Carbohydrates: Functional

Properties
NFS 360
Basil K. Dalaly
Professor
Department of Health and Nutritional
Sciences
South Dakota State University

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 Carbohydrates: Functional
Properties
 Following is a listing of possible roles:
 flavor enhancer and sweetener
 flavor and color due to caramelization and
browning reaction
 serve as water binders

 contribute to texture (starch viscosity)

 serve as a hygroscopic nature/water

absorption

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 Carbohydrates: Functional
Properties
 Yeasts grow on CHO in food
 regulate gelation of pectin

 disperse molecules of protein or starch

 preservation

 control crystallization

 structure due to crystals

 effect osmosis

 effect color of fruits

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 Important Characteristics of
Sugars
 Sweetness
 Solubility
 Hygroscopicity and Water binding
 Reduces aw
 Humectancy
 H2O migration (moisture barrier)
 The smaller, the better
 Formation of colors
 Caramelization
 Maillard reactions

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Relative sweetness of various carbohydrates
fructose 173
invert sugar* 120
HFCS (42% fructose) 120
sucrose 100
xylitol 100
tagatose 92
glucose 74
high-DE corn syrup 70
sorbitol 55
mannitol 50
trehalose (2 glucose units, C1-C1) 45
regular corn syrup 40
galactose 32
maltose 32
lactose 15

* invert sugar is a mixture of glucose and fructose found in fruits.

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 Tagatose

 Tagatose, which is 92% as sweet as sugar

(sucrose) with about a third of the
calories, is currently being evaluated as a
potential diabetes drug. Tagatose is a
stereo-isomer of fructose

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 Sweetness

 Sucrose, glucose and fructose are the

most common sweeteners in nature.
Glucose is always less sweet than sucrose,
whereas the sweetness of fructose is
highly dependent on temperature.

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 Important Characteristics of
Sugars
 Solubility
 Fru > Suc > Glu > Mal > Lac
 Temperature, Solubility
 True solutions.
 Saturated solutions.
 Supersaturated solutions.
 In making candies , solubility and ease of
crystallization are key factors

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 Important Characteristics of
Sugars
 Hygroscopicity
 High number of OH groups.
 Advantage:
 Solvation/ solubilization of sugars
 Disadvantage:
 Caking and lumps
 Fructose is the more hygroscopic.

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 Important Characteristics of
Sugars
Caramelization
 Heat > 160°C (melting point)

 1st step (Mild thermolysis)

 Break down of glycosidic bonds

 Ring size alterations and Anomeric shifts
 Formation of new glycosidic bonds.

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 Important Characteristics of
Sugars
 2nd step (Prolonged heating)
 Dehydration
 Introduction of double bonds in the sugar
rings
 Conjugated double bonds
 Hexose hydroxymethylfurfural (HMF)
 Higher temp and higher pH=higher
reaction rate

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 Important Characteristics of
Sugars
Crystalline forms of sugar: Closely
packed in an organized pattern.
 Table sugar: granulated sucrose
 Confectionary sugar
 Raw sugar
 2-3 % impurities (further purification)
 Brown sugar
 Molasses
 Crystalline glucose

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 Important characteristics of
sugars
Liquid forms
 Corn syrups
 75% carbohydrate and 25% water
 Glucose, maltose and dextrins
 First stage of HFCS
 Molasses
 <25% water and <5% ashes
 Sucrose, fructose and glucose

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 Important characteristics of
sugars
 Maple syrup
 Evaporation of maple sap < 35% water
 Flavor comes from the evaporation process
 Honey
 17% water, 82.5% carbohydrates
 Fructose 38%, Glucose 31%, Maltose 7% and
Sucrose 2%
 Traces of minerals, vitamins and enzymes

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 Polysaccharides Functions in
Foods
Functions in Foods
 Properties and functions
 Sugar units that formed them
 Type of glycosidic bonds
 Degree of branching
 Dietary polysaccharides
 Insoluble and indigestible
 Structure to food (compactness, crispiness)
 Intestinal motility

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 Polysaccharides Functions in
Foods
 Water dispersible
 Thickening agents
 Viscosity used in 0.25-0.5%, indicating their

great ability to produce viscosity and to form

gels
 Gel forming ability

 Mouthfeel

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 Polysaccharides Functions in
Foods
 Viscosity, Interaction PS-H2O depend on
 molecular size
 shape, function of rotations around the

bonds of glycosidic linkages

 Charge, number of OH groups (negative

charge, repulsion of like charges, > viscosity)

 Linear > branched

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 Polysaccharides Functions in
Foods

 Entanglement, highly branched PS will sweep

out much less space than a linear PS (collide
less frequently and produce a much lower
viscosity than will linear molecules of the
same DP).

