Chapter 1 – CARBOHYDRATES Functions of Carbohydrates in the Human Body

The study of living things - Carbohydrate oxidation provides energy

- Carbohydrate storage, in the form of glycogen,
Biochemistry - study of the chemical substances provides a short-term energy reserve
found in living organisms and the chemical - Carbohydrates supply carbon atoms for the
interactions of these substances with each other. synthesis of other biochemical substances
Biochemical substance - chemical substance found (proteins, lipids, and nucleic acids)
within a living organism - Carbohydrates form part of the structural
framework of DNA and RNA molecules
Types of biochemical substances: - Carbohydrates linked to lipids are structural
components of cell membranes
Bioinorganic substances - water and inorganic salts
- Carbohydrates linked to proteins function in a
Bioorganic substances - carbohydrates, lipids, variety of cell-cell and cell-molecule recognition
proteins, and nucleic acids processes

Bioinorganic and Bioorganic Substances CLASSIFICATION OF CARBOHYDRATES

- As isolated compounds, bioinorganic and Empirical formula of simple carbohydrates:

bioorganic substances have no life in and of
themselves.
- When these substances are gathered together in
a cell, their chemical interactions are able to
sustain life. Carbohydrate: Polyhydroxy aldehyde, ketone, or a
compound that produces such substances upon
OCCURENCE AND FUNCTIONS OF CARBOHYDRATES hydrolysis
Plants and Carbohydrates
- It is estimated that more than half of all organic
carbon atoms are found in the carbohydrate
materials of plants
- Human uses for carbohydrates of the plant
kingdom extend beyond food
- Carbohydrates in the form of cotton and linen are
used as clothing Monosaccharides
- Carbohydrates in the form of wood are used for
shelter and heating and in making paper - Contain single polyhydroxy aldehyde or ketone
unit
Carbohydrates - Cannot be broken down into simpler substances
by hydrolysis reactions
- Most of the matter in plants, except water, is
- Contain 3-7 C atoms
carbohydrate material
- 5 and 6 carbon species are more common
- Carbohydrates account for 75% of dry plant
material and are produced by photosynthesis Pure monosaccharides - water soluble white,
crystalline solids
- Cellulose - structural element
Monosaccharides – glucose and fructose
- Starch/glycogen - energy reservoir
Disaccharides
Photosynthesis
- Contain 2 monosaccharide units covalently
- Process in which plants produce carbohydrates bonded to each other
using carbon dioxide, water, and solar energy - Crystalline and water soluble substances
- Common disaccharides - table sugar (sucrose)
and milk sugar (lactose)
- Upon hydrolysis, they produce 2 monosaccharide
units
Oligosaccharides
- Contain three to ten monosaccharide units
covalently bonded to each other
- Free oligosaccharides are seldom encountered in
biochemical systems
- Usually found associated with proteins and lipids
in complex molecules
- Serve structural and regulatory functions Responses of Left and Right Handed Forms of a
Polysaccharides Molecule in a Human Body

- Contain many monosaccharide units covalently - Both forms may be active, one may be more
bonded active, or one may be active and other nonactive
- Number of monosaccharide units varies from a Example:
few 100 units to 50,000 units Response of the body to the right-handed
hormone epinephrine is 20 times greater than
Examples: responses to the left-handed form
Cellulose - paper, cotton, wood - Almost all monosaccharides are right handed
Starch - bread, pasta, potatoes, rice, corn, & beans - Amino acids are always left handed

CHIRALITY: Handedness in Molecules STEREOISOMERISM: Enantiomers and Diastereomers

