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Chapter 1 Carbohydrates
Chapter 1 Carbohydrates
Carbohydrates
Chapter 18
Table of Contents
18.1 Biochemistry—An Overview
18.2 Occurrence and Functions of Carbohydrates
18.3 Classification of Carbohydrates
18.4 Chirality: Handedness in Molecules
18.5 Stereoisomerism: Enantiomers and Diastereomers
18.6 Designating Handedness Using Fischer Projections Formulas
18.7 Properties of Enantiomers
18.8 Classification of Monosaccharides
18.9 Biochemically Important Monosaccharides
18.10 Cyclic Forms of Monosaccharides
18.11 Haworth Projection Formulas
18.12 Reactions of Monosaccharides
18.13 Disaccharides
18.14 General Characteristics of Polysaccharides
18.15 Storage Polysaccharides
18.16 Structural Polysaccharides
18.17 Acidic Polysaccharides
18.18 Glycolipids and Glycoproteins: Cell Recognition
18.19 Dietary Considerations and Carbohydrates
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Photosynthesis
• 75% of dry plant material: Produced by photosynthesis
• Cellulose: structural element
• Starch/glycogen: energy reservoir
- small amount in human body
• Plant products are source of carbohydrates
- average human diet contains 2/3 of carbohydrates
Most of the matter in plants, except water, is carbohydrate
material.
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Photosynthesis
• Simpler Formula:
– CnH2nOn or Cn(H2O)n (hydrates of C)
– n= number of atoms
• Carbohydrates are polyhydroxy aldehydes or ketones or
compounds that produce such substances upon
hydrolysis
CHO CH2 OH
Aldehyde H OH O Ketone
HO H HO H
H OH H OH
H OH H OH
Polyhydroxy ketone
CH2 OH CH2 OH
Polyhydroxy
aldehyde Glucos e Fructose
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Monosaccharide
• Contain single polyhydroxy aldehyde or ketone unit
• They can’t be broken down into simpler substances by
hydrolysis (reaction with water) reactions
• Contains 3-7 C atoms
• 5 and 6 carbon species are more common
• Water soluble white crystalline solids
CHO CH2 OH
H OH O
HO H HO H Glucose and fructose
H OH H OH
H OH
are monosaccharides
H OH
CH2 OH CH2 OH
Oligosaccharides
• Contains ~2-10 monosaccharide units - covalently
bonded to each other
• Disaccharides (contain 2 monosaccharide units) more
common - crystalline water soluble substances
• Table sugar (sucrose) and milk sugar (lactose)
- are common disaccharides
• Upon hydrolysis they produce monosaccharide
• In human body associated with proteins and lipids for
structural and regulatory functions
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Polysaccharides
• Contains many monosaccharide units covalently bonded
• Polymers: May contain 100s of 1000s of
monosaccharide units
• Examples:
• Cellulose: Paper, cotton, wood
• Starch: Bread, pasta, potatoes, rice, corn, beans,
peas, etc.
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Chirality
• Chiral Center: C atom attached to 4 different groups
• A molecule with chiral center is a chiral molecule
– Best way to visualize - look at all C atoms and see if there are at
least two H atoms then that can’t be a chiral center
– C atoms with less than one H atoms are worth looking at for
their chirality.
• Be careful as a C atom may apparently look similar but may not
have four DIFFERENT groups.
– E. g. 3-bromopentane - C has two CH2-CH3 groups – so it is
achiral A chiral C is usually denoted by *
Br
*
3-Bromopentane Return to TOC
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Practice Exercise
Answers:
a. Not a chiral center
b. Not a chiral center
c. Chiral center
d. Not a chiral center Return to TOC
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Stereoisomers
• Stereoisomers are isomers that have the same
molecular and structural formulas but differ in the
orientation of atoms in space.
• Two types:
• Enantiomers are stereoisomers whose molecules are
nonsuperimposable mirror images of each other.
Molecules with chiral center.
• Diastereomers are stereoisomers whose molecules are
not mirror images of each other.
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Tetrahedral Arrangements
• The four groups attached to the atom at the chiral center
assume a tetrahedral geometry and it is governed by the
following conventions
• Vertical lines from the chiral center represent bonds to groups
directed into the printed page.
