CARBOHYDRATE

Kimia Pangan 2018-2019

INTRODUCTION
Carbohydrates are the most widely distributed and
abundant organic compounds on earth.

Roles of carbohydrate:
◦In nutrition point of view:
important source of energy
(except for non-digestible
carbohydrate)
◦In food processing:
Sweetening, gel or paste-forming,
thickening agents, stabilizers, also
precursors of aroma and coloring
Carbohydrate :

Cx(H2O)y carbon + hydrate

◦Most natural carbohydrates present in the form of
oligomers (oligosaccharides) or polymers
(polysaccharides) of simple and modified sugars.

◦Main carbohydrate in food :

•Animal : glucose, glycogen
•Milk : lactose
•Plant : cellulose, pectin, starch
•Seaweed : alginate, carrageenan, agar
◦Carbohydrates are commonly divided into :

Monosaccharides: Oligosaccharides:
consists of 1 unit
consists of 2 – 10
(polyhydroxy-aldehydes or –
monosaccharide units
ketones)

Polysaccharides:
consists of n monosaccharide
units
MONOSACCHARIDES
Carbohydrate molecules that cannot be broken down to
simpler carbohydrate molecule by hydrolysis (=simple sugar)

Aldehyde group Ketone group

Haworth projection
MONOSACCHARIDES
(D and L enantiomer)

• Chiral C  attached to 4 different

groups
• D- and L- form of carbohydrates are
mirror image
• Farthest Chiral C from
aldehyde/ketone has OH on the
right  D
• Farthest Chiral C from
aldehyde/ketone has OH on the
left  L

► D- glucose
The only free aldoses found in natural foods (in small amount).
D-, L-, ᵅ-, ᵝ- form in Haworth projection
 POLYOLS
Polyols Origin
Sorbitol D-glucose
Mannitol D-mannose
xylitol xylose

• Polyols (sugar alcohols) naturally

occurred
• Polyols can be  produced by
catalytic hydrogenation
• Applications in food : noncariogenic,
low-calorie, suitable for diabetic,
nonfermentable sweetener.
 CARBOHYDRATE
Cx(H2O)y

Mono- Di- Oligo- Poly-

saccharides saccharides saccharides saccharides
Hexose (C-6) • Cellulose (a)
a. D-Glucose • Sucrose (a+d) • Rafinose (b+a+d) • Starch (a)
b. D-Galactose • Lactose (a+b) • Stachyose (b+b+a+d) • Chitin
c. D-Mannose • Maltose (a+a) -> • Verbacose • Agar
d. D-Fructose • Cellobiose (a+a) -> • Carrageenan
• Alginat
Pentose (C-5)
1. Xylose
2. Arabinose
3. Ribose
 OLIGOSACCHARIDES

◦Oligosaccharide contains 2 – 10 sugar units, joining by glycosidic

bonds
◦2, 3, 4, 5, 6, …, 10 units : disaccharides, tri-, tetra-, penta-, hexa-, …
◦Most oligosaccharides  produced by hydrolysis of
polysaccharides into smaller units. Or they are formed by
condensation of 2 monosaccharides.

sucrose
maltose

lactose
 DISACCHARIDES

There are 2 types of disaccharides:

 Non-reducing sugars
The monosccharide units are joined by a glycosidic bond
formed between their reducing groups (e.g. sucrose and
trehalose).

 Reducing sugars
•The glycosidic bond links the non-reducing group of one
monosaccharide unit to the non-alcoholic hydroxyl of the
second monosaccharide (e.g. lactose and maltose).
•Reducing sugar is any sugar that in basic solution, forms an
aldehyde or ketone. Therefore, it also includes all
monosaccharides.
POLYSACCHARIDES

◦Polysaccharides are polymers of monosaccharide.

◦DP (Degree of Polymerization)  number of monosaccharide
units in a polysaccharides.
◦Most polysaccharides have DP in the range of 200 – 3000.

