CHAPTER 2

CARBOHYDRATES – STRUCTURE AND FUNCTION

I. OCCURRENCE AND FUNCTIONS OF CARBOHYDRATES

CARBOHYDRATES

● The most abundant class of bioorganic molecules on earth

● produced by the photosynthetic activity of the green plants
● also referred to as saccharides because of the sweet taste of many carbohydrates
● Latin = saccharum, meaning sugar
● storehouse of chemical energy (glucose, starch, glycogen)
- a gram of digested carbohydrate gives about 4 kcal of energy
- complex carbohydrates are best for diet
● supportive structural components in plants and some animals (cellulose, chitin)
● form part of the structural framework of DNA & RNA
● carbohydrate “markers” on cell surfaces play key roles in cell-cell recognition processes.

CLASSIFICATION OF CARBOHYDRATES

● Simpler Formula:
- CnH2nOn or Cn(H2O)n (hydrates of C)
- N = number of atoms
● polyhydroxy aldehydes or polyhydroxy ketones or compounds that produce such substances upon
hydrolysis.
● Classification based on products of acid hydrolysis:
➢ Monosaccharides
- the simple sugars
- contain a single polyhydroxy aldehyde or polyhydroxy ketone unit
- cannot be degraded into simpler products by hydrolysis reactions
- pure monosaccharides are water-soluble, white, crystalline solids
➢ Disaccharides
- contains 2 monosaccharide units covalently bonded to each other
- crystalline and water soluble substances
- upon hydrolysis they produce monosaccharides

➢ Oligosaccharides
- contains 2-10 monosaccharide units -
covalently bonded
- disaccharides are the most common
type
- trisaccharides (raffinose)
- tetrasaccharides (stachyose)
- free oligosaccharides, other than
disaccharides, are less common in nature
 - usually found associated with proteins and lipids in complex molecules that serve structural and
regulatory functions
➢ Polysaccharides
- consist of tens of thousands of monosaccharide units covalently bonded
- homopolysacchrides – polymers of a single monosaccharide (glycogen, cellulose, starch)
- heteropolysaccharides – contain more than one kind of monosaccharide (hyaluronic acid,
heparin, chondroitin sulfate)
➢ Derived​ ​carbohydrates
- those where carbohydrate moieties have undergone some reactions converting them into other
products
- sugar acids, sugar alcohols, deoxysugars, and sugar amines

CLASSIFICATION OF MONOSACCHARIDES

● Carbohydrates that have the general formula CnH2nOn

- n varies from 3 – 8.
● Grouped together according to the number of carbons they contain
- C3H6O3 triose
- C4H8O4 tetrose
- C5H10O5 pentose
- C6H12O6 hexose
- C7H14O7 heptose
- C8H16O8 octose
● May either be:
- An Aldose​ – contains aldehyde group
- A Ketose​ – contains ketone group
- presence of a ketone group is usually indicated by using the ending “___ulose” in naming the
sugar (e.g., levulose)

Exercise

➢ Classify each of the following monosaccharides according to both the number of carbon atoms and
the type of carbonyl group present.
 Answers:

A. Aldopentose; B. Ketohexose; C. Aldohexose; D. Ketopentose

CLASSIFICATION OF MONOSACCHARIDES

● Trioses
- the parent member of the family of monosaccharides
- from them emanates the other members of the monosaccharide family.
- the final form of carbohydrate into which all carbohydrates, regardless of their complexity, are
degraded in the body during carbohydrate metabolism.
- D(+)- glyceraldehyde
-an aldotriose
- Dihydroxyacetone
-a ketotriose
● Pentoses
- Aldopentoses
-D-(-)-lyxose = a constituent of the heart muscle
-D-(-)-ribose = ribose and 2-deoxyribose – present as intermediates in metabolic pathways and are
important building blocks of RNA and DNA
- Ketopentoses
-D-ribulose
-D-xylulose
● Hexoses
- he most common of all the monosaccharides
- Aldohexoses
-D-(+)-mannose
-D-(+)-glucose = A 5% (m/v) glucose solution is often used in hospitals as an intravenous source of
nourishment for patients who cannot take food by mouth.
-D-(+)-galactose
- Ketohexose
–D-(-)-fructose
● D-mannose
- found in certain bacteria, fungi, and plants
- converted to usable glucose in the body, but has no real physiological significance
● Monosaccharides can be classified based on their spatial orientation (stereochemistry).
● A monosaccharide can be classified as a D or L isomer, depending on the spatial orientation of the
–H and –OH groups attached to the carbon atom adjacent to the terminal primary alcohol group.
● The D isomer is represented when the –OH is written to the right of this carbon in the Fischer
projection formula. The L isomer is represented when this –OH is written to the left.

BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

➢ Glucose and Fructose

 ● Most abundant in nature
● Nutritionally most important
● Grape fruit good source of glucose (20 - 30% by mass) -- also named grape sugar, dextrose
and blood sugar (70 - 100 mg/100 mL of blood)
● Six membered cyclic form

● Ketohexose
● Sweetest of all sugars; the fruit sugar
● Found in many fruits and in honey
● Good dietary sugar-- due to higher sweetness
● Five membered cyclic form

➢ Galactose and Ribose

● component of milk sugar
● Synthesized in human
● Also called brain sugar-- part of brain
and nerve tissue
● Used to differentiate between blood
types
● Six membered cyclic form
● Galactosemia
= ​a result of genetic deficiency in the infant – the gene responsible for the enzyme that converts
D-galactose to D-glucose. Such infants cannot metabolize galactose and it builds up in the
blood and tissue.