• Horizontal lines from the chiral center represent bonds to
groups directed out of the printed page
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CHO CHO
H OH HO H
CH2OH CH2OH
D-Glyceroldehyde L-Glyceroldehyde
(-OH on right side) (-OH on left side)
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Exercise
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Monosaccharides
• Triose --- 3 carbon atoms
• Tetrose -- 4 carbon atoms
• Pentoses – 5 carbon atoms
• Hexoses -- 6 carbon atoms
• Aldoses: Monosaccharides with one aldehyde group
• Ketoses: Monosaccharides with one ketone group
• Combined # of C atoms and functional group:
– Example: Aldohexose: Monosaccharide with
aldehyde group and 6 C atoms
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atoms – D-glucose H OH H OH
– Ketohexose: H OH H OH
Monosaccharide with
CH2OH CH2OH
aldehyde group and 6 C
atoms – D-fructose D-Glucose
(aldohexose)
D-Fructose
(ketohexose)
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Exercise
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CH2OH
O 1. Ketohexose
HO H
2. Sweetest tasting of all sugars
H OH
3. Found in many fruits and in honey
H OH
4. Good dietary sugar-- due to higher sweetness
CH2OH
5. Five membered cyclic form
D-Fructose
(ketohexose)
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6 6
CH2 OH CH 2OH
O O OH
5 5
4 1
OH 4 OH
1
2 OH 2
OH OH
3 3
OH OH
-D-Glucose -D-Glucose
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CH2 OH
O CH2OH
CH2OH CH2 OH
O O
OH
OH
OH OH
OH OH
OH OH
OH OH
-D-Glucose -D-Fructose -D-Ribose
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OH Group
• The specific identity of a monosaccharide is determined by the
positioning of the other —OH groups in the Haworth projection
formula.
• Any —OH group at a chiral center that is to the right in a Fischer
projection formula points down in the Haworth projection formula
and any —OH group to the left in a Fischer projection formula points
up in the Haworth projection formula.
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Practice Exercise
Answers:
a. Ribose
b. Fructose
c. Glucose, galactose
d. Fructose
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Oxidation
• Oxidation to acidic sugars: The redox chemistry of
monosaccharides is closely linked to the alcohol
and aldehyde functional groups present in them.
• Oxidation can yield three different types of acidic
sugars depending on the type of oxidizing agent
used:
– Weak oxidizing agents such as Tollens and
Benedict’s solutions oxidize the aldehyde end
to give an aldonic acid.
– A reducing sugar is a carbohydrate that gives a
positive test with Tollens and Benedict’s
solutions. Return to TOC
Oxidizing Agents
• Strong oxidizing agents can oxidize both ends of a
monosaccharide at the same time (the carbonyl group
and the terminal primary alcohol group) to produce a
dicarboxylic acid:
– Such polyhydroxy dicarboxylic acids are known as
aldaric acids.
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Oxidization
• In biochemical systems enzymes can oxidize the primary
alcohol end of an aldose such as glucose, without
oxidation of the aldehyde group, to produce an alduronic
acid.
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Sugar Alcohols
• Reduction to sugar alcohols: The carbonyl group in a
monosaccharide (either an aldose or a ketose) is
reduced to a hydroxyl group using hydrogen as the
reducing agent.
– The product is the corresponding polyhydroxy alcohol
- sugar alcohol.
– Sorbitol - used as moisturizing agents in foods and
cosmetics and as a sweetening agent in chewing
gum
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Glycloside
• Glycoside formation: Cyclic forms of monosaccharides
are hemiacetals, they react with alcohols to form acetals:
– Monosaccharide acetals are called glycoside
• A glycoside is an acetal formed from a cyclic
monosaccharide by replacement of the hemiacetal
carbon —OH group with an —OR group:
– A glycoside produced from glucose - glucoside
– A glycoside produced from galactose – galactoside
– Glycosides exist in both Alpha and Beta forms
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Blood Types
• In the United States type O blood is the most common
and type A the second most common.
• The biochemical basis for the various blood types
involves monosaccharides present on plasma
membranes of red blood cells.
• The monosaccharides responsible for blood groups
are D-galactose and its derivatives.
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Cellobiose
• Cellobiose is produced as an intermediate in the
hydrolysis of the polysaccharide cellulose:
– Cellobiose contains two b - D-glucose
monosaccharide units linked through a b (1—4)
glycosidic linkage.
CH2OH
O OH
CH2OH (1-4)
H
O OH
O
OH
OH
OH
OH
Cellobiose
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Maltose
• Maltose is digested easily by humans because we have
enzymes that can break a (1-4) linkages but not b (1-4)
linkages of cellobiose. Therefore cellobiose cannot be
digested by humans.
CH2 OH CH2 OH
O O
OH OH
O OH
OH (1-4)
OH OH
Maltose
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Lactose
• Lactose is made up of b-D-galactose unit and a b-D-
glucose unit joined by a b(1-4) glycosidic linkage
CH2OH
O OH
(1-4)
CH2OH H
OH
OH O O
OH
OH
OH
Lactose
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Lactose
• Lactose - principal carbohydrate in milk.
