Starch derivatives formation

Polyols are unique among simple carbohydrates in their low ability to be fermented. This characteristic enables them to impart sweetness to foods while exhibiting lower caloric values than other carbohydrates and reducing the formation of dental caries. Polyols are used in a variety of applications in foods, confections, pharmaceuticals and industrial uses. Rising demand for low- and reduced-calorie foods and confections that contribute to a reduction in dental caries has contributed to the growth of these starch-derived products. 

Specific interactions between starch and proteins were observed as early as the beginning of the twentieth century. Berczeller996 noted that the surface tension of aqueous soap solutions did not decrease with the addition of protein (egg albumin) alone, but it did decrease when starch and protein were added. This effect was observed to increase with time. Sorption of albumin on starch is inhibited by bi- and trivalent ions and at the isoelectric point. Below the isoelectric point, bonding between starch and albumin is ionic in character, whereas nonionic interactions are expected above the isoelectric point.997 The Terayama hypothesis998 predicts the formation of protein complexes with starch, provided that starch exhibits the properties of a polyelectrolyte. Apart from chemically modified anionic starches (such as starch sulfate, starch phosphate, and various cross-linked starch derivatives bearing ionized functions), potato starch is the only variety that behaves as a polyelectrolyte. Its random phosphate ester moieties permit proteins to form complexes with it. Takeuchi et a/.999-1002 demonstrated such a possibility with various proteins and a 4% gel of potato starch. 

Starches have been chemically modified to improve their solution and gelling characteristics for food applications. Common modifications involve the cross linking of the starch chains, formation of esters and ethers, and partial depolymerization. Chemical modifications that have been approved in the United States for food use, involve esterification with acetic anhydride, succinic anhydride, mixed acid anhydrides of acetic and adipic acids, and 1-octenylsuccinic anhydride to give low degrees of substitution (d.s.), such as 0.09 [31]. Phosphate starch esters have been prepared by reaction with phosphorus oxychloride, sodium trimetaphosphate, and sodium tripolyphosphate the maximum phosphate d.s. permitted in the US is 0.002. Starch ethers, approved for food use, have been prepared by reaction with propylene oxide to give hydroxypropyl derivatives [31]. 

Many interactions are of a pure chemical nature and may result from the presence of aldehydes and their reactivity toward amino and thiol groups of proteins. Another frequently occurring type of interaction is the formation of hydrogen bonds between food compounds and polar flavor components such as alcohols. Starch, starch-derived maltodextrins, and (3-cyclodextrin are able to form inclusion complexes with many flavor components. Many other interactions, although of great influence on flavor perception, are of a physical nature and therefore not mentioned in this chapter. 

The main drawback to the widespread use of polymer-polymer aqueous two-phase extraction has been the high cost of fractionated dextran. Crude dextran has been used with some success for the purification of enzymes but is much too viscous for many applications. Conversely, polymer-salt systems have relatively low viscosities, separate rapidly, and are inexpensive. Unfortunately, they lack selectivity and cannot be used for affinity partitioning in most cases since the high salt concentrations interfere with the protein-ligand interaction. The starch derivatives are reasonable alternatives for bottom phase polymers but have been hampered by low solubilities and the tendency for gel formation. Tjemeld has reported that chemically modified starches i.e. hydroxypropyl starch... 

The formation of a trinicotinate was reported.2409 The best method of preparing this starch derivative involved reacting nicotinoyl chloride hydrochloride and starch in boiling pyridine.2410 Starch isonicotinates and 4-(sulfinylamino)benzoates were subsequently prepared. Starch isonicotinate was further cationized by treating it in nitromethane solution with methyl 2-(chloroacetyl)lactate or benzoylhydrazide A-chloroacetate and l-[2-(chloroacetoxy)propanoyl]-3-methylpyrazole.2411... 

The pentose phosphate pathway is an alternative route for the metabolism of glucose. It does not generate ATP but has two major functions (1) The formation of NADPH for synthesis of fatty acids and steroids and (2) the synthesis of ribose for nucleotide and nucleic acid formation. Glucose, fructose, and galactose are the main hexoses absorbed from the gastrointestinal tract, derived principally from dietary starch, sucrose, and lactose, respectively. Fructose and galactose are converted to glucose, mainly in the liver. 

Starch can be vinylated with acetylene in the presence of potassium hydroxide in an aqueous tetrahydrofuran medium.1 1 The mechanism possibly involves the addition of the potassio derivative of starch across the carbon-carbon triple bond of acetylene, with subsequent hydrolysis of the organometallic intermediate to give the vinyl ether. Such a mechanism has been postulated for the formation of vinyl ethers from monohydric alcohols and acetylene, in the presence of an alkali metal base as catalyst.1 2 The vinylation of amylose is very similar to the vinylation of amylopectin, except for the relative ratio of mono- to di-substitution. With amylopectin, the proportion of disubstitution is greater. In both starches, the hydroxyl group on C-2 is slightly more reactive than the hydroxyl group on C-6 there is little substitution at the hydroxyl group on C-3. 

Steam treatment of an industrial process stream, denoted starch-free wheat fiber, was investigated to improve the formation of monomeric sugars in subsequent enzymatic hydrolysis for further bioconversion into ethanol. The solid fraction in the process stream, derived from a combined starch and ethanol factory, was rich in arabinose (21.1%), xylose (30.1%), and glucose (18.6%), in the form of polysaccharides. Various conditions of steam pretreatment (170-220°C for 5-30 min) were evaluated, and their effect was assessed by enzymatic hydrolysis with 2 g of Celluclast + Ultraflo mixture/ 100 g of starch-free fiber (SFF) slurry at 5% dry matter (DM). The highest overall sugar yield for the combined steam pretreatment and enzymatic hydrolysis, 52 g/100 g of DM of SFF, corresponding to 74% of the theoretical, was achieved with pretreatment at 190°C for 10 min followed by enzymatic hydrolysis. 

New starch products might be derived from emulsion copolymerization with synthetic monomers and the replacement of all-synthetic polymers. Potential applications could be in flocculation, sizing, modified rheological characteristics, bonding to a wide range of substrates, film formation and in effluent treatment. A critical requirement will be the removal of hazardous residuals and Food and Drug Administration (FDA) approval for use in specific paper grades. 

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