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Chemical and Functional Properties of Food Saccharides

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© 2004 by CRC Press LLC<br />

methods, such as multivariate data, discriminant <strong>and</strong> principal component analysis,<br />

artificial neural network, <strong>and</strong> principal variables, it was shown that modified starches<br />

can be qualitatively <strong>and</strong> quantitatively differentiated. 7,8 Starch gelatinization or melting<br />

<strong>and</strong> the subsequent retrogradation processes (gelation, syneresis, helix formation,<br />

crystallization) are <strong>of</strong> great importance to the quality <strong>of</strong> products.<br />

Studies that used sample techniques such as diffuse reflectance (DRIFT) <strong>and</strong><br />

attenuated total reflectance (ATR) showed the usefulness <strong>of</strong> IR for the determination<br />

<strong>of</strong> conformational changes during processing <strong>and</strong> storage. But absolute determination<br />

<strong>of</strong> the conformation <strong>of</strong> starch is still not possible. The O–H stretching vibrations<br />

between 3000 <strong>and</strong> 3700 cm –1 <strong>and</strong> the C–C <strong>and</strong> C–O stretching <strong>and</strong> C–O–H bending<br />

vibrations between 800 <strong>and</strong> 1300 cm –1 are sensitive to conformation, short-range<br />

order, crystallinity, <strong>and</strong> hydration. 7–9 Recently, the relationship between baking behavior<br />

<strong>and</strong> chemical structure <strong>of</strong> cassava starch was studied with IR 10 (Figure 23.1).<br />

23.2.1.3 Other Polysaccharides<br />

Pectins have a backbone <strong>of</strong> (1→4)-linked α-D-galacturonan with side chains <strong>of</strong> α-<br />

D-galactopyranose, α-L-arabin<strong>of</strong>uranose, <strong>and</strong> α-(1→2) rhamnopyranosyl residues.<br />

Most studies focused on the carboxyl groups in pectic derivatives or the degree <strong>of</strong><br />

esterification <strong>of</strong> carbonyl groups in pectins. 7,11,12 Characteristic b<strong>and</strong> shifts <strong>of</strong> the<br />

C=O ring, <strong>and</strong> the symmetric or asymmetric carboxylate vibrations showed the<br />

interaction <strong>of</strong> divalent cations with pectate or pectinate, indicating a metal coordination<br />

in agreement with the egg-box hypothesis <strong>and</strong> complex formation.<br />

Xylan structure depends on the nature <strong>of</strong> the xylopyranan backbone, β-(1→4)<br />

or β-(1→3), <strong>and</strong> the presence <strong>of</strong> glucuronic acid side chains <strong>and</strong> arabinose. This<br />

results in marked spectral differences, which depend on water content, sorption, <strong>and</strong><br />

hydration. 7 It was shown that water influences the molecular orientation <strong>and</strong> degree<br />

<strong>of</strong> ordering. Spectral features <strong>of</strong> (1→4) xylans are affected by the α-L-arabin<strong>of</strong>uranose<br />

substitution <strong>of</strong> the C-3, but not significantly by arabin<strong>of</strong>uranose or glucuronic<br />

120 100 80 60 40 20 0<br />

<strong>Chemical</strong> shift (ppm)<br />

FIGURE 23.1 Solid-state 13 C-CP/MAS NMR spectrum <strong>of</strong> pregelatinized waxy corn starch.

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