Carbohydrates in Foods

A general overview

Dr. Nguyen Van Toan (PhD)

 CARBOHYDRATES
▪ What are carbohydrates?
- Carbon compounds that contain many hydroxyl groups(-OH).
- The simplest carbohydrates also contain either an aldehyde or a ketone

▪ The presence of the hydroxyl groups (–OH) allows

carbohydrates to
✓ Interact with the aqueous environment, and
✓ To participate in hydrogen bonding, both within and between
chains.
 Types of Carbohydrates
Classifications of carbohydrates based on number of sugar units
in total chain.

Chaining relied on ‘ bridging ‘ of oxygen atoms- glycosidic bonds

▪ SUGARS contain 2 important and very reactive functional
groups:
– -OH (hydroxyl group): important for
➢Solubility and sweetness
– -C=O (carbonyl group): important for
➢Reducing ability and Maillard/ browning reactions
❖ GLUCOSE is an ALDOSE sugar with one C atom external to the 6-
membered ring

❖ FRUCTOSE is a KETOSE hexose with two carbon atoms external to the 6-

membered ring

GLUCOSE FRUCTOSE
https://www.youtube.com/watch?v=rs1JLYXROVU
 Monosaccharides
▪ The monosaccharides commonly found in foods are classified
according to the number of carbons they contain in their
backbone structures.

▪ The major food monosaccharides contain six carbon atoms.

Carbohydrate Classifications
▪ Hexose = six-carbon sugars
❖ Glucose,
❖ Galactose,
❖ Fructose
Chair form of a-D-Glucose

Haworth Projection of a-D-Glucose

Fischer Projection of a-D-Glucose
 Disaccharides
▪ Bonds between sugar units are termed glycosidic bonds, and
the resultant molecules are glycosides.

▪ The linkage of two monosaccharides to form disaccharides

involves a glycosidic bond.

▪ The important food disaccharides are sucrose, lactose, and

maltose.

Sucrose: prevalent in sugar cane and sugar beets, is composed

of glucose and fructose through an α-(1,2) glycosidic bond.
Lactose:
is found exclusively in the milk of mammals and consists of
galactose and glucose in a β-(1,4) glycosidic bond.

Maltose:
Is the major degradation product of starch, and is composed of 2 glucose
monomers in an α-(1,4) glycosidic bond.
 Polysaccharides
▪ Most of the carbohydrates found in nature occur in the form of high
molecular weight polymers called polysaccharides.

▪ The monomeric building blocks used to generate polysaccharides can be

varied; in all cases, however, the predominant monosaccharide found in
polysaccharides is D-glucose.

▪ When polysaccharides are composed of a single monosaccharide building

block, they are termed homopolysaccharides.
FUNCTIONAL PROPERTIES OF CARBOHYDRATES
▪ Reducing sugars
▪ Browning reactions (caramelization and Maillard)
▪ Sweetness and flavors
▪ Crystallization
▪ Humectancy
▪ Inversion
▪ Oxidation and reduction
▪ Texturizing
▪ Viscosity
▪ Gelling (gums, pectins, other hydrocolloids)
▪ Gelatinization (Starch)
Aldose (aldehyde) and Ketose (ketone)
 Properties of Glucose
▪ C1 of glucose is the carbonyl carbon
▪ Glucose has 4 chiral centers
– Non-super-imposable on its mirror
image
▪ Carbons 2, 3, 4, 5 are chiral carbons

▪ The carbonyl carbon (C1) is also the site

of many reactions involving glucose
– They have two enantiomeric forms, D
and L, depending on the location of the
hydroxyl group at the chiral carbons.
Sugar Reactions
Reduction of Monosaccharide

▪ In this reaction the carbonyl group is reduced to an alcohol

by a metal catalyzed reaction of hydrogen gas under
pressure.
 Sugar Alcohols
▪ Not commonly found in nature
– Generally lower in calories (2 to 3
kcal/g)
– A CHO for labeling purposes
– Not digested by oral bacteria
– “does not promote tooth decay”
Some examples
▪ Xylitol (from xylose)
▪ Sorbitol (from glucose)
▪ Mannitol (from mannose)
▪ Lactitol (from lactose)
▪ Maltitol (from maltose)
 Sucrose

Where does sucrose come from?

