Citrate process

Activation of acetyl-CoA carboxylase from rat liver in vitro. Citrate activates the enzyme and converts it to a polymer. Either palmitoyl-CoA or malonyl-CoA can reverse this process. Citrate does not activate or polymerize the E. coli enzyme. 

In the first control point, citrate synthase catalyzes the condensation of acetyl-CoA with oxaloacetate to produce citrate (AG° = -32.2 kJ mol ). Although the reaction is reversible, the equilibrium lies very much in favor of citrate formation because of the hydrolysis of a bond in the intermediate compound, citroyl-CoA (Fig. 12-4). Citroyl-CoA is bound to citrate synthase, and the hydrolysis of the thioester bond, to produce citrate and coenzyme A, is an exergonic process. Citrate synthase is inhibited by its substrates (acetyl-CoA and oxaloacetate), and its activity is affected by... 

Two nucleation processes important to many people (including some surface scientists ) occur in the formation of gallstones in human bile and kidney stones in urine. Cholesterol crystallization in bile causes the formation of gallstones. Cryotransmission microscopy (Chapter VIII) studies of human bile reveal vesicles, micelles, and potential early crystallites indicating that the cholesterol crystallization in bile is not cooperative and the true nucleation time may be much shorter than that found by standard clinical analysis by light microscopy [75]. Kidney stones often form from crystals of calcium oxalates in urine. Inhibitors can prevent nucleation and influence the solid phase and intercrystallite interactions [76, 77]. Citrate, for example, is an important physiological inhibitor to the formation of calcium renal stones. Electrokinetic studies (see Section V-6) have shown the effect of various inhibitors on the surface potential and colloidal stability of micrometer-sized dispersions of calcium oxalate crystals formed in synthetic urine [78, 79]. 

Definitive SO Control Process Evaluation Eimestone Double Alkali and Citrate EGD Process, EPA Pub. EPA-600/7-79-177, Aug. 1979. 

The complete chemistry of TSP production has been studied and reported in great detail (34). As in the production of NSP there are also reactions with impurity minerals. In fact, the increasing amounts of such impurities in U.S. commercial phosphate rocks, especially those from Florida, are now reflected in somewhat lowered amounts of citrate-soluble P2O5 product. The range of constituents in commercial TSP from wet-process acid and phosphate... 

Resorcinol or hydroquinone production from m- or -diisopropylben2ene [100-18-5] is realized in two steps, air oxidation and cleavage, as shown above. Air oxidation to obtain the dihydroperoxide (DHP) coproduces the corresponding hydroxyhydroperoxide (HHP) and dicarbinol (DC). This formation of alcohols is inherent to the autooxidation process itself and the amounts increase as DIPB conversion increases. Generally, this oxidation is carried out at 90—100°C in aqueous sodium hydroxide with eventually, in addition, organic bases (pyridine, imidazole, citrate, or oxalate) (8) as well as cobalt or copper salts (9). 

Two and twelve moles of ATP are produced, respectively, per mole of glucose consumed in the glycolytic pathway and each turn of the Krebs (citrate) cycle. In fat metaboHsm, many high energy bonds are produced per mole of fatty ester oxidized. Eor example, 129 high energy phosphate bonds are produced per mole of palmitate. Oxidative phosphorylation has a remarkable 75% efficiency. Three moles of ATP are utilized per transfer of two electrons, compared to the theoretical four. The process occurs via a series of reactions involving flavoproteins, quinones such as coenzyme Q, and cytochromes. 

Calcium is essential to several steps in the enzyme cascade of the blood clotting process, such as the conversion of prothrombin to thrombin (23). Clotting can be inhibited in stored blood suppHes by addition of complexing agents such as EDTA or citrate which reduce the levels of the free ion, Ca(Il). 

Chelate Formation. Citric acid complexes with many multivalent metal ions to form chelates (9,10). This important chemical property makes citric acid and citrates useful in controlling metal contamination that can affect the color, stabiUty, or appearance of a product or the efficiency of a process. 