Objects and Handedness Stereoisomers

- Isomers that have the same molecular and
- Most biological molecules, including
structural formulas but differ in the orientation
carbohydrates, exhibit the property
of atoms in space
"handedness" (form of isomerism
Two types:
- Most molecules that possess "handedness" exist
- Enantiomers - Stereoisomers whose molecules
in two forms:
are non-superimposable mirror images of each
"Left-handed" form
other (molecules with chiral center)
"Right-handed" form
- Diastereomers - Stereoisomers whose
- Related in the same manner as two hands that
molecules are not mirror images of each other
are "mirror images" of each other
Example: Cis-trans isomers
Mirror Images
Designating Handedness Using Fischer Projection
- Reflection of an object in a mirror Formulas
Classes of objects based on mirror images: Fischer Project Formula
- Two-dimensional structural notation for showing
- Superimposable mirror images: Images that
the spatial arrangement of groups about chiral
coincide at all points when the images are laid
centers in molecules
upon each other (achiral molecule)
- According to this formula, a chiral center is
- Nonsuperimposable mirror images: Images
represented as the intersection of vertical and
where not all points coincide when the images
horizontal lines
are laid upon each other (Chiral molecule,
handedness) - Functional groups of high priority will be written
at the top
Chirality
Tetrahedral Arrangements
- Chiral center: C atom attached to 4 different - The four groups attached to the atom at the
groups chiral center assume a tetrahedral geometry
- A molecule with chiral center is said to be chiral governed by the following conventions:
- a C atom must have four different groups - Vertical lines from the chiral center represent
attached to it in order to be a chiral center. bonds to groups directed into the printed page
- A chiral C is usually denoted by * - Horizontal lines from the chiral center represent
- Bromochloroiodomethane is a chiral organic bonds to groups directed out of the printed page
molecule
Fischer Project Formulas Interaction of Enantiomers with Plane-Polarized Light
- Land D system used to designate the handedness
Properties of light:
of glyceraldehyde enantiomers are shown below
- Ordinary light waves - Vibrate in all directions
- Plane polarized light waves - Vibrate only in
one direction
- Plane-polarized light is rotated clockwise (to
The D OH is the most common or the most usable by right - D) or counterclockwise (to left - L) when
the system because it has a 20% effect than the L passed through enantiomers
- We now consider Fischer projection formulas for - Direction and extent of rotation will depend
the compound 2,3,4-trihydroxybutanal, a upon the concentration of the enantiomer
monosaccharide with four carbons and two - Same concentration of two enantiomers rotates
chiral centers light to same extent but in opposite directions
- There are four stereoisomers for this compound
and two pairs of enantiomers

- The D,L system used to designate the handedness

of glyceraldehyde enantiomers can be extended
to other monosaccharides with more than one
chiral center Dextrorotatory and Levorotatory Compounds
- The carbon chain is numbered starting at the
carbonyl group end of the molecule, and the - Enantiomers are optically active, i.e., they are
highest-numbered chiral center is used to compounds that rotate the plane of polarized
determine D or L configuration. light
- Dextrorotatory compound - Chiral compound
that rotates light towards right (clockwise; +)
- Levorotatory compound - Chiral compound
that rotates light towards left (counterclockwise; -)
- There is no correlation between D, L and +,
- In D and L system, the structure is viewed - + and
- can be determined using a polarimeter

Epimers – diastereomers wholes molecules differ Interactions Between Chiral Compounds

only in configuration at on chiral center
- Right- and left-handed baseball players cannot
Properties of Enantiomers use the same glove (chiral) but can use the same
hat (achiral)
Constitutional Isomers and Diastereomers - Two members of the enantiomer pair (chiral)
react differently with other chiral molecules
- Constitutional isomers differ in most chemical
Enantiomeric pairs have same solubility in
and physical properties
achiral solvents like ethanol and have different
- Have different boiling points and melting points
solubility in chiral solvent like D-2-butanol
- Diastereomers also differ in most chemical and
physical properties
Interactions Between Chiral Compounds
- Have different boiling points and freezing points
- In contrast, nearly all the properties of a pair of - Enantiomers have same boiling points, melting
enantiomers are the same points, and densities
Two differences: - All these are dependent upon intermolecular
1. Their interaction with plane polarized light forces, whereas chirality doesn't depend on such
2. Their interaction with other chiral substances forces
- Our body responds differently to different
enantiomers
- One may give higher rate or one may be inactive
Example: Body response to D isomer of hormone
epinephrine is 20 times greater than its response to D-Ribose
L isomer - Part of a variety of complex molecules which
include:
Classification of Monosaccharides RNA D
Monosaccharides АТР
DNA
Classification based on number of carbon atoms: - Five-membered cyclic form
Triose - 3 carbon atoms
Tetrose - 4 carbon atoms Cyclic Forms of Monosaccharides
Pentoses - 5 carbon atoms Cyclic Hemiacetal Forms of D-Glucose
Hexoses - 6 carbon atoms
Classification based on functional groups: - Dominant forms of monosaccharides with 5 or
Aldoses - Monosä ccharides with one aldehyde group more C atoms
Ketoses – monosaccharides with one ketone group - Cyclic structures are in equilibrium with open
Combined number of C atoms and functional group: chain forms
Aldohexose – monosaccharide with aldehyde group - Cyclic structures are formed by the reaction of
and 6 C atoms carbonyl group (C=O) with hydroxyl (-OH) group
Ketopentose – monosaccharide with ketone group on carbon 5
and 5 C atoms
Anomers
Biochemically Important Monosaccharides
- Cyclic monosaccharides that differ only in the
D-Glucose
position of the substituents on the anomeric
- Most abundant in nature carbon atom
- Most important source of human nutrition
- Grape fruit and ripe fruits are good sources of
glucose (20-30% by mass)
- Also named grape sugar
Other names Cyclic Forms of Other Monosaccharides
- Dextrose - Intramolecular cyclic hemiacetal formation and
- Blood sugar (70-100 mg/dL) the equilibrium between various forms are not
- Six-membered cyclic form restricted to glucose
D-Galactose - All aldoses with five or more carbon atoms
establish similar equilibria, but with different
- Milk sugar percentages of the alpha, beta, and open-chain
- Synthesized in human beings Also called brain forms
sugar - Fructose and other ketoses with a sufficient
- Part of brain and nerve tissue number of carbon atoms also cyclize
- Used to differentiate between blood types
- Six-membered cyclic form Pyranose and Furanose

