Carbohydrates depolymerization

Effective utilization of biomass for value-added chemical product synthesis will require development of new applications of important unit operations. Carbohydrate recovery from the biomass is the key near-term application for production of commodity chemicals. Protein recovery will continue to have an important niche market in tlie purified form as food and a larger low-value market in the crude form as animal feed. Important processing information for carbohydrate depolymerization can be found in the literature from biochemical conversion of biomass. New process applications of separation technologies are just now being developed and refined for use with biomass-derived carbohydrate and protein streams. The use of an aqueous processing environment for carbohydrates will require careful consideration of the differences that type of environment entails, such as the effect on catalyst formulations. 

For the most part, low molecular weight carbohydrates of commerce are made by depolymerization via enzyme- or acid catalyzed hydrolysis of polysaccharides. Only sucrose and, to a very much lesser extent, lactose, both disaccharides, are commercial low molecular weight carbohydrates not made in this way. 

Since polysaccharides are the most abundant of the carbohydrates, it is not surprising that they comprise the greatest part of industrial utiliza tion (9,22). Most of the low molecular weight carbohydrates of commerce are produced by depolymerization of starch. Polysaccharide materials of commerce can be thought of as falling into three classes cellulose, a water-insoluble material starches, which are not water-soluble until cooked and water-soluble gums. 

HPAEC analyses were carried out to determine the oligomeric products released from various pectic substrates after depolymerization by the PL isoenzymes. Action pattern analyses for the concerted action of PL isoenzymes utilized 68% esterified pectin as substrate. One-ml reaction mixtures in a buffer system as detailed in section 2.2. comprising 0.5% (w/v) substrate and 5 U of enzyme were incubated for 30 s to 18 h, and then thermoinactivated. Samples of 750 pi were applied to a Carbopac PA-1 (Dionex) column before the carbohydrates were eluted over a period of 70 min using a gradient of 0.2 M KOH, 0.05 M K-acetate to 0.2 M KOH, 0.7 M K-acetate. Detection employed a Pulsed Electrochemical Detector (PED, Dionex) in the integrated amperometry mode according to the manufacturer s recommendations. 

Kravtchenko T.P., Amould I., Voragen A.G.J. Pilnik W. (1992) Improvement of the selective depolymerization of pectic substances by chemical P-elimination in aqueous solution. Carbohydrate Polymers 19,237-242. 

III. Analysis of Permethylated Carbohydrates without Depolymerization of the Sample... 

Depolymerization of the permethylated carbohydrate is achieved by hydrolysis with acid. Under these conditions, the amino sugar residues are N-deacetylated, and the aminohexosidic linkages become resistant to hydrolysis. Stellner and coworkers29 showed that, when the acid degradation is conducted in 95% acetic acid, the amino sugar residues are also liberated, and can be analyzed by the methylation technique.29 Therefore, acetolysis followed by acid hydrolysis is now commonly used, as it allows the analysis both of hexose and hexosamine residues. 

Even less is known about the effects of ozone on carbohydrates. Buell et al. observed a decrease in the depolymerization of hyaluronic acid after treatment of the lungs of ozone-exposed rabbits (1 ppm for 1 h) with hyaluronidase. B. Goldstein et al. reported a loss in membrane neuraminic acid of red cells exposed in vitro to high concentrations of ozone. It would be important to study the effects of ozone on respiratory tract mucus, which is rich in carbohydrates, including neuraminic acid. This could indude determination of foe extent to which ozone is able to penetrate mucus that is unaltered, whether foe reaction of ozone with mucus results in the formation of cytotoxic intermediates, and evaluation of the interaction in mucus of ozone with other air pollutants, particularly sulfur dioxide. Of possible pertinence is a study by Falk et who observed that ozone produced a loss in foe viral hemagglutinating ability of snail mucus. 

Water is not just the solvent in which the chemical reactions of living cells occur it is very often a direct participant in those reactions. The formation of ATP from ADP and inorganic phosphate is an example of a condensation reaction in which the elements of water are eliminated (Fig. 2-22a). The reverse of this reaction— cleavage accompanied by the addition of the elements of water—is a hydrolysis reaction. Hydrolysis reactions are also responsible for the enzymatic depolymerization of proteins, carbohydrates, and nucleic acids. Hydrolysis reactions, catalyzed by enzymes called... 

Condensed-Phase Mechanisms. The mode of action of phosphorus-based flame retardants in cellulnsic sy stems is probably best understood. Cellulose decomposes by a noncalalyzed route lo tarry depolymerization products, notably levoglucosan, which then decomposes to volatile combustible fragments such as alcohols, aldehydes, ketones, and hydrocarbons. However, when catalyzed by acids, the decomposition of cellulose proceeds primarily as an endothermic dehydration of the carbohydrate to water vapor and char. Phosphoric acid is particularly efficaceous in this catalytic role because of its low volatility (see Phosphoric Acids and Phosphales). Also, when strongly heated, phosphoric acid yields polyphosphoric acid which is even more effective in catalyzing the cellulose dehydration reaction. The flame-retardanl action is believed to proceed by way of initial phosphory lation of the cellulose. 

The cellulosic substrate is depolymerized by water (or possibly other agents) so that simple sugars can be obtained. If the pretreatments totally separate cellulose from hemicellulose, the simple sugar would be glucose. Otherwise, the glucose will be mixed with other carbohydrates that may interfere with the fermentation. 

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