Total synthesis of acetate from carbon dioxide. VI. Retention of deuterium during carboxylation of trideuteriomethyltetrahydrofolate or trideuteriomethylcobalamin

Parker, Donald J.; Wood, Harland G.; Ghambeer, R. K.; Ljungdahl, Lars G.

doi:10.1021/bi00766a021

Cited by 22 publications

(5 citation statements)

References 24 publications

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“…Furthermore, in the mid-1980’s, it was unclear whether the methyl group reacted as an anion as a cation. Since alkylcobamides had been considered to act as biological Grignard reagents [79] (although we now recognize that the alkyl group is actually transferred as an carbocation, i.e., CH 3 + [80]), a mechanism of acetate synthesis involving attack of the methyl carbanion on a carboxy group, forming an acetoxycorrinoid was proposed [81]. This mechanism was based partly on the finding that M. thermoacetica extracts catalyzed the incorporation of approximately 50% of the deuterium from CD 3 -H 4 folate or [CD 3 ]-methylcobalamin to trideuteromethyl-acetate.…”

Section: Importance Of the Wood-ljungdahl Pathwaymentioning

confidence: 99%

Acetogenesis and the Wood–Ljungdahl pathway of CO2 fixation

Ragsdale

Pierce

2008

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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816

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I. SummaryConceptually, the simplest way to synthesize an organic molecule is to construct it one carbon at a time. The Wood-Ljungdahl pathway of CO 2 fixation involves this type of stepwise process. The biochemical events that underlie the condensation of two one-carbon units to form the two-carbon compound, acetate, have intrigued chemists, biochemists, and microbiologists for many decades. We begin this review with a description of the biology of acetogenesis. Then, we provide a short history of the important discoveries that have led to the identification of the key components and steps of this usual mechanism of CO and CO 2 fixation. In this historical perspective, we have included reflections that hopefully will sketch the landscape of the controversies, hypotheses, and opinions that led to the key experiments and discoveries. We then describe the properties of the genes and enzymes involved in the pathway and conclude with a section describing some major questions that remain unanswered.

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Section: Importance Of the Wood-ljungdahl Pathwaymentioning

confidence: 99%

Acetogenesis and the Wood–Ljungdahl pathway of CO2 fixation

Ragsdale

Pierce

2008

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

1,060

816

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“…transferred to a corrinoid-protein, after which carboxylation occurs with the formation of acetate. Evidence for the pathway of synthesis of acetate from CO2 has been reviewed (27) and has been presented in more recent publications (14,32,33).…”

Section: Downloaded Frommentioning

confidence: 99%

Fermentation of Glucose, Fructose, and Xylose by Clostridium thermoaceticum : Effect of Metals on Growth Yield, Enzymes, and the Synthesis of Acetate from CO ₂

et al. 1973

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Clostridium thermoaceticum ferments xylose, fructose, and glucose with acetate as the only product. In fermentations with mixtures of the sugars, xylose is first fermented, then fructose, and last, glucose. Fructose inhibits the fermentation of glucose, and this inhibition appears to be due to a repression of the synthesis of an enzyme needed for glucose utilization. Addition of metals to the culture medium increases the cell yield drastically from about 7 to 18 g per liter, and Y(glucose) values between 40 and 50 are obtained. According to the postulated pathways of the fermentation of glucose and synthesis of acetate from CO2 by C. thermoaceticum, 3 mol of ATP are available as energy for growth. Thus a Y(adenosine 5'-triphosphate) of 13 to 16 is obtained. Because the normal Y(ATP) value is 10.5, this could mean that an additional source of ATP is available by an unknown mechanism. The addition of metals also increases the nicotinamide adenine dinucleotide phosphate-dependent formate dehydrogenase activity, the overall reaction ("CO2-p acetate), and the incorporation of the

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“…(see Scheme I [3] [6a] [7b]). Further support was also obtained [l] [5b] concerning the involvement of vitamin B,, derivatives as intervening CH,-group carriers in bacterial acetate synthesis from 2 CO,'), discovered earlier by way of the (intact [9]) incorporation of the cobalt-bound CH,-group of methyl-cobalamin (1) during acetate biosynthesis in Clostridium thermoaceticum [ …”

Section: Discussionmentioning

confidence: 65%

Acetyl‐cobalamin from Photoinduced Carbonylation of Methyl‐cobalamin

Kräutler

1984

Helvetica Chimica Acta

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SummaryIrradiation with visible light of a deoxygenated aqueous solution of methyl-cobalamin (1) under an atmosphere of CO and at ambient temperature converts 1 into acetyl-cobalamin (2). This carbonylation has potential relevance with respect to bacterial acetate biosynthesis from CO,.Thauer recently suggested') bacterial synthesis of CH,COOH (or of a coenzyme A bound CH,CO-group) from two CO, to proceed via carbonylution of methyl-Co (111)-corrinoids analogous to methyl-cobalamin (1). This contrasted with earlier proposals, where C-C bond formation in the course of bacterial acetate synthesis from CO, was considered to occur by carboxylation of vitamin B,, derivatives (reviewed in [I] [l] [5b] concerning the involvement of vitamin B,, derivatives as intervening CH,-group carriers in bacterial acetate synthesis from 2 CO,'), discovered earlier by way of the (intact [9]) incorporation of the cobalt-bound CH,-group of methyl-cobalamin (1) during acetate biosynthesis in Clostridium thermoaceticum [ 101.On the other hand, for the presumed participation of methyl-cobyrinates in the assembly of the CH,CO-group from 'one-carbon' precursors, a chemical model has not yet been established (experimentally). In particular, a carboxylation of the axial CH,-group of the organo-corrinate was considered originally [ 11 [I I] as the C-C bond forming step, but in extensive (non-enzymatic) studies with methyl-Co(II1)-corrinoids and with CO,, formation of CH,COOH was achieved merely as a minor, barely detec-I)

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Total synthesis of acetate from carbon dioxide. VI. Retention of deuterium during carboxylation of trideuteriomethyltetrahydrofolate or trideuteriomethylcobalamin

Cited by 22 publications

References 24 publications

Acetogenesis and the Wood–Ljungdahl pathway of CO2 fixation

Acetogenesis and the Wood–Ljungdahl pathway of CO2 fixation

Fermentation of Glucose, Fructose, and Xylose by Clostridium thermoaceticum : Effect of Metals on Growth Yield, Enzymes, and the Synthesis of Acetate from CO ₂

Acetyl‐cobalamin from Photoinduced Carbonylation of Methyl‐cobalamin

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Total synthesis of acetate from carbon dioxide. VI. Retention of deuterium during carboxylation of trideuteriomethyltetrahydrofolate or trideuteriomethylcobalamin

Cited by 22 publications

References 24 publications

Acetogenesis and the Wood–Ljungdahl pathway of CO2 fixation

Acetogenesis and the Wood–Ljungdahl pathway of CO2 fixation

Fermentation of Glucose, Fructose, and Xylose by Clostridium thermoaceticum : Effect of Metals on Growth Yield, Enzymes, and the Synthesis of Acetate from CO 2

Acetyl‐cobalamin from Photoinduced Carbonylation of Methyl‐cobalamin

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Fermentation of Glucose, Fructose, and Xylose by Clostridium thermoaceticum : Effect of Metals on Growth Yield, Enzymes, and the Synthesis of Acetate from CO ₂