D-Fructose - Pyranose - Cyclic monosaccharide containing a

six-atom ring
- Ketohexose - Furanose - Cyclic monosaccharide containing a
- Sweetest tasting of all sugars five-atom ring
- Found in many fruits and in honey - Their ring structures resemble the ring
- Good dietary sugar due to higher sweetness structures in the cyclic ethers pyran and furan,
- Five-membered cyclic form respectively
 - Glucose will be used as the monosaccharide
reactant
- Other aldoses, as well as ketoses, undergo similar
reactions
Monosaccharides in nature have cyclic forms because
they can form an internal hemiacetals that are stable.
Oxidation to Produce Acidic Sugars
Haworth Projection Formulas
- The redox chemistry of monosaccharides is
- Haworth projection formula - Two-
closely linked to the alcohol and aldehyde
dimensional structural notation that specifies the
functional groups
three dimensional structure of a cyclic form of a
- Oxidation can yield three different types of acidic
monosaccharide
sugars depending on the type of oxidizing agent
used
- Aldonic acid - Formed when weak oxidizing
agents such as Tollens and Benedict's solutions
oxidize the aldehyde end
- Reducing sugar - Carbohydrate that gives a
positive test with Tollens and Benedict's
a (alpha) and B (beta) Configuration solutions
- Determined by the position of the -OH group on Reduction to Produce Sugar Alcohols
C1 relative to the -CH2OH group that determines
R or L series - The carbonyl group in a monosaccharide (either
- In a B configuration, both of these groups point an aldose or a ketose) is reduced to a hydroxyl
in the same direction group using hydrogen as the reducing agent
- In an a configuration, the two groups point in - The product is the corresponding polyhydroxy
opposite directions alcohol called sugar alcohol or alditol
- Sorbitol - Used as a moisturizing agent in foods
and cosmetics and as a sweetening agent in
chewing gum (a sugar alcohol)
Glycloside Formation
Glycoside
- Acetal formed from a cyclic monosaccharide by
OH Group Position replacement of the hemiacetal carbon -OH group
- The specific identity of a monosaccharide is with an -OR group
determined by the positioning of the other -OH - Glucoside - Glycoside produced from glucose
groups in the Haworth projection formula - Galactoside - Glycoside produced from galactose
- Any -OH group at a chiral center that is to the - Exist in both a and 3 forms
right in a Fischer projection formula points down Phosphate Ester Formation
in the Haworth projection formula
- Any -OH group to the left in a Fischer projection - Hydroxyl groups of a monosaccharide can react
formula points up in the Haworth projection with inorganic oxyacids to form inorganic esters
formula - Phosphate esters of various monosaccharides are
stable in aqueous solution and play important
Reactions of Monosaccharides roles in the metabolism of carbohydrates
Five important reactions of monosaccharides: Amino Sugar Formation
1. Oxidation to acidic sugars
2. Reduction to sugar alcohols Amino sugar - Formed when one of the hydroxyl
3. Glycoside formation groups of a monosaccharide is replaced with an
4. Phosphate ester formation amino group
5. Amino sugar formation
- In naturally occurring amino sugars, the C2 Lactose Intolerance or Lactase Persistence
hydroxyl group is replaced by an amino group
- Amino sugars and their N-acetyl derivatives are - Lactose is the principal carbohydrate in milk
important building blocks of polysaccharides - Human mother's milk - 7%-8% lactose
such as chitin and hyaluronic acid - Cow's milk - 4%-5% lactose
- Lactose intolerance is a condition in which
people lack the enzyme lactase needed to
hydrolyze lactose to galactose and glucose
- Deficiency of lactase can be caused by a genetic
defect, physiological decline with age, or by
injuries to intestinal mucosa
Maltose (Malt Sugar) - When lactose is undigested, it attracts water
causing fullness, discomfort, cramping, nausea,
- Structurally made of 2 D-glucose units, one of
and diarrhea
which must be a-D-glucose, linked via an a (1→
- Bacterial fermentation of the lactose further
4) glycosidic linkage
along the intestinal tract produces acid (lactic
- Digested easily by humans because of an enzyme
acid) and gas, adding to the discomfort
that can break a(1->4) linkages
- Baby foods are rich in maltose Sucrose (Table Sugar)
- The most abundant of all disaccharides and
found in plants
- Produced commercially from the juice of sugar
cane and sugar beets
- Sugar cane contains up to 20% by mass sucrose
- Sugar beets contain up to 17% by mass sucrose
- Nonreducing sugar.
Cellobiose
- Produced as an intermediate in the hydrolysis of
the polysaccharide cellulose
- Contains two D-glucose monosaccharide units,
one of which must have a configuration, linked
through a B(1-4) glycosidic linkage
- Cannot be digested by humans

