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Chemical and Functional Properties of Food Saccharides

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© 2004 by CRC Press LLC<br />

precipitates in less dense domains. Within the granules, the tendency for separation<br />

increases with increasing percentage <strong>of</strong> lcb-glucans in a mixture <strong>of</strong> both types. No<br />

instance <strong>of</strong> a homogeneous scb-/lcb-glucan blend in a starch granule is known.<br />

In the native environment (plant cell), starch granules are hydrated, <strong>and</strong> thus in<br />

a swollen state, similar to the conditions <strong>of</strong> industrially hydrated starch granules: in<br />

both cases, the granules show increased order (birefringence) <strong>and</strong> reduced hilum<br />

opening. In the swollen state, lcb-glucans diffuse out <strong>of</strong> amorphous regions, <strong>and</strong><br />

transfer <strong>of</strong> ionic compounds into <strong>and</strong> out <strong>of</strong> the granules is enabled. Extraction<br />

procedures (leaching) <strong>and</strong> drying result in the formation <strong>of</strong> compact granules with<br />

a cracked hilum.<br />

Based on differences in swelling behavior in aqueous environment, there are<br />

reasonable suggestions for preferred localizations <strong>of</strong> scb- (amylopectin) <strong>and</strong> lcbglucans<br />

(amylose) within starch granules: (1) Waxy maize starch granules represent<br />

an arrangement <strong>of</strong> more or less 100% scb-glucans (amylopectin) <strong>and</strong> no lcb-glucans<br />

(amylose). The scb-glucans are closely packed in concentric layers in dry waxy<br />

maize granules <strong>and</strong> exp<strong>and</strong> on swelling in aqueous media. These concentric layers<br />

<strong>of</strong> scb-glucans represent the framework for the majority <strong>of</strong> starch granules. (2) Potato<br />

starch granules represent a mix <strong>of</strong> a major fraction <strong>of</strong> ∼80% scb-glucans (amylopectin)<br />

<strong>and</strong> a minor fraction <strong>of</strong> ∼20% lcb-glucans (amylose). The lcb-glucans are<br />

localized in distinct concentric layers alternating with scb-glucan layers. On hydration,<br />

these granules swell due to the exp<strong>and</strong>ing layers <strong>and</strong> simultaneously reduce<br />

the volume for amorphous lcb-glucans by encapsulation. From such granules, even<br />

lcb-glucans (amylose) may be extracted by leaching processes, which similarly<br />

reduce the amorphous layer fraction. (3) Amylomaize starch granules are composed<br />

<strong>of</strong> a minor fraction <strong>of</strong> ∼30% <strong>of</strong> scb-glucans (amylopectin) <strong>and</strong> a major fraction <strong>of</strong><br />

∼70% <strong>of</strong> lcb-glucans (amylose), with a pronounced separation <strong>of</strong> scb- <strong>and</strong> lcbglucans.<br />

On hydration, lcb-glucans <strong>of</strong> such granules are kind <strong>of</strong> diluted but granules<br />

do not swell. From such granules lcb-glucans may be extracted by leaching processes.<br />

22.4 MOLECULAR LEVEL<br />

Investigations on the molecular level in most cases require dissolution <strong>of</strong> the materials<br />

<strong>of</strong> interest. Although starch polysaccharides are rather polar, due to pronounced<br />

H-bond-binding they can hardly be dissolved in neutral aqueous media. For most<br />

technical purposes, they get dissolved or suspended in H-bond-“breaker” alkaline<br />

media; however, for analytical purposes dissolution in aprotic polar medium such<br />

as dimethylsulfoxide (DMSO) is preferable as problems with ionic strength variations<br />

can be avoided. A number <strong>of</strong> chemical, enzymatically supported, <strong>and</strong> physical<br />

techniques are available to investigate molecular-level characteristics <strong>of</strong> starch glucans.<br />

However, due to the multiple <strong>and</strong> superimposed heterogeneities <strong>of</strong> these materials,<br />

the most important are fractionation <strong>and</strong> separation techniques, in particular<br />

precipitation–complexation <strong>and</strong> chromatography (Table 22.3). As the major quality<br />

<strong>of</strong> starch polysaccharides, like any polysaccharides, is to fill up volume in a more<br />

or less structurized way, any analytical approach has to qualify <strong>and</strong> quantify this<br />

performance. Size-exclusion chromatography (SEC) is a perfect tool to obtain such

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