Carbon dioxide, enzymatic

Protonated and diprotonated carbonic acid and carbon dioxide may also have implications in biological carboxylation processes. Although behavior in highly acidic solvent systems cannot be extrapolated to in vivo conditions, related multidentate interactions at enzymatic sites are possible. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

In keeping with its biogenetic origin m three molecules of acetic acid mevalonic acid has six carbon atoms The conversion of mevalonate to isopentenyl pyrophosphate involves loss of the extra carbon as carbon dioxide First the alcohol hydroxyl groups of mevalonate are converted to phosphate ester functions—they are enzymatically phosphorylated with introduction of a simple phosphate at the tertiary site and a pyrophosphate at the primary site Decarboxylation m concert with loss of the terti ary phosphate introduces a carbon-carbon double bond and gives isopentenyl pyrophos phate the fundamental building block for formation of isoprenoid natural products... 

A non-linear regression analysis is employed using die Solver in Microsoft Excel spreadsheet to determine die values of and in die following examples. Example 1-5 (Chapter 1) involves the enzymatic reaction in the conversion of urea to ammonia and carbon dioxide and Example 11-1 deals with the interconversion of D-glyceraldehyde 3-Phosphate and dihydroxyacetone phosphate. The Solver (EXAMPLEll-l.xls and EXAMPLEll-3.xls) uses the Michaehs-Menten (MM) formula to compute v i- The residual sums of squares between Vg(,j, and v j is then calculated. Using guessed values of and the Solver uses a search optimization technique to determine MM parameters. The values of and in Example 11-1 are ... 

Through a series of enzymatic steps, carbon dioxide and water undergo photosynthesis to produce glucose and oxygen according to the equation... 

Details are given of the enzymatic transformation of polycaprolactone into repolymerisable oligomers in supercritical carbon dioxide. The object was to establish a sustainable chemical recycling system for polycaprolactone. 14 refs. 

Campbell LL (1960) Rednctive degradation of pyrimidines V. Enzymatic conversion of V-carbamoyl- 3-alanine to [5-alanine, carbon dioxide, and ammonia. J Biol Chem 235 2375-2378. 

PGA degrades by hydrolysis to produce carbon dioxide and glycolic acid (Fig. 13.1.2), which is either excreted or enzymatically converted to other metabo-... 

The same authors proposed a complex system for the electrochemically driven enzymatic reduction of carbon dioxide to form methanol. In this case, methyl viologen or the cofactor PQQ were used as mediators for the electroenzymatic reduction of carbon dioxide to formic acid catalyzed by formate dehydrogenase followed by the electrochemically driven enzymatic reduction of formate to methanol catalyzed by a PQQ-dependent alcohol dehydrogenase. With methyl viologen as mediator, the reaction goes through the intermediate formation of formaldehyde while with PQQ, methanol is formed directly [77],... 

An enzyme is a protein that speeds up a biochemical reaction without itself experiencing any overall change. In chemical language, such a compound is called a catalyst and is said to catalyze a reaction. Chemists employ a variety of compounds as laboratory catalysts, and many industrial chemical processes would be impracticably slow without catalysis. An automobile s catalytic converter makes use of a metal catalyst to accelerate conversion of toxic carbon monoxide in the exhaust to carbon dioxide. Similarly, our bodies biochemical machinery effects thousands of different reactions that would not proceed without enzymatic catalysis. Some enzymes are exquisitely specific, catalyzing only one particular reaction of a single compound. Many others have much less exacting requirements and consequently exhibit broader effects. Specific or nonspecific, enzymes can make reactions go many millions of times faster than they would without catalysis. 

Another environmental issue is the use of organic solvents. The use of chlorinated hydrocarbons, for example, has been severely curtailed. In fact, so many of the solvents favored by organic chemists are now on the black list that the whole question of solvents requires rethinking. The best solvent is no solvent, and if a solvent (diluent) is needed, then water has a lot to recommend it. This provides a golden opportunity for biocatalysis, since the replacement of classic chemical methods in organic solvents by enzymatic procedures in water at ambient temperature and pressure can provide substantial environmental and economic benefits. Similarly, there is a marked trend toward the application of organometal-lic catalysis in aqueous biphasic systems and other nonconventional media, such as fluorous biphasic, supercritical carbon dioxide and ionic liquids. ... 

The metabolism of chloroform is well understood. Approximately 50% of an oral dose of 0.5 grams of chloroform was metabolized to carbon dioxide in humans (Fry et al. 1972). Metabolism was dose-dependent, decreasing with higher exposure. A first-pass effect was observed after oral exposure (Chiou 1975). Approximately 38% of the dose was converted in the liver, and < 17% was exhaled unchanged from the lungs before reaching the systemic circulation. On the basis of pharmacokinetic results obtained in rats and mice exposed to chloroform by inhalation, and of enzymatic studies in human tissues in vitro, in vivo metabolic rate constants (V, 3,C =15.7 mg/hour/kg, = 0.448 mg/L) were defined for humans (Corley et al. 1990). The metabolic activation of chloroform to its toxic intermediate, phosgene, was slower in humans than in rodents. 

Berger R, Libby WE. 1969. Equilibration of atmospheric carbon dioxide with sea water possible enzymatic control of the arte. Science 164 1395-1398. 

Biological. Complete microbial degradation to carbon dioxide was reported under anaerobic conditions by mixed or pure cultures. Under enzymatic conditions formaldehyde was the only product reported (Vogel et al., 1987). In a static-culture-flask screening test, methylene chloride (5 and 10 mg/L) was statically incubated in the dark at 25 °C with yeast extract and settled domestic wastewater inoculum. After 7 d, 100% biodegradation with rapid adaptation was observed (Tabak et al., 1981). 

Soil. Hydrolyzes in soil forming 3-chloroaniline (Bartha, 1971 Hartley and Kidd, 1987 Smith, 1988). In soil. Pseudomonas striata Chester, a Flavobacterium s >., an Agrobacterium s >., and an Achromobacter sp. readily degraded chlorpropham to 3-chloroaniline and 2-propanol. Subsequent degradation by enzymatic hydrolysis yielded carbon dioxide, chloride ions, and unidentified compounds (Kaufman, 1967). 

In nature, an enzyme requiring two co-factors, thiamine diphosphate 2 and flavin adenine dinucleotide, accomplishes the oxidation of pyruvate to acetyl phosphate. The thiazole ring in thiamine condenses at the 2-position with pyruvat eliminating carbon dioxide to give an activated species that is oxidised by the flavin. An enzymatic oxidation process then reactivates the reduced flavin. The redox... 

J.L. Panza, A.J. Russell, E.J. Beckman, Synthesis of fluorinated NAD as a soluble coenzyme for enzymatic chemistry in fluorous solvents and carbon dioxide. Tetrahedron 58 (2002) 4091-4104. 

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