ADVANCED

FOOD CHEMISTRY

Carbohydrates

Structural Representation (Haworth Projection)

Starches, which are assembled from -glucose units, are soluble and easily digested. Cellulose, synthesized from -glucose units, is insoluble and cannot be digested as a food source by most animals.

Disaccharides

Monosaccharides in the ring form can link together to form disaccharides or in greater numbers to form polysaccharides. Disaccharides are formed when two monosaccharides are coupled together. The coupling is of a specific type: an oxygen atom forms a bridge between the units coupled together This oxygen atom must be part of an acetal or ketal group.

Disaccharides

Linkage of two monosaccharide molecules to form the disaccharides such as maltose, lactose and sucrose. The linkages are designated as alpha () or beta () depending on the orientation of the -OH group at the number C1 forming the bond. The linkage are called glycosidic linkages and are know as alpha () or beta () 1-2, 1-3, 1-4, and1-6.

Disaccharides

Oligosaccharides

Formed when small numbers of monosaccharides are coupled together. Example: raffinose, stachyose, fructooligosaccharides, maltodextrin

Polysaccharides

Starch (amylose & amylopectin) Cellulose Hemicellulose pectins, hydrocolloids

Starch

The primary source of stored energy in plants It occurs in nature as water-insoluble granules and is available in unlimited quantities The most common starches used in the food industries are extracted either from cereals or roots and tubers

Starch

Amyloplast (leucoplast): responsible for starch synthesis Hilum: where the synthesis of starch began Starch is unique among carbohydrates because it occurs naturally as discrete granules (or grains), which is water-insoluble and is available in unlimited quantities The most common starches used in the food industries are extracted either from cereals or roots and tubers

Starch

In addition to their nutritive value, starches are used to affect the properties of many foods They are used in gelling, thickening, adhesion, moisture-retention, stabilising, film forming, texturising, etc.

Starch

Starch consists of two types of molecules, amylose (normally 20-30%) and amylopectin (normally 70-80%). Both consist of polymers of a-D-glucose units in the conformation (D-glucopyranose molecules). In amylose these are linked -(14)-, with the ring oxygen atoms all on the same side, whereas in amylopectin about one residue in every twenty or so is also linked -(16)- forming branch-points. The relative proportions of amylose to amylopectin and (16)- branch-points both depend on the source of the starch, e.g. amylomaizes contain over 50% amylose whereas 'waxy' maize has almost none (~3%)

Starch Production in Food Industry

Corn starch is extracted from the kernel through a process of wet milling. The process employs techniques of grinding, screening and centrifugation to separate purified starch from fiber, oil and tightly bound protein. (Fig. 1).

Amylopectin A naturally occurring branched polymer of glucose found in starch whose linear portions are connected by -1,4-glycosidic linkages and the branch points are -1,6-glycosidic linkages Amylose A naturally occurring polymer of glucose found in starch comprised of anhydroglucose units with 1,4-glycosidic linkages in straight chain

Amylose/amylopectin ratio

Generally, about one part of amylose to every three parts of amylopectin for normal grain sources Waxy varieties contain 0% amylose and 100% amylopectin used in non-gelling starch applications, starch-thickened frozen products, and many modified starches High amylose varieties: 60-85% amylose, the rest in amylopectin. Useful as binders and film formers

The polymerization of glucose into amylose

The difference between amylose and cellulose

Polysacharides

Amylopectin

Structure of Amylopectin

Properties of starch components

Property
General structure Linkage Average chain length Molecular weight DP Iodine complex Gelling Film forming

Amylose
Essentially linear - 1,4 103 <0.5 million 103 Blue Firm Strong

Amylopectin
Branched - 1,4 and - 1,6 20-25 50-500 million 104-105 Reddish brown Soft Weak

Specific characteristics to differ among starch

Granule size and shape Amylose content Gelatinization temperature Viscosity and pasting properties Setback or cold viscosity Gel strength Paste clarity

Granules

This is the small (5-25 microns) grain-like particle in which amylose and amylopectin molecules are deposited and stored by a plant. In the case of corn, they are located in the endosperm of the seed or kernel