Sucrose is a type of sugar that is found in many plants but
extracted as ordinary sugar mainly from sugar cane and sugar
beets.
 Invert sugar
▪ Invert sugar is a liquid carbohydrate sweetener in which all
or a portion of the sucrose present has been inverted:
– The sucrose molecule is split and converts to an equimolar mixture
of glucose and fructose.
▪ Invert sugars have properties from sucrose; they help
baked goods retain moisture, and prolong shelf-life.
▪ Candy manufacturers use invert sugar to control graining.
▪ Invert sugar is different from high fructose sweeteners

▪ SUCROSE + invertase enzyme  glucose + fructose

 Corn syrups
▪ Corn syrups are manufactured by treating corn
starch with acids or enzymes.
▪ Corn syrups, used extensively by the food
industry and in the home kitchen, contain primarily
glucose (dextrose) but other sugars as well.
▪ High-fructose corn syrup (HFCS) is made by
treating dextrose-rich corn syrup with enzymes
(isomerase).
▪ The resulting HFCS is a liquid mixture of dextrose
and fructose used by food manufacturers in soft
drinks, canned fruits, jams and other foods.

▪ HFCS contains 42, 55, 90 or 99 percent fructose.

PROCESSING OF CORN STARCH  HFCS
▪ Corn starch is treated with α-amylase, of bacterial origin, to
produce shorter chains of sugars (dextrins) as starch
fragments.

▪ Next, an enzyme called glucoamylase, obtained from the

fungus Aspergillus niger, breaks the fragments down even
further to yield the simple sugar glucose.

▪ A third enzyme, glucose isomerase, is expensive, and

converts glucose to varous amounts of frutose.
– HFCS-55 has the exact same sweetness intensity as sucrose (cola)
– HFCS-42 is less sweet, used with fruit-based beverages and for
baking

▪ Glucose isomerase is so expensive that it is commonly

immobilized on a solid-based “resin” bead and the glucose
syrup passed over it. Can be used many times over before
it slowly looses its activity.
 HFCS
▪ HFCS is selected for different purposes.
Selection is based on specific desired properties:

▪ Retain moisture and/or prevent drying out

▪ Control crystallization
▪ Produce a higher osmotic pressure (more molecules in solution)
than for sucrose
▪ Control microbiological growth

▪ Provide a ready yeast-fermentable substrate

▪ Blend easily with sweeteners, acids, and flavorings
▪ Provide a controllable substrate for browning and Maillard
reaction.
▪ Impart a degree of sweetness essentially = to invert liquid sugars

▪ High sweetness
▪ Low viscosity
▪ Reduced tendency toward crystallization
▪ Costs less than liquid sucrose or corn syrup blends
▪ Retain moisture and/or prevent drying out of food product
Starch
 Starch
Starch is the major form of stored carbohydrate in
plant cells.
▪ Its structure is identical to glycogen, except for a much lower
degree of branching (about every 20-30 residues).

▪ Unbranched starch is called amylose

▪ Branched starch is called amylopectin.
 Starches- #1 Hydrocolloid
▪ Hydrocolloids are substances that will form a gel or
add viscosity on addition of water.
▪ Most hydrocolloids are polysaccharides and all
interact with water.

▪ The most common hydrocolloids is starch

▪ Starch is a mixture of amylose and amylopectin.

