts but retained comparable ATP usage efficiency.

Related Concepts:

  • What does ancestral sequence reconstruction reveal about early nitrogenases?: Ancestral sequence reconstruction has been used to reconstruct early Group I nitrogenases, such as Anc2 (representing the ancestor to all sampled nitrogenases in Gammaproteobacteria) and Anc1 (representing a smaller group including *Azotobacter vinelandii*). These reconstructed ancestral enzymes were found to operate more slowly than the modern *A. vinelandii* version but maintained a similar efficiency in ATP usage, with a largely unchanged ratio between formed H₂ and reduced N₂ (around 2.1), except for Anc1B which was more efficient.

What is the relationship between the NifEN maturase and nitrogenase component I (NifDK)?

Answer: NifEN is structurally similar to NifDK and is involved in assembling and transferring P-cluster and M-cluster precursors to NifDK.

The NifEN maturase exhibits structural homology to nitrogenase component I (NifDK) and is functionally involved in the assembly and transfer of P-cluster and M-cluster precursors.

Related Concepts:

  • How is the NifEN maturase related to nitrogenase component I (NifDK)?: The NifEN maturase, which is responsible for assembling the precursor to the P-cluster (called an O-cluster) and transferring it to NifDK, and also for assembling the M-cluster with NifH before its transfer to NifDK, has a structure quite similar to the nitrogenase component I (NifDK). NifEN typically carries a P-cluster and an L-cluster (the precursor to the M-cluster).

What evidence supports the hypothesis that NifEN and NifDK evolved from a gene duplication event?

Answer: The structural similarity between NifEN and NifDK, and NifEN's nitrogen-fixing ability in *E. coli*.

The structural resemblance between NifEN and NifDK, coupled with NifEN's demonstrated nitrogen-fixing capability when expressed in *E. coli*, provides evidence for their evolutionary origin from a gene duplication event.

Related Concepts:

  • What evidence supports the idea that NifEN and NifDK evolved from a gene duplication event?: One interpretation of the structural similarity between NifEN and NifDK, along with NifEN's nitrogen-fixing ability when expressed in *E. coli*, suggests that there was an ancestral single nitrogenase with P- and L-clusters. This ancestral gene then underwent duplication, leading to the evolution of NifEN (which gained the M-cluster) and NifDK (which lost the P-cluster), possibly influenced by increased molybdenum availability after the Great Oxidation Event.

According to isotopic data, what is the approximate age of molybdenum-based nitrogen fixation?

Answer: At least 3.2 gigayears old.

Isotopic analyses suggest that molybdenum-based nitrogen fixation is an ancient process, with an estimated age of at least 3.2 gigayears.

Related Concepts:

  • What is the approximate age of Mo-based nitrogen fixation according to isotopic data?: Isotopic data suggests that molybdenum-based nitrogen fixation is at least 3.2 gigayears old, indicating its ancient origin in Earth's history.

To which other enzyme do nitrogenase subunits show significant sequence similarity, placing them in the same superfamily?

Answer: Light-independent protochlorophyllide reductase (DPOR).

Nitrogenase subunits exhibit substantial sequence similarity to the subunits of light-independent protochlorophyllide reductase (DPOR), indicating their membership in the same enzyme superfamily.

Related Concepts:

  • How are nitrogenase subunits structurally similar to protochlorophyllide reductase?: The three subunits of nitrogenase exhibit significant sequence similarity to three subunits of the light-independent version of protochlorophyllide reductase (DPOR, composed of (ChlNB)₂ + ChlL₂). This structural similarity places nitrogenase in the same superfamily as DPOR, an enzyme that converts protochlorophyllide to chlorophyll in gymnosperms, algae, and photosynthetic bacteria.

What is a known function of 'Class IV' *nif* genes in methanogens?

Answer: Producing coenzyme F430 (CfbC type) or synthesizing methionine, ethylene, and methane (Mar type).