Structure of Starch Granules

H H H H H

Granule size and shape

Starch granules come in a wide variety of sizes ranging from 3 microns to over 100 microns. With some starches the granule size is polymodal, meaning the granules can be grouped into more than one size range. Wheat starch, for example, has a distribution of both large and small granules. Some granules exhibit their shape smoothly, while others are polyhedrons with a faceted surface. Not directly related to functional properties, but us useful information along with size for identification of the species

Starch Granules

Corn

Potato

Rice

Tapioca

Starch Granules

Starch Granules Maltose cross

(birefrigence)

Physical properties of starch from various sources

Type of starch Sago Granule shape Cut ellipse Granule size () 20-60 Ratio Gelatinizatio amylose/ n temp (oC) amylopectin 27:73 60-72

Rice
Maize Potato Tapioca Wheat Sweet potato

Polygonal
Polygonal Round Ovoid Ellipse Polygonal

3-8
5-25 15-100 5-35 2-35 16-25

17:83
26:74 24:76 17:83 25:75 18:82

61-78
62-74 56-69 52-64 52-64 58-74

Birefrigence

Indicates that starch granules are semicrystalline When ungelatinized starch is viewed under a microscope with a polarized light, the intact crystalline structure of the starch refracts the light in a Maltose Cross pattern

Starch-lipid interaction

Cereals commonly contain a high percentage of lipids (0.8-0.9%). The lipid molecules may form a complex (helix) with amylose molecules. Effects of lipid:

Repress the swelling and solubilization of starch granules. Increase the pasting temperature and reduce the water-bindingability of the starches Causes turbidity and starch pastes and starch solution opaque/cloudy The oxidation of unsaturated lipid formation of undesirable flavors

Formation of amylose-lipid complex

+
Dissolved amylose molecule Free lipid molecule Amylose-lipid complex (helix)

Gelatinization

Swelling and disorganization of starch granules heated in water When starch suspension is heated, the granules absorb water swell in size irreversibly. Measures of starch gelatinization: Swelling of granules Increased viscosity Increased translucency Increased solubility

Gelatinization

Starch gelatinization is the collapse of molecular order within the starch granule manifested in irreversible changes in properties such as granular swelling, native crystalline melting, loss of birefrigence, starch solubilization, increased suspension viscosity. The point of initial gelatinization and the range of over which it occurs is governed by starch concentration, method of observation, granule type, and heterogeneities within the granule population under observation.

Gelatinization temperature

The temperature range over which starch losses its crystallinity in a water suspension. Above this temperature range starch rapidly swells and absorbs water to become a viscous or colloidal dispersion. Gelatinization temperature range is characteristics for each type of starch, that is for each botanical sources

A. Starch granules prior to heating in excess water B. Starch granules after heating to a temperature that melts the crystallites C. The starch granules swell more during processing because they absorbed more water, and are therefore more gelatinized. D. Highly gelatinized starch granules are ruptured due to over processing. The starch granules completely disappear

Steps of starch gelatinization

Granules hydrate and swell to several times their original sizes Granules lose their birefrigence (optical property of starch) Clarity of the mixture increases Marked and rapid increase in consistency occurs and reaches a maximum Linear molecules (amylose) dissolve and diffuse from the ruptured granules Upon cooling, uniformly dispersed matrix forms a gel or paste-like mass

Starch gelatinization, pasting, gelling and retrogradation

The initial suspension of insoluble starch in water contains crystalline amylose and amylopectin starch polymers associating with each other via H-bonding within starch granules. Heated starch undergoes gelatinization, losing its crystalline order through melting and interpolymer Hbond breakage. The system is a sol of low viscosity, consisting of a liquid continuous phase and a solid dispersed phase. With continuous heating, the system becomes a paste, and is less pourable due to an increase in viscosity as molecular material enters the intergranule matrix while the granules become swollen with water.

Starch gelatinization, pasting, gelling and retrogradation

As the gelatinized paste cools, an elastic, twophase system forms consisting of a solid continous phase of mainly amylose polymers holding a liquid dispersed phase, water, through intermolecular H-bonds starch gels. The gelatinized starch regions of high amylose content revert back to more crystalline structure during storage retrogradation. Retrograded starch expels water from its threedimensional structure via syneresis, which causes gel shrinkage and increased starch polymer intermolecular associations.