Oligosaccharides
- Carbohydrates that contain 3-10 monosaccharide
units bonded to each other via glycosidic linkages
Lactose - Generally present in association with other
complex molecules
- Made up of B-D-galactose unit and a D-glucose
unit joined by a B(1→4) glycosidic linkage Raffinose - Made of 1 galactose, 1 glucose, and 1
- Milk is rich in the disaccharide lactose fructose
- Lactase hydrolyzes (1→4) glycosidic linkages Stachyose - Made of 2 galactose, 1 glucose, and 1
fructose units
- Commonly found in onions, cabbage, broccoli,
and whole wheat.
Blood Types and Oligosaccharides
- Human blood is classified into four types
(A, B, AB, and O)
- The basis for the difference is the type of sugars - Glucose is the monomeric unit
(oligosaccharides) present - Storage polysaccharide in plants
- Blood of one type cannot be given to a recipient
with blood of another type Types of Polysaccharides Isolated From Starch:
- A transfusion of wrong blood type can cause the Amylose
blood cells to form clumps, a potentially fatal
reaction - Unbranched-chain polymer and accounts for
- People with type O blood are universal donors, 15%-20% of the starch
and those with type AB blood are universal - Has a(1 → 4) glycosidic bonds
recipients
Amylopectin
- In the United States, type O blood is the most
common and type A the second most common - Branched chain polymer and accounts for 80%-
- The biochemical basis for the various blood types 85% of the starch
involves oligosaccharides present on plasma - Has an alpha (1->4) and an alpha (1→6)
membranes of red blood cells glycosidic bonds
- The oligosaccharides responsible for blood - Up to 100,000 glucose units are present
groups are D-galactose and its derivatives. - Amylopectin is digested more readily by humans
(can hydrolyze a linkages but not ß linkages)
Other Oligosaccharides
Glycogen
- Solanine, a potato plant toxin, is a
oligosaccharide found in association with an - Glucose storage polysaccharide in humans and
alkaloid animals
- Bitter taste of potatoes is due to relatively higher - Contains only glucose units
levels of solanine - Branched chain polymer with an alpha (1 →4)
glycosidic bonds in straight chains and an alpha
The Polymer Chain
(1 →6) in branches
- Polysaccharides are polymers of many - Three times more highly branched than
monosaccharide units bonded with glycosidic amylopectin in starch
linkages - Contains up to 1,000,000 glucose units

Two types:
- Homopolysaccharide
- Heteropolysaccharide
General Characteristics of Polysaccharides
Cellulose
- Polysaccharides are not sweet and do not show
positive tests with Tollen's and Benedict's - Linear homopolysaccharide with beta (1→4)
solutions, whereas monosaccharides are sweet glycosidic bond
and show positive tests - Contains up to 5000 glucose units with molecular
- Limited water solubility mass of 900,000 amu
- Cotton has 95% cellulose and wood 50%
Examples: cellulose
Cellulose and glycogen – storage polysaccharides - Humans do not have enzymes that hydrolyze
beta (1→4) linkages and so they cannot digest
Chitin – structural polysaccharide cellulose
- Animals also lack these enzymes, but they can
Hyaluronic acid – acidic polysaccharide
digest cellulose due to the presence of cellulase-
Storage Polysaccharide producing bacteria
- It serves as dietary fiber in food and readily
- Polysaccharide that is a storage form for absorbs water resulting in softer stools
monosaccharides and used as an energy source - 20-35 g of dietary fiber is desired everyday
in cells
Starch
Chitin
- Similar to cellulose structurally and functionally
- Linear polymer with all 3(1 -4) glycosidic
linkages
- It has an N-acetyl amino derivative of glucose
- Function is to give rigidity to the exoskeletons of
crabs, lobsters, shrimp, insects, and other
arthropods
Acidic Polysaccharides
Acidic polysaccharides
- Polysaccharides with a repeating disaccharide
unit containing an amino sugar and a sugar with
a negative charge due to a sulfate or a carboxyl
group
- They are heteropolysaccharides, i.e., different
monosaccharides exist in an altering pattern
Examples:
Hyaluronic acid
Heparin
Hyaluronic Acid
- Alternating residues of N-acetyl- B-D-
glucosamine and D-glucuronate
- Highly viscous and serve as lubricants in the fluid
of joints as well as vitreous humor of the eye