▪ The size distribution of these hydrocolloids is the most

important factor in the texture and physical features of
foods
 STARCH
➢Polymers of glucose
▪ AMYLOSE linear chain of glucose
– Glucose polymer linked α-1,4

▪ AMYLOPECTIN branched polymer of glucose

Amylose

Amylopectin
 AMYLOSE

▪ Linear polymer of glucose

▪ α 1 - 4 linkages
▪ Digestible by humans (4 kcal/g)
▪ 250-350 glucose units on average
▪ Corn, wheat, and potato starch
– ~10-30% amylose
 AMYLOPECTIN

▪ Branched chain polymer of glucose

▪ α 1 - 4 and α 1 - 6 glycosidic linkages
▪ Fully digestable by humans
▪ 1,000 glucose units is common
– Branch points every ~15-25 units
Starch

▪ Amylopectin (black)
▪ Amylose (blue)
 Modified Starches
▪ Gelatinization is the easiest modification
– Heated in water then dried.
▪ Acid and/heat will form “dextrins”
▪ α-Amylase
– hydrolyzes α (1-4) linkage
– random attack to make shorter chains
▪ β-Amylase
– Also attacks α (1 - 4) linkages
– Starts at the non-reducing end of the starch chain
– Gives short dextrins and maltose
▪ Both enzymes have trouble with α (1 - 6) linkages
DEXTRINS are considered to be hydrolysis products of
incompletely broken down starch fractions
Polysaccharide Breakdown
Products
Maltodextrins and enzyme-converted starch:

STARCH fermentation SUGARS

ETHANOL

MODIFIED STARCHES

GELATINIZED STARCH alpha amylase Maltodextrins

Corn Syrups

Sugars
The smaller the size of the products in these reactions, the
higher the dextrose equivalence (DE), and the sweeter
they are

Starch DE = 0
Glucose (dextrose) DE = 100

Maltodextrin (MD) DE is <20

Corn syrup solids (CS) DE is >20

Low DE syrup alpha amylase MD beta amylase High

DE
Syrup
 Hydrocolloids

Binding water with carbohydrates

“Gums”
 “Vegetable gum” polysaccharides are substances derived
from plants, including seaweed and various shrubs or trees,
have the ability to hold water, and often act as thickeners,
stabilizers, or gelling agents in various food products.

Plant gums - exudates, seeds

Marine hydrocolloids - extracts from seaweeds

Microbiological polysaccharides - exocellular polysaccharides

Modified, natural polysaccharides

 FUNCTIONS IN FOOD

▪ Gelatin
▪ Viscosity
▪ Suspension
▪ Emulsification and stability
▪ Whipping
▪ Freeze thaw protection
▪ Fiber (dietary fiber)
– Gut health
– Binds cholesterol
STRUCTURAL CONSIDERATIONS

▪ Electrical charge, pH sensitive

– Interactions with oppositely charged molecules
– Salts
– Low pH effects
▪ Chain length
– Longer chains are more viscous
▪ Linear vs Branched chains
– Inter-entangled, enter-woven molecules
 Gums

▪ GUAR (Guran Gum)

– Most used, behind starch, low cost
– Guar bean from India and Pakistan
– Cold water soluble, highly branched galactomannan
– Stable over large pH range, heat stable
– Thickening agent, not a gel
– Often added with xanthan gum (synergistic)
▪ XANTHAN
▪ Extracellular polysaccharide from Xanthomonas
campestris
– Very popular, inexpensive from fermentations
– Forms very thick gels at very low concentrations
 Gums

▪ LOCUST BEAN
– Branched galactomannan polymer (like guar),
but needs hot water to solubilize
– Bean from Italy and Spain
– Jams, jellies, ice cream, mayonnaise
 SEAWEED EXTRACTS

▪ Carrageenans (from red seaweed)