◦Homoglycans : polysaccharides consists of the same sugar

type, e.g. starch amylose, starch amylopectin, cellulose
◦Heteroglycans : polysaccharides consists of different sugar
types, e.g. alginates, agar, carrageenan
◦Polysaccharides have 3 functions: as sources of energy, as
structural components of cells, and as water-binders.
POLYSACCHARIDES
◦Plant and animal cells store energy in the form of glucans
(starch and glycogen).
◦Polysaccharides occurs as several structural types: linear
e.g. amylose, cellulose), branched (e.g. amylopectin,
glycogen), interrupted (e.g. pectin), block (e.g. alginate)
or alternate repeat (e.g. agar, carragenan).
 PROPERTIES OF POLYSACCHARIDES

◦Polysaccharides are relatively less stable to hydrolytic

cleavage.
◦Depolymerization may be achieved by enzyme-catalyzed
hydrolysis and microbial attack (e.g. high fructose corn syrup
(HFCS) and tape).
◦Polysaccharides can form aqueous gels that contribute to
food structure and textural properties.
HYDROLYSIS - HFCS

A : amylose and amylopectin; B : a-

amylase; C : debranching enzyme; D :
amyloglucosidase and debranching
enzyme
POLYSACCHARIDE - STARCH

◦Commercial starches are obtained from cereal grain seeds.

◦Starch granules are insoluble, they hydrate only slighty in cold
water.
◦The viscosity building (thickening) power of starch is pronounced
only when a slurry of granules is cooked.
◦Starch consists of amylose and amylopectin.
◦Any difference in starch properties may be attributed to the
difference of amylose : amylopectin ratio.
AMYLOSE & AMYLOPECTIN

◦Amylose is a linear chain of (1→ 4)-ὰ-D-glucose units. Most

starches contain about 25% amylose.
◦Amylopectin is a highly branched molecule, with branch point
linkages in (1→ 6)-ὰ-D-glucose units consisting 4 – 5% of the total
linkages. Amylopectin constitues about 75% of most common
starches.
103 glucose units
per molecule

106 glucose units

per molecule
 STARCH GRANULES

◦Starch granules are made up of amylose and/or amylopectin

molecules arranged radially in crystalline and non-crystalline
regions in alternating layers (like onion).
◦All commercial starches contain small amounts of ash, lipid,
and protein.
◦Potato starch contains phosphate ester groups, which give
slight negative charge that may contribute in rapid swelling of
potato starch granules in warm water.
◦Cereal granules contains endogenous lipid in the granules.
STARCH – DOUBLE HELIX

◦Starch granules are partly crystalline, native starches contain

between 15 – 45% crystalline material.
◦Crystallinity results from intertwining of amylopection chains
with a linear component of over 10 glucose units to form a
double helix.
CELLULOSE

◦Cellulose is the main constituent of plant cell walls

◦Cellulose is a high-molecular-weight, linear, insoluble
homopolymer of repeating β-D-glucose units joined by (1→4)
glycosidic linkages.
◦Cellulose  can associate with each other via hydrogen
bonding over extended regions, forming polycrystalline, fibrous
bundles.
CELLULOSE DERIVATIVES
◦Cellulose can be alkylated into a number of derivatives
with good swelling properties and improved solubility. Such
derivatives have a wide field of application.

(CMC)
 XANTHAN GUM
◦Xanthan gum, the extracellular polysaccharide from Xanthomonas
campestris and some related microorganisms,
◦Xanthan gum can be regarded as a cellulose derivative. The main
chain consists of 1,4 linked β-glucose with side chain (Mannose
residue)
◦Helps in particle-suspending and emulsion-stabilizing. Due to its high
thermal stability, it is useful as a thickening agent in food canning.
CARRAGEENAN
TYPES OF CARRAGEENAN
AGAR
AGAR
 DIETARY FIBER

◦SERAT PANGAN (DIETARY FIBER):

