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Chemical and Functional Properties of Food Saccharides

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© 2004 by CRC Press LLC<br />

Wheat consists <strong>of</strong> an lcb population (ca. 22%), which may be precipitate with nbutanol<br />

from aqueous solution <strong>and</strong> contains significantly less A-chains, <strong>and</strong> an scb<br />

population (ca. 78%), which is very similar to that <strong>of</strong> waxy maize starch.<br />

22.4.3 SUPERMOLECULAR STRUCTURES<br />

As no obvious differences <strong>of</strong> molecular dimensions in terms <strong>of</strong> occupied volume (V e<br />

→ R e) will be found for different starch glucans such as wheat <strong>and</strong> waxy maize, <strong>and</strong><br />

molecular weight at least appears somewhat ambiguous, strongly depending on applied<br />

approach, branching pattern characteristics are strongly suspected to control macroscopic<br />

material qualities by promoting formation <strong>of</strong> more or less stable supramolecular<br />

structures. Investigation <strong>of</strong> segment mobility in starch glucan solutions by noninvasive<br />

techniques such as photon correlation spectroscopy is a perfect tool to check such<br />

supermolecular structures. Dynamic light scattering (DLS) <strong>and</strong> photon correlation<br />

spectroscopy (PCS) experiments provide data on diffusive mobility <strong>of</strong> individual glucan<br />

molecules <strong>and</strong> mobility <strong>of</strong> supramolecular segments, in particular, on translational<br />

diffusion <strong>of</strong> glucans <strong>and</strong> glucan aggregates. If laser light is applied to starch glucan<br />

solutions, mobility <strong>of</strong> the segments in such solutions cause Doppler shifts, which may<br />

be monitored as the autocorrelation function, G 2(τ), (Equation 22.3a):<br />

1<br />

G2 () ? = I( t) ⋅ I( t + ?) dt<br />

T<br />

(22.3a)<br />

where T is the temperature (K), t the time, I the intensity <strong>of</strong> scattered laser light,<br />

<strong>and</strong> τ the correlation period.<br />

Indirect Laplace transformation <strong>of</strong> G 2(τ) yields G 2(t), which contains the translational<br />

diffusion coefficient, D T, 44 (Equation 22.3b):<br />

where h is the scattering vector, <strong>and</strong> A <strong>and</strong> C are coefficients.<br />

According to Stokes <strong>and</strong> Einstein (Equation 22.3c), D T <strong>of</strong> observed glucans <strong>and</strong><br />

glucan aggregates can be correlated with radius, R H, or diameter, d, <strong>of</strong> moving<br />

equivalent spheres. As in particular supramolecular structures are dynamically<br />

formed by individual glucan molecules, d is rather the length <strong>of</strong> coherently moving<br />

segments, <strong>and</strong> thus, for practical purposes, coherence length, l coh, <strong>of</strong> supramolecular<br />

segments replaces the equivalent sphere diameter d:<br />

(22.3c)<br />

where k B is the Boltzmann constant, T the temperature (K), <strong>and</strong> η the viscosity <strong>of</strong><br />

solution.<br />

?<br />

∫<br />

0<br />

2<br />

⎡ ⎛ τmax<br />

t ⎞ ⎤ −<br />

⎢ DT()<br />

?<br />

G2()<br />

t = A⋅ + C⎜ τ<br />

⎢ i ⋅e<br />

d ⎟<br />

⎥<br />

1<br />

1 τ with (22.3b)<br />

⎜ ∫ 2<br />

⎟<br />

⎥ τ = 2<br />

τ<br />

D<br />

⎢<br />

⎣<br />

⎝ τmin<br />

⎠ ⎥<br />

T h<br />

⎦<br />

D<br />

T<br />

kBT = →<br />

6π ηR<br />

H<br />

l<br />

coh

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