– Kappa (gel)
– Iota (gel)
– Lambda (thickener only)
– Milk, baking, cheese, ice cream
▪ Agar
▪ Alginates
 “Structural” Polysaccharides
Cellulose
▪ Polymer of glucose linked ß-1,4
Hemicellulose
▪ Similar to cellulose
▪ Consist of glucose and other
monosaccharides
– Arabinose, xylose, other 5-carbon sugars
Pectin
▪ Polymer of galacturonic acid
 MODIFIED CELLULOSES
▪ Chemically modified cellulose
▪ Do not occur naturally in plants
▪ Similar to starch, but β-(1,4) glycosidic
bonds
▪ Carboxymethyl cellulose (CMC) most
common
– Acid treatment to add a methyl group
– Increases water solubility, thickening agent
– Sensitive to salts and low pH
▪ Fruit fillings, custards, processed cheeses,
high fiber filler
 PECTINS
▪ Linear polymers of galacturonic acid
– Gels form with degree of methylation of its carboxylic
acid groups
– Many sources, all natural, apple and citrus pomace
▪ Susceptible to degrading enzymes
– Polygalacturonase (depolymerize)
– Pectin esterases (remove methyl groups)
▪ Longer polymers, higher viscosity
▪ Lower methylation, lower viscosity
▪ Increase electrolytes (ie. metal cations), higher
viscosity
▪ pH an soluble solids impact viscosity
PECTIC SUBSTANCES: cell cementing compound; fruits and vegetables;
pectin will form gel with appropriate concentration, amount of sugar and pH.

Basic unit comprised of galacturonic acid.

Composition: polymer of galacturonic acids; may be partially esterified.

Pectic Acid

Pectin Molecule
 PECTINS
▪ Pectins are important because they form gels

▪ Mechanism of gel formation differs by the degree of esterification (DE)

of the pectin molecules
– DE refers to that percentage of pectin units with a methyl group
attached

▪ Free COOH groups can crosslink with divalent cations

▪ Sugar and acid under certain conditions can contribute to gel structure
and formation

▪ LM pectin “low methoxyl pectin” has DE < 50% ; gelatin is controlled

by adding cations (like Ca++ and controlling the pH)

▪ HM pectin “high methoxyl pectin” has DE >50% and forms a gel under
acidic conditions by hydrophobic interactions and H-bonding with
dissolved solids (i.e. sugar)
Hydrophobic attractions between neighboring pectin polymer chains
promote gelation
 BETA-GLUCANS

▪ Extracts from the bran of barley and oats

▪ Long glucose chains with mixed ß-linkages
▪ Very large (~250,000 glucose units)
– Water soluble, but have a low viscosity
– Can be used as a fat replacer
– Responsible for the health claims (cholesterol)
for whole oat products
– Formulated to reduce the glycemic index of a
food
 Others
CHITIN
▪ Polymer of N-Acetyl-D-glucosamine
▪ Found in the exoskeleton of insects and shellfish
▪ Many uses in industry, food and non-food.

INULIN
▪ Chains of fructose that end in a glucose molecule
– Generally a sweet taste
– Isolated from Jerusalem artichokes and chicory
– Act as a dietary fiber
– Potentially a pre-biotic compound
 COMPONENTS OF DIETARY FIBER

SOURCE
COMPONENT

Cellulose All food plants

All food plants, especially cereal

Hemicellulose
bran

Pectin Mainly fruit

Mainly cereals and 'woody'

Lignin
vegetables

Gums and some food Food additives in processed

thickeners foods
 HYDROCOLLOIDS
▪ A key attribute of gums is to produce viscous dispersions in water

▪ Viscosity depends on:

▪ Gum type
▪ Temperature
▪ Concentration of gum
▪ Degree of polymerization of gum
▪ Linear or branched polymers
▪ Presence of other substances in the system

▪ Solubility (dispersability in water) varies among gums

▪ Agar is insoluble in cold water; dissolves in boiling water

▪ Methylcellulose is insoluble in hot water, but soluble in cold !

 Suggested questions for review
1) Show your understanding upon the roles of hydroxyl group in
food, discuss and give examples, where possible.
2) Compare food dehydration and food concentration, and
reasons for drying foods
3) Discuss about the classification of carbohydrates as well as the
nutritional aspect of carbohydrates
Thank you for your attention

Good luck to you!