Viscosity and granular changes during pasting

Viscosity

Time/Temperature

Relationship between starch gelatinization, pasting, gelling and retrogradation

H2O H2O

Raw, uncooked starch granules heated in water

Swelling is evident

Relationship between starch gelatinization, pasting, gelling and retrogradation

H2O

Some granules have collapse

Gelatinization and pasting are complete

Starch Gelatinization and Pasting, Gelation, and Uglification

Go to Slide Show mode and click to begin

Starch granules contain both linear amylose and branched amylopectin.

Raw, uncooked starch granules heated in water

Swelling is evident

Notice loss of amylose from the granules

Some granules have collapsed

Gelatinization and pasting are complete

Gelation

Now we start to cool

Notice areas of association. These are called junction zones

This picture is not yet complete as we havent accounted for the water in the system.

water water

water

water
water

water

This is a starch gel

Uglification
WATER

This picture ignores swollen and collapsed granules Junction zones will naturally enlarge over time or in response to processes such as freezing.

WATER

+ WATER of SYNERESIS that has been squeezed out of the gel structure

The texture gets very ugly when this happens

Pasting

Pasting is the phenomenon following gelatinization in the dissolution of starch. It involves granular swelling, exudation of molecular components from the granule, an eventual, total disruption of the granules.

Profile of starch gelatinization process

Heating
50 65 80 95 1000
Corn (40 g)

Cooling
95 80 65 50 50

Temperature (C)

800

Viscosity (BU)

600
Potato (40 g)

400 200

Waxy sorghum (40 g)

0
30 60 90 120 150 180

Time (min)

Behaviour of Amylose in solution

The amylose molecules will re-associate into aggregates and precipitate at low concentrations or set to a gel at higher amylose concentrations

Gelation

The formation of a gel from a cooled paste. A starch gel is rigid, thickened starch and water mixture that has the properties of a solid. Starches with high amylose content form gels more easily than do starches high in amylopectin. Pastes derived from high amylopectin starches are considered to be non-gelling but have a gummy, cohesive texture. They are useful as thickening agents due to their ability to create an increase in viscosity.

Gelation

Amylose is the glue that holds gel together Therefore, waxy starches do not gel. They form thick, cooked pastes and are frequently the starting materials in the production of modified food starch

Retrogradation

A process which occurs when the polymers comprising gelatinized starch begin to reaasoaciate in an ordered structure. In its initial phases, two or more amylose or amylopectin chains may form a simple juncture point which then may develop into more extensively ordered regions Retrogradation is especially evident when amylose containing starches are cooled, resulting in water release (syneresis).

Paste Clarity

Influenced by the retrogradation tendency of the starch, which also affects the texture of the cooked structure Ruber, tuber, and waxy starches have relatively low retrogradation tendencies and provide clearer gels Cereal starches retrograde easily and give gels with less clear to opaque

Properties of starch-water pastes with nearly the same maximum viscosity in viscometer
Cooked to max viscosity T (oC) 90 89 71 91 94 92 Visc (g-cm) 105 105 108 113 101 105
Gel strength (g-cm)

Starch

% (DB) 1.96 2.98 3.54 4.90 5.49 6.44

20 cooking beyond maksimum T (oC) 95 95 94 95 97 94 Visc (g-cm) 49 65 59 77 54 62

Gel strength (g-cm)

Potato Waxy corn Tapioca Corn Rice Wheat

0 0 0 52 31 345

0 0 0 142 30 440

Indicators of a proper starch cook

Under-cook Poor clarity Low viscosity Thin Poor shelf stability Proper Cook Clear Full viscosity Short, spoonable Optimum stability Over-Cook Clear Low viscosity Cohesive Poor stability

Starchy flavor
Birefringence/ incompletely swollen granules

Clean flavor
Fully swollen granules

Clean flavor
Fragmented granules

Effect of ingredients and conditions on gelatinization

Sugars Acids Enzymes