Carbon Dioxide Fixation Catalyzed

Carbon Dioxide Fixation Catalyzed by Metal Complexes Koji Tanaka... 

CARBON DIOXIDE FIXATION CATALYZED BY METAL COMPLEXES... 

Leitner, W. Carbon-Dioxide as a Raw-Material - The Synthesis of Formic-Acid and Its Derivatives from CO2, Angew. Chem. Int. Ed. Engl. 1995, 34, 2207. (c) Tanaka, K. Carbon dioxide fixation catalyzed by metal complexes Adv. Inorg. Chem. 1995, 43, 409. (d) Ayers, W. M. Ed. Catalytic Activation of Carbon Dioxide, ACS Symposium Series 363, Washington, DC 1988. (e)... 

The way biotin participates in carbon dioxide fixation was established in the early 1960s. In 1961 Kaziro and Ochoa using propionyl CoA carboxylase provided evidence for 14C02 binding in an enzyme-biotin complex. With excess propionyl CoA the 14C label moved into a stable position in methyl malonyl CoA. In the same year Lynen found biotin itself could act as a C02 acceptor in a fixation reaction catalyzed by B-methylcrotonyl CoA carboxylase. The labile C02 adduct was stabilized by esterification with diazomethane and the dimethyl ester shown to be identical with the chemically synthesized molecule. X-ray analysis of the bis-p-bromanilide confirmed the carbon dioxide had been incorporated into the N opposite to the point of attachment of the side chain. Proteolytic digestion and the isolation of biocytin established the biotin was bound to the e-NH2 of lysine. 

Carbon dioxide fixation is catalyzed by the enzyme ribulosebisphosphatecar-boxylase oxygenase (RuBisCO), which is the most abundant natural enzyme worldwide, and the least selective. In fact, RuBisCO does not follow the usual selectivity of enzymes, and at the same time promotes the carboxylation of ribulose (a C-5 sugar) to afford a C-6 sugar (with carbon fixation) and the oxidation of the same C-5 sugar, with a selectivity close to 50% [2]. 

Biocatalytic synthetic reactions also include carbon dioxide fixation with the production of methanol in artificial multi-enzyme systems [188]. Formate dehydrogenase (FDH, EC 1.2.1.2) can catalyze the reduction of carbon dioxide to formate, and methanol dehydrogenase (MDH, EC 1.1.99.8) can catalyze the reduction of formate to methanol. Both of these enzymes require NAD+-NADE1 cofactor, and in the presence of the reduced dimethyl viologen mediator (MV+), they can drive a sequence of enzymatic reactions. The cascade of biocatalytic reactions results in the reduction of CO2 to formate catalyzed by FDEI followed by the reduction of formate to methanol catalyzed by MDH. A more complex system composed of immobilized cells of Parococcus denitrificans has been demonstrated for the reduction of nitrate and nitrite [189]. 

Biotin is a coenzyme for the carbon dioxide fixation reactions catalyzed by acetyl-CoA carboxylase (Chapter 19), propionyl-CoA carboxylase, pyruvate carboxylase, and S-methylcrotonyl-CoA carboxylase. Car-boxylation reactions that do not require biotin are the addition of Ce to the purine ring (Chapter 27), the formation of carbamoyl phosphate (Chapter 17), and the y-carboxylation of glutamyl residues of several of the clotting factors, which requires vitamin K (Chapter 36). 

RuBP is the intermediate of the Calvin cycle onto which C02 is added in the process of carbon dioxide fixation. The reaction below -is catalyzed by the enzyme called 0 rubisco... 

Superoxide radicals are inevitably photoproduced in chloroplasts, and hydrogen peroxide is formed from superoxide. Hydrogen peroxide not only inhibits the enzymes for the cycle of carbon dioxide fixation, but also produces the hydroxyl radical by metal-catalyzed Haber-Weiss reaction (1). AsA peroxidase takes an important part in scavenging hydrogen peroxide in chloroplasts (1), which lack catalase and glutathione peroxidase (2). We have purified two types of AsA peroxidase from tea leaves (3), and one of them (isoz3nne II) is localized in chloroplasts (4, Chen and Asada, unpublished). 

An extract has been prepared from spinach leaves which catalyzes the formation of D-ribulose diphosphate from adenosine triphosphate and D-ribose 5-phosphate (225). The D-ribulose diphosphate appears to be an intermediate in a carbon dioxide fixation system in which D-ribose 5-phosphate was the added substrate (226). 

Tsuda T (1995) Utilization of carbon dioxide in organic synthesis and polymer synthesis by the transition metal-catalyzed carbon dioxide fixation into unsaturated hydrocarbons. Gazz Chim Ital 125 101-110... 

In reaction (10), carbon dioxide was added to AIR to produce the car-boxylated product of AIR (carboxy-AIR) (Fig. 10). It is not known whether carbon dioxide or bicarbonate was the actual substrate for this condensation. An interesting feature of this reaction was the absence of a requirement for ATP. Other carbon dioxide fixation reactions were found to be coupled with TPNH oxidation 1S7,128), participation of phosphate 129, ISO), or degradation of ATP ISl). The enzyme which catalyzed reaction (10) was called AIR-carboxylase, and has been partially purified 1S2). In the next step [Eq. (11)] succino-AICAR was formed when carboxy-AIR reacted with aspartic acid and ATP other nucleoside triphosphates such as GTP, uridine triphosphate (UTP), CTP were ineffective in replacing ATP. This finding of ATP speiMcity may be contrasted with the specific... 

Y.-M. Shen, W.-L. Duan, M. Shi, Chemical fixation of carbon dioxide co-catalyzed by a combination of Schiff bases or phenols and organic bases, Eur. J. Qrg. Chem. (2004) 3080-3089. 

Bai, D. Duan, S. Hai, L. Jing, H. Carbon Dioxide Fixation by Cycloaddition with Epoxides, Catalyzed by Biomimetic Metalloporphyrins. Chem Cat Chem. 2012, 4, 1752-1758. 

Equations 1 to 3 show some of fixation reactions of carbon dioxide. Equations la and lb present coupling reactions of CO2 with diene, triene, and alkyne affording lactone and similar molecules [2], in a process catalyzed by low valent transition metal compounds such as nickel(O) and palladium(O) complexes. Another interesting CO2 fixation reaction is copolymerization of CO2 and epoxide yielding polycarbonate (equation 2). This reaction is catalyzed by aluminum porphyrin and zinc diphenoxide [3],... 

The light independent reactions take place in the stroma with the help of ATP and NADPH. In a process called the Calvin-Benson cycle, or carbon fixation, carbon dioxide from the atmosphere is captured and converted into carbohydrates [135]. The reaction is catalyzed by the enzyme RuBisCO (ribulose-1,5-biphosphate... 

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