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 Polysaccharides Functions in
Foods
Gel formation
 Polysaccharides can form gels that do not

involve normal junction zones

 Cross-linking
 Interaction of 2 different polysaccharides
 1st increase of viscosity
 2nd gelation

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 Polysaccharides Functions in
Foods
Starch
 Amylose (~25%)

 a, 1-4 Glu (+ linear)

 Gelation in cooled, cooked pastes
 DP 350-1000

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 Polysaccharides Functions in
Foods
 Amylopectin
 a, 1-4 Glu , a 1-6 Glu (+ branched)
 Waxy Corn, rice, sorghum
 Non gelling
 Stable to freezing and thawing
 DP 1000s+++

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 Amylose vs. Amylopectin

Amylose Amylopectin
MW lower higher
Glucosidic a 1-4 a1-4 & a1-6
bond
Shape Linear branched
Gelation Yes No
Retrogradation higher lower

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 Polysaccharides Functions in
Foods
Starch : Organization

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 Polysaccharides Functions in
Foods
 Proportion of Amylose to Amylopectin is
Important

 Grains 15-30 % amylose

 Legums 30-70 % amylose
 Waxy 0% amylose

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 Amorphous Region
loose association of starch
molecules that is accessible
to water

Crystalline Region
close association of starch
molecules. Causes the reflectance of
polarized light
(birefringence)

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 Starch

 Reversible swelling
 Undamaged, raw starch granules + cold water
 Small increase in volume

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 Polysaccharides Functions in
Foods
 Gelatinization: swelling and disorganiza- tion of
starch granules heated in water
 Measures of gelatinization

 Swelling of granules
 Increased viscosity

 Increased translucency

 Increased solubility

 Loss of birefringence

 Increased susceptibility to enzymes

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 Starch Gelatinization

 Heating causes the following:

 Water absorption
 Rupturing

 Starch network formed

 Hydrated network with water pockets

 Point at which rupture occurs differs

 Gelatinization!

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 Starch Gelatinization

 Molecular explanation:
 Heat = vibration of atoms
 Vibration = breaks hydrogen bonds

 Rupture and parting of starch strands

 Water trapped = increased viscosity

 Forming of hydrogen bonds = gels

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 Starch Gelatinization

 Gelatinization only occurs with heat and water

 Dry heating = dextrinization

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 Starch Gelatinization

 5% Corn starch = start of heating only has

water absorbed onto granule surfaces
 Granules still clumping

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 Starch Gelatinization

 At 40oC more water as absorbed and granules

start to separate

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 Starch Gelatinization

 At 65oC more water as absorbed and granules

start to rupture

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 Starch Gelatinization

 At 70oC further rupture, leakage

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Starch Gelatinization

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Starch Gelatinization

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 Starch Gelatinization

 Main determinants of gelatinization:

 Water content
 Starch concentration
 Nature of starch
 Degrading enzymes
 Other environmental factors

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Starch Granule - Gelatinization

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Starch granules contain both linear amylose
and branched amylopectin.

amylose forms a gel due to hydrogen

bonding between the linear chains.
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Raw, uncooked starch granules
heated in water

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Some granules have collapsed.

Gelatinization and pasting are complete

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Now we start to cool.

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 Polysaccharides Functions in
Foods
 Starch Gelation: Amylose is the “glue”
that holds the gel together
 Therefore, waxy starches do not gel
 They form thick, cooked pastes and are

frequently the starting material in the

production of modified food starches

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Notice areas of association. These are
called junction zones.

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 water
water

water

water water
water

This is a starch gel

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Gelatinization to Gelation

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 Polysaccharides Functions in
Foods
 Retrogradation and Synersis

 Amylose network is held in place by H bonds

 H bonds are continuously breaking and reforming
 Constant rearrangement of amylose liquid
escapes = Syneresis
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Reversal of retrogradation depends on the percentage of amylose
vs amylopectin. The more amylose, the harder it is to reverse.

