Phosphoenolpyruvate carboxykinase formation

Fig. 5 Speculative metabolic schemes of the main pathways in carbohydrate metabolism in Trimyema compressum (after Goosen et al. 1990). End products are in boxes. Abbreviations AcCoA, acetyl-Co A, Hyd, hydrogenase, PEP, phosphoenolpyruvate carboxykinase, PFL, pyruvate formate lyase, PFO, pyruvate ferredoxin oxidoreductase, PYR, pyruvate, Xox, red> unknown electron carrier...

Biotin acts to induce glucokinase, phosphofructokinase, and pyruvate kinase (key enzymes of glycolysis), phosphoenolpyruvate carboxykinase (a key enzyme of gluconeogenesis), and holocarboxylase synthetase, acting via a cell-surface receptor linked to formation of cGMP and increased activity of RNA polymerase. The activity of holocarboxylase synthetase (Section 11.2.2) falls in experimental biotin deficiency and increases with a parallel increase in... 

Finally, oxaloacetate is simultaneously decarboxylated andphosphorylated by phosphoenolpyruvate carboxykinase in the cytosol. The CO2 that vv as added to pyruvate by pyruvate carboxylase comes off in this step. Recall that, in glycolysis, the presence of a phosphoryl group traps the unstable enol isomer of pyruvate as phosphoenolpyruvate (Section 16.1.7). In gluconeogenesis, the formation of the unstable enol is driven by decarboxylation—the oxidation of the carboxylic acid to CO2 —and trapped by the addition of a phosphate to carbon 2 from GTP. The two-step pathway... 

Finally, oxaloacetate is simultaneously decarboxylated and phosphorylated by phosphoenolpyruvate carboxykinase in the cytosol. The CO2 that was added to pyruvate by pyruvate carboxylase comes off in this step. Recall that, in glycolysis, the presence of a phosphoryl group traps the unstable enol isomer of pyruvate as phosphoenolpyruvate (Section 16.1.7). In gluconeogenesis, the formation of the unstable enol is driven by decarboxylation—the oxidation of the carboxylic acid to CO2—and trapped by the addition of a phosphate to carbon 2 from GTP. The two-step pathway for the formation of phosphoenolpyruvate from pyruvate has a AG° of + 0.2 kcal mol ( + 0.13 kj moP ) in contrast with +7.5 kcal mol ( + 31 kj mol ) for the reaction catalyzed by pyruvate kinase. The much more favorable AG° for the two-step pathway results from the use of a molecule of ATP to add a molecule of CO2 in the carboxylation step that can be removed to power the formation of phosphoenolpyruvate in the decarboxylation step. Decarboxylations often drive reactions otherwise highly endergonic. This metabolic motif is used in the citric acid cycle (Section IS.x.x), the pentose phosphate pathway (Section 17.x.x), and fatty acid synthesis (Section 22.x.x). 

The carboxylation reaction produces an activated carboxyl group in the form of a high-energy carboxybiotin intermediate. The cleavage of this bond and release of CO2 in the phosphoenolpyruvate carboxykinase reaction or the transfer of the CO2 to acceptors in other reactions in which biotin participates allows endergonic reactions to proceed. Thus, the formation of phosphoenolpyruvate from oxaloacetate is driven by the release of CO2 (AG° = -4.7 kcal/mol) and the hydrolysis of GTP (AG° = -7.3 kcal/mol). 

The correlation between CA formation and manganese limitation in A. niger was studied through transcriptome and proteome profiling. Beside the three already described responses, two novel responses were observed, including strong down regulation of phosphoenolpyruvate carboxykinase (PEPCK) and two cation transporters. ... 

Anaplerotic reactions refer to C3-carboxylation and C4-decarboxylation around the phosphoenolpyruvate-pyruvate-oxaloacetate node, which interconnect the TCA cycle with glycolysis. These reactions result in direct oxaloacetate formation or depletion. Carboxylation of phosphoenolpyruvate catalyzed by phosphoenolpyruvate carboxylase and that of pyruvate by pyruvate carboxylase contribute to its formation. Accordingly, decarboxylation of oxaloacetate catalyzed by phosphoenolpyruvate carboxykinase and oxaloacetate decarboxylase form phosphoenolpyruvate and... 

Fig. 10.9. Role of malic acid in the production of energy (ATP) and the formation of different substrates in the grape (Ruffner, 1982b). MDH, malate dehydrogenase ME, malic enzyme PEPC, phosphoenolpyruvate carboxylase PEPCK, phosphoenolpyruvate carboxykinase...

Cocoa bean fermentation is a mixed-culture process, consisting initially of fermentations by yeast and lactic acid bacteria followed by oxidation of the fermentation products ethanol and lactic acid into acetic acid and acetoin by several Acetohacter strains, of which /I. pasteurianus is the prominent one (Moens et al. 2014). A C-based carbon flux analysis of Acetohacter during cocoa pulp fermentation-simulating conditions revealed a functionally separated metabolism during co-consumption of ethanol and lactate. Acetate was almost exclusively derived from ethanol, whereas lactate served for formation of acetoin and biomass building blocks. This switch was attributed to the lack of phosphoenolpyruvate carboxykinase and malic enzyme activities, which prevents conversion of oxalo-acetate and malate formed by acetate metabolism in the TCA cycle to PEP and pyruvate and subsequently to acetoin (Adler et al. 2014). Lactate, on the other hand, can be converted to pyruvate, which is then used for acetoin formation or, after conversion to PEP by pymvate phosphate dikinase, for gluconeogenesis. The inability of conversion of TCA cycle intermediates to PEP resembles the situation in G. oxydans, where in addition no enzyme for conversion of pyruvate to PEP is present. 

The oxidative decarboxylation reaction above is part of the TCA cycle and leads to the formation of oxaloacetate, which maybe used to synthesize citrate (with acetyl-CoA) or may be used as a substrate by phosphoenol pyruvate carboxykinase, PEPCK. It should be noted that the phosphoenolpyruvate generated by PEPCK reaction shown above is... 

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