In methanogens, 'Class IV' *nif* genes, while not involved in nitrogen fixation, are known to perform other functions, such as the CfbC type producing coenzyme F430, or the Mar type synthesizing methionine, ethylene, and methane.

Related Concepts:

  • What are 'Class IV' *nif* genes, and what are their known functions in methanogens?: 'Class IV' *nif* genes are homologs of nitrogenase subunits (NifD and NifH) found in methanogens, such as *Methanocaldococcus jannaschii*, that do not fix nitrogen. While their full function was unclear as of 2004, they are known to interact and are constitutively expressed. More recent analysis suggests they are monophyletic, with two known functions: the CfbC type produces coenzyme F430, and the Mar type can synthesize methionine, ethylene, and methane.

Assay Methods

The acetylene reduction assay (ARA) measures nitrogenase activity by quantifying the conversion of ethylene gas to acetylene gas.

Answer: False

The acetylene reduction assay (ARA) quantifies nitrogenase activity by measuring the conversion of *acetylene gas to ethylene gas*, not the reverse.

Related Concepts:

  • What is a common method for estimating nitrogenase activity in a laboratory setting?: A common method for estimating nitrogenase activity is the acetylene reduction assay (ARA). This assay takes advantage of the enzyme's ability to reduce acetylene gas to ethylene gas, both of which can be easily quantified using gas chromatography.

A limitation of the acetylene reduction assay (ARA) is that dihydrogen (H₂) competes with N₂ but not acetylene, which can lead to an overestimation of nitrogenase activity.

Answer: True

A known limitation of the acetylene reduction assay (ARA) is that dihydrogen (H₂) competes with dinitrogen (N₂) for the enzyme's active site but does not compete with acetylene, potentially leading to an inflated estimation of nitrogenase activity.

Related Concepts:

  • What are some limitations of the acetylene reduction assay (ARA) for measuring nitrogenase activity?: The acetylene reduction assay (ARA) has several limitations. Converting data from ARA to actual moles of N₂ reduced is not always straightforward and can lead to overestimation or underestimation of the true rate. For example, dihydrogen (H₂) competes with N₂ but not acetylene for nitrogenase, which can cause ARA to overestimate nitrogenase activity. Additionally, bottle or chamber-based assays may negatively impact microbial systems due to containment or disruption of the microenvironment, leading to underestimation.

What is a common laboratory method for estimating nitrogenase activity?

Answer: The acetylene reduction assay (ARA).

The acetylene reduction assay (ARA) is a widely employed laboratory technique for quantifying nitrogenase activity, leveraging the enzyme's ability to reduce acetylene to ethylene.

Related Concepts:

  • What is a common method for estimating nitrogenase activity in a laboratory setting?: A common method for estimating nitrogenase activity is the acetylene reduction assay (ARA). This assay takes advantage of the enzyme's ability to reduce acetylene gas to ethylene gas, both of which can be easily quantified using gas chromatography.

Which of the following is a limitation of the acetylene reduction assay (ARA)?

Answer: It can overestimate nitrogenase activity because dihydrogen (H₂) competes with N₂ but not acetylene.

A significant limitation of the acetylene reduction assay (ARA) is its potential to overestimate nitrogenase activity due to dihydrogen (H₂) competing with dinitrogen (N₂) for the enzyme, but not with acetylene.

Related Concepts:

  • What are some limitations of the acetylene reduction assay (ARA) for measuring nitrogenase activity?: The acetylene reduction assay (ARA) has several limitations. Converting data from ARA to actual moles of N₂ reduced is not always straightforward and can lead to overestimation or underestimation of the true rate. For example, dihydrogen (H₂) competes with N₂ but not acetylene for nitrogenase, which can cause ARA to overestimate nitrogenase activity. Additionally, bottle or chamber-based assays may negatively impact microbial systems due to containment or disruption of the microenvironment, leading to underestimation.

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