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Chemical and Functional Properties of Food Saccharides

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© 2004 by CRC Press LLC<br />

associations. Unfortunately, pectin solubility is reduced at acidic pH, which is why<br />

presumably elevated temperatures are required to increase the effectiveness <strong>of</strong> water<br />

as a solvent for the polysaccharide.<br />

Commercial acid-extracted citrus pectins typically have a uronic acid content <strong>of</strong><br />

85–90%, a neutral sugar content <strong>of</strong> less than 10%, <strong>and</strong> a degree <strong>of</strong> esterification <strong>of</strong><br />

55–80%. 2 In comparison, careful purification <strong>of</strong> cell wall material <strong>and</strong> extraction<br />

with CDTA yields pectins with 80% uronic acid, 15% neutral sugars, <strong>and</strong> a degree<br />

<strong>of</strong> methyl esterification <strong>of</strong> 68%. 29 Acid extraction appears to cause some degradation<br />

<strong>of</strong> the pectin, but the overall chemical composition is broadly similar to that <strong>of</strong> the<br />

native material. In contrast, in a recent study <strong>of</strong> pectin extraction from sugar beet<br />

pulp, 30 acid-extracted pectins had a uronic acid content <strong>of</strong> 30 to 52%, depending on<br />

the conditions <strong>of</strong> pH <strong>and</strong> temperature used. Decreasing pH led to the extraction <strong>of</strong><br />

pectins richer in RG-I. The difference observed between acid-extracted citrus <strong>and</strong><br />

sugar beet pectins clearly reflects differences in pectin composition <strong>of</strong> the starting<br />

material rather than variability in method <strong>of</strong> extraction.<br />

12.4 PECTIN MODIFICATION<br />

The ester content <strong>of</strong> pectin may be modified through the use <strong>of</strong> acid or alkali to<br />

deesterify the pectin. If ammonia is used as the alkali, some <strong>of</strong> the uronic acid<br />

residues become amides, <strong>and</strong> an amidated pectin is formed. 2 <strong>Chemical</strong> deesterification<br />

occurs in a r<strong>and</strong>om way. Pectin may also be deesterified with pectin methyl<br />

esterases. Fungal enzymes have a r<strong>and</strong>om attack pattern, whereas plant pectin<br />

methyl esterases tend to result in a block distribution <strong>of</strong> deesterified uronic acid<br />

residues. 4,31 This categorization may require some modification in the future, as in<br />

higher plants there is a whole range <strong>of</strong> pectin methyl esterases whose mode <strong>of</strong><br />

action has not been fully characterized. The conditions <strong>of</strong> deesterification are also<br />

important. For an apple pectin methyl esterase, 31 a blockwise distribution <strong>of</strong> uronic<br />

acid residues was generated. At pH 7, only a fraction <strong>of</strong> the chains in the pectin<br />

polysaccharide preparation were modified in this way. At pH 4.5, shorter blocks<br />

were produced in the entire chain population. One <strong>of</strong> the reasons for the interest<br />

in different methods <strong>of</strong> deesterification is that pectins produced should behave<br />

differently in terms <strong>of</strong> their interactions with counterions. It is suggested that<br />

blockiness should favor network formation, whereas more r<strong>and</strong>omly distributed<br />

charge might have a more pronounced effect on the affinity <strong>of</strong> the polysaccharide<br />

for water. The combination <strong>of</strong> methodologies for the production <strong>of</strong> different patterns<br />

<strong>of</strong> esterification <strong>and</strong> those for characterizing the pattern <strong>of</strong> charge distribution in<br />

pectins should help provide structure–function relationships for patterns <strong>of</strong> charge<br />

distribution.<br />

The availability <strong>of</strong> different pectin methyl esterases <strong>and</strong> enzymes for selective<br />

cleavage <strong>of</strong> neutral sugar pectin side chains makes it possible to produce a range <strong>of</strong><br />

pectins with different functional behavior. For example, 32 it was found that removal<br />

<strong>of</strong> side chains decreased the viscosity <strong>of</strong> semidilute aqueous solutions <strong>of</strong> pectins in<br />

the absence <strong>of</strong> calcium, whereas the use <strong>of</strong> pectin methyl esterase enhance gel<br />

properties.

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