Reductive citrate cycle

Wachtcrshauser s prime candidate for a carbon-fixing process driven by pyrite formation is the reductive citrate cycle (RCC) mentioned above. Expressed simply, the RCC is the reversal of the normal Krebs cycle (tricarboxylic acid cycle TCA cycle), which is referred to as the turntable of metabolism because of its vital importance for metabolism in living cells. The Krebs cycle, in simplified form, can be summarized as follows ... 

Dark phase (CO2 fixation phase) 0/ photosynthesis. The various aspects of this phase of photosynthesis are described in the following separate articles, which are best read in the following sequence (i) Calvin cycle, which can be regarded as the basic COj fixation process, (ii) Hatch-Slack-Kortschak cycle, which deals with CO2 fixation in C -plants, such as sugar cane, (iii) Crassulacean acid metabolism, which deals with COj fixation in plants, such as cacti, growing in arid climates, and (iv) Reductive citrate cycle, which describes COj fixation in green sulfur bacteria. 

The reductive citrate cycle irt the Chlorobiaceae (purple sulfur bacteria). 

Mn " " also activates several oxidases. The role of manganese in oxidation-reduction processes of plants is its most important function, and is related to the valency change between Mn " " and Mn (Kabata-Pendias and Pendias 2001). Because of its high redox potential, manganese is the main metallic activator of enzymes in the citrate cycle and controls oxidation, reduction, and carboxylation reactions in carbohy-... 

Figure 17.15 Major metabolic pathways involved in SA production in Saccbaromyces cerevisiae. Bold arrows indicate the major routes for succinate synthesis starting from glucose (a) via the reductive TCA cycle and (b) via the giyoxyiate cycle. PEP, phos-phoenolpyruvate OAA, oxaloacetate MAL, malate FUM, fumarate Suc-CoA, sucdnyl-CoA cr-KG, cr-ketoglutarate ICT, isodtrate CIT, citrate, ppc, PEP carboxykinase pyc, pyruvate carboxylase pyk, pyruvate kinase ...

Iron Sulfur Compounds. Many molecular compounds (18—20) are known in which iron is tetrahedraHy coordinated by a combination of thiolate and sulfide donors. Of the 10 or more stmcturaHy characterized classes of Fe—S compounds, the four shown in Figure 1 are known to occur in proteins. The mononuclear iron site REPLACE occurs in the one-iron bacterial electron-transfer protein mbredoxin. The [2Fe—2S] (10) and [4Fe—4S] (12) cubane stmctures are found in the 2-, 4-, and 8-iron ferredoxins, which are also electron-transfer proteins. The [3Fe—4S] voided cubane stmcture (11) has been found in some ferredoxins and in the inactive form of aconitase, the enzyme which catalyzes the stereospecific hydration—rehydration of citrate to isocitrate in the Krebs cycle. In addition, enzymes are known that contain either other types of iron sulfur clusters or iron sulfur clusters that include other metals. Examples include nitrogenase, which reduces N2 to NH at a MoFe Sg homocitrate cluster carbon monoxide dehydrogenase, which assembles acetyl-coenzyme A (acetyl-CoA) at a FeNiS site and hydrogenases, which catalyze the reversible reduction of protons to hydrogen gas. 

A carrier molecule containing four carbon atoms (the C4 unit) takes up a C2 unit (the activated acetic acid ), which is introduced into the cycle. The product is a six-carbon molecule (the C6 unit), citric acid, or its salt, citrate. CO2 is cleaved off in a cyclic process, so that a C5 unit is left this loses a further molecule of CO2 to give the C4 unit, oxalacetate. In the living cell, this process involves ten steps, which are catalysed by eight enzymes. However, the purpose of the TCA cycle is not the elimination of CO2, but the provision of reduction equivalents, i.e., of electrons, and... 

If nitrogen (in the form of ammonia) is growth limiting, the potential applications of acetyl-CoA and NAD(P)H are restricted. Liberated NAD(P)H cannot be consumed for reductive syntheses, for instance of amino acids, it remains available and starts to inhibit citrate synthase [45, 46]. To the extent that the TCA cycle is thereby inhibited, acetyl-CoA should become available for the 3-ketothiolase, and could flow into poly(3HB) (Fig. 1, Table 1). 

One of the first persons to study the oxidation of organic compounds by animal tissues was T. Thunberg, who between 1911 and 1920 discovered about 40 organic compounds that could be oxidized by animal tissues. Salts of succinate, fumarate, malate, and citrate were oxidized the fastest. Well aware of Knoop s (3 oxidation theory, Thunberg proposed a cyclic mechanism for oxidation of acetate. Two molecules of this two-carbon compound were supposed to condense (with reduction) to succinate, which was then oxidized as in the citric acid cycle to oxaloacetate. The latter was decarboxylated to pyruvate, which was oxidatively decarboxylated to acetate to complete the cycle. One of the reactions essential for this cycle could not be verified experimentally. It is left to the reader to recognize which one. 

To understand why isocitrate dehydrogenase is so intensely regulated we must consider reactions beyond the TCA cycle, and indeed beyond the mitochondrion (fig. 13.15). Of the two compounds citrate and isocitrate, only citrate is transported across the barrier imposed by the mitochondrial membrane. Citrate that passes from the mitochondrion to the cytosol plays a major role in biosynthesis, both because of its immediate regulatory properties and because of the chain of covalent reactions it initiates. In the cytosol citrate undergoes a cleavage reaction in which acetyl-CoA is produced. The other cleavage product, oxaloacetate, can be utilized directly in various biosynthetic reactions or it can be converted to malate. The malate so formed can be returned to the mitochondrion, or it can be converted in the cytosol to pyruvate, which also results in the reduction of NADP+ to NADPH. The pyruvate is either utilized directly in biosynthetic processes, or like malate, can return to the mitochondrion. 

Reductive citric acid cycle 5 3 NAD(P)H, 1 unknown donor", 2 ferredoxin 2-Oxoglutarate synthase Isocitrate dehydrogenase6 Pyruvate synthase PEP carboxylase C02 C02 C02 HCOJ Acetyl-CoA, pyruvate, PEP, oxaloacetate, succinyl-CoA, 2-oxoglutarate 2-Oxoglutarate synthase, ATP-citrate lyase... 

Three modifications of the conventional oxidative citric acid cycle are needed, which substitute irreversible enzyme steps. Succinate dehydrogenase is replaced by fumarate reductase, 2-oxoglutarate dehydrogenase by ferredoxin-dependent 2-oxoglutarate oxidoreductase (2-oxoglutarate synthase), and citrate synthase by ATP-citrate lyase [3, 16] it should be noted that the carboxylases of the cycle catalyze the reductive carboxylation reactions. There are variants of the ATP-driven cleavage of citrate as well as of isocitrate formation [7]. The reductive citric acid... 

Figure 3.2 Reductive citric acid cycle, ffi, ATP-citrate lyase 2-oxoglutarate ferredoxin oxidoreductase (2-oxoglutarate synthase)

Fig. 2.15. The first cycles at two identical poly(aniline)/po y(vinylsulfonate)-coated glassy carbon electrodes (deposition charge 150 mC, geometric area 0.38 cm2) recorded at 2 mV s in oxygen-free 0.1 mol dm 3 citrate/phosphate buffer at pH 7, in the absence of NADH ( —), and in the presence of 4.4 mmol dm 3 NADH (—). Before each scan, the electrode was held at -0.3 V for 3 min to ensure complete reduction of the film.

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