Bagian tumbuhan yang dapat dimakan atau karbohidrat analog,
yang tahan pencernaan dan absorpsi di dalam usus halus
manusia dan mengalami fermentasi sebagian atau seluruhnya di
dalam usus besar. Serat pangan meliputi polisakarida,
karbohidrat analog, oligosakarida, lignin dan bahan yang terkait
dengan dinding sel tanaman (waxes, cutin, suberin). (AACC,
2001)
Enzymes Substance Product formed
digested
Saliva
α-Amylase Starch Maltose
Pancreatic
juice Starch Maltose
α-Amylase
Intestinal
enzymes Sucrose Glucose and
Sucrase Lactose fructose
Lactase Maltose Glucose and
Maltase galactose
Glucose
Contoh Serat Pangan
CLASS TYPE FOODS
Plant structural All cell walls of fruits &
Cellulose
Polysaccharides vegetables
Pectins/pectic substances Fruits, vegetables, legumes
Hemicelluloses Cereals, Fruits, vegetables,
Plant non-structural
Resistant starch Cereals, legumes
polysaccharides
Mucilages Tree exudates,
gums Seed extracts, food additives
Gums i.e. alginate
Algal polysaccharides Food additives
carrageenan
Gums i.e. xanthan gum, gellan
Bacterial polysaccharides Food additives
gum
Fructans Inulin, small polysaccharides Cereal, onion, artichokes
 REACTIONS OF
CARBOHYDRATES
Crystallization
◦The purer a solution of sugar, the easier it will
crystallize.

◦In certain foods, crystallization is undesirable,

such as the crystallization of lactose in
sweetened condensed milk or ice cream.

◦Seeding is a commonly used procedure to

prevent the slow crystallization of lactose in
some dairy products. Finely ground lactose
crystals are introduced into the concentrated
product, therefore many small crystals are
formed rapidly without opportunity to grow.
ROCK CANDY
Caramelization

◦Caramelization : non-enzymatic browning reaction in the

absence of nitrogenous compound.
◦Condition : little presence/absence of water, heat (±200 C).
◦The reaction is facilitated by small amounts of acids and
certain salts (e.g. ammonium bisulfite).
◦The rate of formation increases with increasing temperature
and pH.
 Caramelization

◦The reaction series :

160° C Sucrose melts,

Formation of glucose
and fructose
anhydride (levulosan)
200° C 35 min 55 min 55 min
Weight loss of 4.5% Weight loss of 9% Weight loss of 14%
Isasaccrosan Formation of Formation of Formation of
formation caramelan caramelen humin/caramelin
 Maillard Reaction
Common browning (non-enzymatic browning) of foods on
heating or on storage is usually due to a chemical reaction
between reducing sugars (mainly D-glucose) and a primary
amino group (a free amino acid or amino group on a side
chain of protein).

MR produces numerous compounds, i.e. flavors, aromas,

and dark-colored polymeric materials, which may be either
desirable or undesirable.

MR may be produced by frying, roasting, baking, or storage.

 Maillard Reaction

The Maillard reaction involved the formation of Schiff base

which will transformed via Amadori rearrangements into
intermediates of Maillard reaction, so-called Amadori
compound.

This intermediates will undergo complex transformation to

form furan derivates i.e. hydroxymethylfurfural / HMF (from
hexose) or furfural (from pentose).

Under pH>5, HMF and furfural and compounds containing

amino groups polymerize to a dark-colored, nitrogen-
containing pigment called melanoidin.
Schiff base
Maillard Reaction

(+) (-)

◦ The formation of ◦Destroy the essential

desirable flavor, aroma, amino acids (i.e. L-lysine,
and color compounds. methionine, cystein).
◦Formation of mutagenic
compounds (e.g.
mutagenic heterocyclic
amines, acrylamide).
Maillard Reaction

MR requires heat (>100oC)

The reaction is accelerated in an alkaline environment
(the amino acids are deprotonated, so the nucleophilicity
increases).
Pentoses (e.g. ribose, xylose, and arabinose) are more
reactive than hexoses (e.g. glucose, fructose, and
galactose).
Different sugars give different unique flavor and color
compounds.
SIFAT FUNGSIONAL

1. Sweetness & sweeteners

2. Hygroscopicity
1. Reduced Aw  preservative
2. Adsorbent  baby care products
3. Moisture  beauty care
products
3. Textural contribution
1. Rigidity : bread
2. Viscosity : sauces
FUNCTIONAL PROPERTIES

Carrageenan synergy with milk proteins