Synergistic inhibition of phosphoenolpyruvate carboxylase by aspartate and 2-oxoglutarate in Brevibacterium flavum. 1985

M Mori, and I Shiio

Purification procedures for phosphoenolpyruvate carboxylase from B. flavum were improved by using hydrophobic chromatography. The carboxylase showed optimum pH values of 7.2 and 8.0 with Mn2+ and Mg2+ as metallic activators, respectively. Purified phosphoenolpyruvate carboxylase was found to be synergistically inhibited by aspartate and 2-oxoglutarate in the absence or presence of an activator, acetyl-CoA. Similarly to the aspartate inhibition, 2-oxoglutarate alone inhibited the enzyme competitively with respect to both substrates, with an inhibitor constant of 4.7 mM. The dissociation constant for the combination of enzyme-2-oxoglutarate (-aspartate) complex with aspartate (2-oxoglutarate) was found to be one-third of that for the combination of the enzyme with aspartate (2-oxoglutarate). The Hill coefficient for phosphoenolpyruvate was increased from 1.0 to 2.3 by the simultaneous addition of the two inhibitors in a certain concentration range of phosphoenolpyruvate where strong synergistic effects were observed. Outside this concentration range, the coefficient was not altered or was slightly increased by the addition of aspartate, 2-oxoglutarate, or both. The synergistic action seems to be caused by these effects, in addition to the decrease in dissociation constants of the inhibitors. Hill coefficients for aspartate and 2-oxoglutarate were both approximately 2.0. The coefficient for one inhibitor did not vary with the addition of the other inhibitor. Although many structural analogues of the two inhibitors, such as 2-oxoadipate and 3-hydroxyaspartate, were very weak inhibitors, their synergistic effects with aspartate or 2-oxoglutarate were comparable to the effects of the two natural inhibitors. On the other hand, malate and succinate, which markedly inhibited the enzyme, did not show synergistic action with aspartate or 2-oxoglutarate. Hill coefficients for the structural analogues showing synergistic effects were approximately 2.0 or above, whereas those for malate and succinate, which did not enhance the inhibitions, were about 1.0. Phosphoenolpyruvate carboxylase from an aspartate-producing mutant had the inhibitor constant of 5.8 mM for 2-oxoglutarate, i.e., slightly higher than wild-type enzyme. The inhibitor constant for aspartate was three times higher than that of the wild-type enzyme as reported previously. The dissociation constant for aspartate of the enzyme-aspartate-2-oxoglutarate complex in the mutant enzyme was 8 times that in the wild-type enzyme, indicating that weaker synergistic inhibition was observed with the mutant enzyme.

UI MeSH Term Description Entries
D007656 Ketoglutaric Acids A family of compounds containing an oxo group with the general structure of 1,5-pentanedioic acid. (From Lehninger, Principles of Biochemistry, 1982, p442) Oxoglutarates,2-Ketoglutarate,2-Ketoglutaric Acid,2-Oxoglutarate,2-Oxoglutaric Acid,Calcium Ketoglutarate,Calcium alpha-Ketoglutarate,Ketoglutaric Acid,Oxogluric Acid,alpha-Ketoglutarate,alpha-Ketoglutaric Acid,alpha-Ketoglutaric Acid, Calcium Salt (2:1),alpha-Ketoglutaric Acid, Diammonium Salt,alpha-Ketoglutaric Acid, Dipotassium Salt,alpha-Ketoglutaric Acid, Disodium Salt,alpha-Ketoglutaric Acid, Monopotassium Salt,alpha-Ketoglutaric Acid, Monosodium Salt,alpha-Ketoglutaric Acid, Potassium Salt,alpha-Ketoglutaric Acid, Sodium Salt,alpha-Oxoglutarate,2 Ketoglutarate,2 Ketoglutaric Acid,2 Oxoglutarate,2 Oxoglutaric Acid,Calcium alpha Ketoglutarate,alpha Ketoglutarate,alpha Ketoglutaric Acid,alpha Ketoglutaric Acid, Diammonium Salt,alpha Ketoglutaric Acid, Dipotassium Salt,alpha Ketoglutaric Acid, Disodium Salt,alpha Ketoglutaric Acid, Monopotassium Salt,alpha Ketoglutaric Acid, Monosodium Salt,alpha Ketoglutaric Acid, Potassium Salt,alpha Ketoglutaric Acid, Sodium Salt,alpha Oxoglutarate,alpha-Ketoglutarate, Calcium
D007700 Kinetics The rate dynamics in chemical or physical systems.
D008274 Magnesium A metallic element that has the atomic symbol Mg, atomic number 12, and atomic weight 24.31. It is important for the activity of many enzymes, especially those involved in OXIDATIVE PHOSPHORYLATION.
D008293 Malates Derivatives of malic acid (the structural formula: (COO-)2CH2CHOH), including its salts and esters.
D008345 Manganese A trace element with atomic symbol Mn, atomic number 25, and atomic weight 54.94. It is concentrated in cell mitochondria, mostly in the pituitary gland, liver, pancreas, kidney, and bone, influences the synthesis of mucopolysaccharides, stimulates hepatic synthesis of cholesterol and fatty acids, and is a cofactor in many enzymes, including arginase and alkaline phosphatase in the liver. (From AMA Drug Evaluations Annual 1992, p2035)
D010730 Phosphoenolpyruvate Carboxylase An enzyme with high affinity for carbon dioxide. It catalyzes irreversibly the formation of oxaloacetate from phosphoenolpyruvate and carbon dioxide. This fixation of carbon dioxide in several bacteria and some plants is the first step in the biosynthesis of glucose. EC 4.1.1.31. Carboxylase, Phosphoenolpyruvate
D001951 Brevibacterium A gram-positive organism found in dairy products, fresh and salt water, marine organisms, insects, and decaying organic matter.
D002262 Carboxy-Lyases Enzymes that catalyze the addition of a carboxyl group to a compound (carboxylases) or the removal of a carboxyl group from a compound (decarboxylases). EC 4.1.1. Carboxy-Lyase,Decarboxylase,Decarboxylases,Carboxy Lyase,Carboxy Lyases
D004357 Drug Synergism The action of a drug in promoting or enhancing the effectiveness of another drug. Drug Potentiation,Drug Augmentation,Augmentation, Drug,Augmentations, Drug,Drug Augmentations,Drug Potentiations,Drug Synergisms,Potentiation, Drug,Potentiations, Drug,Synergism, Drug,Synergisms, Drug
D006863 Hydrogen-Ion Concentration The normality of a solution with respect to HYDROGEN ions; H+. It is related to acidity measurements in most cases by pH pH,Concentration, Hydrogen-Ion,Concentrations, Hydrogen-Ion,Hydrogen Ion Concentration,Hydrogen-Ion Concentrations

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