– Human - 7%–8% lactose
– cow’s milk - 4%–5% lactose
– Lactose intolerance: a condition in which people lack the
enzyme lactase needed to hydrolyze lactose to galactose and
glucose.
– Lactase hydrolyzes b(1-4) glycosidic linkages.
– Deficiency of lactase can be caused by a genetic defect,
physiological decline with age, or by injuries to intestinal
mucosa.
– When lactose is undigested it attracts water causing fullness,
discomfort, cramping, nausea, and diarrhea. Bacterial
fermentation of the lactose further along the intestinal tract
produces acid (lactic acid) and gas, adding to the discomfort. Return to TOC
Sucrose
• Sucrose (table sugar): The
CH2 OH
most abundant of all O
disaccharides and found in CH2 OH
OH
plants. OH OH
O
• It is produced commercially OH OH
+ OH (1-2)
and sugar beets. CH2 OH CH2 OH
O
Linkage
O OH O
– Sugar cane contains up to
OH OH
20% by mass sucrose
CH 2OH CH 2OH
– Sugar beets contain up to OH OH
17% by mass sucrose -D-Fructose Sucrose
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Practice Exercise
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Starch
• A storage polysaccharide is a polysaccharide that is a
storage form for monosaccharides and is used as an
energy source in cells.
• Starch:
– Glucose is the monomeric unit
– Storage polysaccharide in plants
– Two types of polysaccharidse isolated from starch:
– Amylose: Straight chain polymer - 15 - 20% of the
starch and has a (1 → 4) glycosidic bonds
– Molecular Mass: 50,000 (up to 1000 glucose units)
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Amylopectin Stucture
• Amylopectin:
– Branched chain polymer - 80 - 85 % of the starch a
(1→4) glycosidic bond for straight chain and a (1→6)
for branch
– Molecular Mass: 300,000 (up to 100,000 glucose
units) - higher than amylose
– Human can hydrolyze alpha linkage but not beta
linkage
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Glycogen
– Humans and animals storage polysaccharide
– Contains only glucose units
– Branched chain polymer – a (1→4) glycosidic bonds in straight
chains and a (1→6) in branches
– Molecular Mass: 3,000,000 (up to 1,000,000 glucose units)
– Three times more highly branched than amylopectin in starch
– Excess glucose in blood stored in the form of glycogen
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Cellulose
• Linear homopolysaccharide with b (1 → 4) glycosidic bond
• Up to 5000 glucose units with molecular mass of 900,000 amu
– Cotton ~95% cellulose and wood ~50% cellulose
– Humans don’t have enzymes that hydrolyze b (1 → 4) - so humans
can not digest cellulose -- animals also lack these enzymes but they
can digest cellulose because they have bacteria in their guts to
hydrolyze cellulose
– It serves as dietary fiber in food-- readily absorbs water and results in
softer stools HO
– 20 - 35 g of dietary fiber is desired everyday O HO O
OH
HO O O
OH (1-4) OH
HO O O
OH (1-4)
O O OH
OH (1-4)
O OH
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Chitin
– Similar to cellulose in both function and structure
– Linear polymer with all b (1→4) glycosidic linkages - it has a N-
acetyl amino derivative of glucose
– Function is to give rigidity to the exoskeleton s of crabs,
lobsters, shrimp, insects, and other arthropods
HO
HO O O
OH
HO O
O N-Acetyl
OH HN -D-Glucoseamine
O O
HO
OH HN O
O O
O OH HN O
HN O
O
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Nutrition
• Foods high in carbs content constitute over 50% of the diet of most
people of the world -- a balanced dietary food should contain about
60% of carbohydrate:
– Corn in South America
– Rice in Asia
– Starchy root vegetables in parts of Africa
– Potato and wheat in North America
• Nutritionist divide dietary carbs into two classes:
– Simple carb: dietary monosaccharides or disaccharides - sweet
to taste commonly referred to as sugars - 20 % of the energy in
the US die
– Complex carbs: Dietary polysaccharides -- starch and cellulose -
normally not sweet to taste
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Glycemic Foods
• A developing concern about intake of carbohydrates
involves how fast the given dietary carbs are broken
down to glucose within the human body
• Glycemic effect refers to:
– how quickly carbs are digested
– how high blood glucose rise
– how quickly blood glucose levels return to normal
• Glycemic index (GI) has been developed for rating foods
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