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 Polysaccharides Functions in
Foods
 Examples of starch retrogradation

 Staling of bakery goods

 Separation in gravies and old pudding
 Reversed by re-heating

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 Polysaccharides Functions in
Foods
 Factors affecting gelatinization,
retrogradation, and gel formation
 Sugar

 Competes for water and plasticizes junction

zones; decreases gelatinization and gel
strength, increases gelatinization temp.

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 Polysaccharides Functions in
Foods
 Acid
 Hydrolysis of acid sensitive glycosidic
linkages produces smaller pieces of
starch molecules; decreases gel strength,
Faster gelatinization.

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 Polysaccharides Functions in
Foods
 Polar lipids retard gelatinization
 form complexes with amylose
 Stirring/shearing/pumping
 Collapses swollen granules; this decreases
gel formation and gel strength

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 Polysaccharides Functions in
Foods
Thickening ability
 Potato>waxy corn>waxy rice>waxy
sorghum>tapioca>wheat
 Wheat flour is less effective
 + protein, - starch
 Pastry and cake flour better than wheat
flour
 - protein

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 Polysaccharides Functions in
Foods
 Role of sugar
 Competes with starch for water
 > translucency, < gelatinization rate, < viscosity,<
gel strength
 Reduces swelling and interferes with junction zones
 Role of lipids
 Retards swelling and interferes with junction zones.
 Role of acid
 Breaks down starch (runny product)

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 Polysaccharides Functions in
Foods
 Modified starches
 The definition for modified starch is: “Starch
which has been treated physically or
chemically to modify one or more of its key
physical or chemical properties.”
 Modified starches can have functional

properties used in large scale food

production that native starches do not provide.

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 Polysaccharides Functions in
Foods
 In modified starches, only very few of the
OH groups are modified. Normally, ester or
ether groups are attached at a very low DS.
DS values are often <0.1 and range 0.002-
0.2. Thus, there is, ~ one substitution group
on every 5-500 glucose units.
 DS, average # of esterified or etherfied
groups/monosaccharide unit

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 Polysaccharides Functions in
Foods
Modified starches
 Pre-gelatinized
 Heat, swell and dry again
 Minute rice, Instant puddings, oat meal.
 Acid
 Breaks glycosidic bond outside (amorphous region)
 Crystalline region is more difficult to swell: requires a
lot of energy.
 <viscosity, > gelatinization temp, < gel strength
 Gum candies and confections
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 Polysaccharides Functions in
Foods
 Starch can be Chemically Modified to
create a wide range of functionalities
 Hydroxyethyl starches
 Cationic starches

 Starch acetates

 Starch succinates

 Starch Phosphates

 Hydroxypropyl starches

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 Polysaccharides Functions in
Foods
 Pregelatinized Starches
 Bleached Starches, treatment with low

concentrations of oxidizing agents

 Dextrins/Maltodextrins

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 Polysaccharides Functions in
Foods
Cross linked Starch
 Reinforced with covalent bonds

 Higher stability
 Heat
 Agitation
 Low pH
 Sterilized or canned products
 Baby foods, cream corn

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 Polysaccharides Functions in
Foods
Production of HFCS from Starch
 Corn starch Glu Fru
 DE = weight of Glu/ total weight * 100=
 % of reducing sugar
 Methods
 Acid (HCl-0.12%) + temperature (120-160°C)
 Acid + enzyme (amylases and glucoamylase)
 Gelatinization + enzyme
 Glu Fru ; Isomerase
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 Polysaccharides Functions in
Foods
Vegetable Gums
 Hydrocolloids
 Long chain of monosaccharides
 Sources
 Seaweed
 Carrageenan & salts; Agar; Alginates

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 Polysaccharides Functions in
Foods
 Seeds
 Guar, Locust bean gum

 Bark (exudates)
 Gum arabic, Gum tragacanth, Karaya

 Microorganisms
 Xanthan, Dextran, Gellan

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 Polysaccharides Functions in
Foods
Uses of vegetable gums
 Crystallization Inhibitor
 Whipping aid
 Foam Stabilizer
 Form and stabilize emulsions
 Coating agent
 Prevent syneresis
 Suspend solids
 Act as a carrier (flavor)
 Bulking agents/fat replacers

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