Lime-Sulfuric. Recovery of citric acid by calcium salt precipitation is shown in Figure 3. Although the chemistry is straightforward, the engineering principles, separation techniques, and unit operations employed result in a complex commercial process. The fermentation broth, which has been separated from the insoluble biomass, is treated with a calcium hydroxide (lime) slurry to precipitate calcium citrate. After sufficient reaction time, the calcium citrate slurry is filtered and the filter cake washed free of soluble impurities. The clean calcium citrate cake is reslurried and acidified with sulfuric acid, converting the calcium citrate to soluble citric acid and insoluble calcium sulfate. Both the calcium citrate and calcium sulfate reactions are generally performed in agitated reaction vessels made of 316 stainless steel and filtered on commercially available filtration equipment. 

Pasteurized Process Cheese. Sodium citrate is used in pasteurized process and sHced cheese as an emulsifying salt to stabilize the water and oil emulsion and improve process cheese body and texture (64). 

J. B. Rosenbaum, D. R. George, and L. Crocker, "The Citrate Process for Removing SO2 and Recoveriag Sulfur from Waste Gases," paper presented at the MIME Environmental Quality Conference, Washiagton, D.C., June 7—9,1971. 

Of the removal processes that have attained commercial status, the current favorite employs a shiny of lime or limestone. The activity of the reagent is promoted by the addition of small amounts of carboxylic acids such as adipic acid. The gas and the shiny are contacted in a spray tower. The calcium salt is discarded. A process that employs aqueous sodium citrate, however, is suited for the recoveiy of elemental sulfur. The citrate solution is regenerated and recycled. (Kohl and Riesenfeld, Gas Purification, Gulf, 1985, p. 356.)... 

Citrate process Copper oxide adsorption Caustic scrubbing... 

Citrate is isomerized to isocitrate by aconitase in a two-step process involving aconitate as an intermediate (Figure 20.7). In this reaction, the elements... 

Finally, citrate can be exported from the mitochondria and then broken down by ATP-citrate lyase to yield oxaloacetate and acetyl-CoA, a precursor of fatty acids (Figure 20.23). Oxaloacetate produced in this reaction is rapidly reduced to malate, which can then be processed in either of two ways it may be transported into mitochondria, where it is reoxidized to oxaloacetate, or it may be oxidatively decarboxylated to pyruvate by malic enzyme, with subse-... 

It may seem surprising that isocitrate dehydrogenase is strongly regulated, because it is not an apparent branch point within the TCA cycle. However, the citrate/isocitrate ratio controls the rate of production of cytosolic acetyl-CoA, because acetyl-CoA in the cytosol is derived from citrate exported from the mitochondrion. (Breakdown of cytosolic citrate produces oxaloacetate and acetyl-CoA, which can be used in a variety of biosynthetic processes.) Thus, isocitrate dehydrogenase activity in the mitochondrion favors catabolic TCA cycle activity over anabolic utilization of acetyl-CoA in the cytosol. 

Ketone body synthesis occurs only in the mitochondrial matrix. The reactions responsible for the formation of ketone bodies are shown in Figure 24.28. The first reaction—the condensation of two molecules of acetyl-CoA to form acetoacetyl-CoA—is catalyzed by thiolase, which is also known as acetoacetyl-CoA thiolase or acetyl-CoA acetyltransferase. This is the same enzyme that carries out the thiolase reaction in /3-oxidation, but here it runs in reverse. The second reaction adds another molecule of acetyl-CoA to give (i-hydroxy-(i-methyl-glutaryl-CoA, commonly abbreviated HMG-CoA. These two mitochondrial matrix reactions are analogous to the first two steps in cholesterol biosynthesis, a cytosolic process, as we shall see in Chapter 25. HMG-CoA is converted to acetoacetate and acetyl-CoA by the action of HMG-CoA lyase in a mixed aldol-Claisen ester cleavage reaction. This reaction is mechanistically similar to the reverse of the citrate synthase reaction in the TCA cycle. A membrane-bound enzyme, /3-hydroxybutyrate dehydrogenase, then can reduce acetoacetate to /3-hydroxybutyrate. 

Ammoniated citric acid (pH 10)/air, sodium nitrite or bromate (Citrosolve process). This is a multiple-step process, first using ammoniated citric acid (approximately monoammonium citrate)... 

Citrate/iron/nitrite passivator The Citrosolve process using air or 0.5 to 1.0% NaNOz or NaBr03. 

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