● Part of RNA
● Part of ATP
● Part of DNA
● Five membered cyclic form

CYCLIC FORMS OF MONOSACCHARIDES

➢ Hemiacetals and Hemiketals

● The dominant form of monosaccharides with 5 or more C atoms is cyclic
● Hemiacetals and hemiketals are formed from the reaction between two functional groups:
aldehyde or ketone and alcohol
 -May take place either intermolecularly or intramolecularly as in the case of sugars,
provided there are sufficient number of carbons between the aldehyde or ketone and
the alcohol group to permit a stable ring formation
- five- or six-membered hemiacetal rings are stable
● Two types of ring structures are possible:
- five-membered ring, or furanose ring, derived from parent compound furan
- six-membered ring, or pyranose ring, derived from parent compound pyran

➢ Cyclic Hemiacetal Forms of D-Glucose

● In the cyclic hemiacetals of glucose, C1*,
is now a chiral center (an anomeric carbon)
- two anomers of D-glucose:
-D-glucose & -D-glucose
● The cyclic hemiacetals are readily
interconvertible in aqueous solution
- this intercoversion of - and
-anomers in solution is accompanied by a change in
specific rotation called ​MUTAROTATION​.
- only sugars that form hemiacetal or hemiketal structure mutarotate
-

● 2 anomeric forms of D-glucose:

- Alpha-form:​ -OH of C1
and CH2OH of C5 are on opposite sides
- Beta-form:​ -OH of C1 and
CH2OH of C5 are on same sides
● Anomers: Cyclic monosaccharides
that differ only in the position of the substituents
on the anomeric carbon atom.
● 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.
 ● All aldoses with five or more carbon atoms establish similar equilibria, but with different
percentages of the alpha, beta, and open-chain forms
● Fructose and other ketoses with a sufficient number of carbon atoms also cyclize

Haworth Projection Formulas

Practice Exercise

➢ Which of the monosaccharides

glucose, fructose, galactose, and ribose
has each of the following structural
characteristics? (There may be more than one
correct answer for a given characteristic)

a. It is a pentose.

b. It is a ketose.

c. Its cyclic form has a 6-membered ring.

d. Its cyclic form has two carbon atoms outside the ring.

Answers​: A. Ribose; B. Fructose; C. Glucose, galactose; D. Fructose

REACTIONS OF MONOSACCHARIDES

➢ Five important reactions of monosaccharides:

- Oxidation to acidic sugars
- Reduction to sugar alcohols
- Phosphate ester formation
- Amino sugar formation
- Glycoside formation
➢ These reactions will be considered with respect to glucose; other aldoses, as well as ketoses, undergo
similar reactions

➢ Oxidation
● Gives three
different types of acidic sugars
depending on the type of oxidizing agent used:
- Weak oxidizing agents like Tollens and Benedict’s solutions oxidize the aldehyde end
to give an aldonic acid.
- Strong oxidizing agents can oxidize both ends of a monosaccharide at the same time
to produce aldaric acid.
 - 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.

➢ Reduction
● The carbonyl group in a
monosaccharide (either an aldose or a ketose) is
reduced to a hydroxyl group using hydrogen as the
reducing agent.
- product is the corresponding
polyhydroxy alcohol, sugar alcohol
- e.g., Sorbitol (glucitol) - used as moisturizing agents in foods and cosmetics and as a
sweetening agent in chewing gum

➢ Redox Reactions of Monosaccharides

● Under prescribed conditions, some sugars reduce silver ions to free silver and copper(II) ions
to copper(I) ions. Such sugars are called reducing sugars.
● A reducing sugar will have one of the following groups.
● An aldehyde group (as in glyceraldehyde)
● A hydroxyketone (as in fructose)
● A cyclic hemiacetal group (as in glucose and maltose)
● The Benedict, Barfoed, and Fehling tests are based on the formation of a brick red copper(I)
oxide precipitate as a positive result while the Tollens test is based on the formation of a
silver mirror.
● The Barfoed test is more sensitive in that it can distinguish a reducing monosaccharide from a
reducing disaccharide.
● The sugars are oxidized to carboxylic acids and the metal ions are reduced

➢ Reducing sugars
● Sugars with the
hemiacetal structure can be reducing
sugars under alkaline conditions
because the ring opens forming an
aldehyde group
● Many clinical tests
that monitor color change are based
on the oxidation reaction shown
here.

➢ Phosphate Ester Formation

● The hydroxyl groups of a monosaccharide can react with inorganic oxyacids to form
inorganic esters.
● Phosphate esters of various monosaccharides are stable in aqueous solution and play
important roles in the metabolism of carbohydrates.

➢ Amino Sugar Formation

● One of the hydroxyl groups of a
monosaccharide is replaced with an amino group
● In naturally occurring amino sugars the
carbon 2 hydroxyl group is replaced by an amino group
● Amino sugars and their N-acetyl derivatives
are important building blocks of polysaccharides such as
chitin and hyaluronic acid
 ➢ Glycoside Formation
● The cyclic forms of
monosaccharides, the hemiacetals, react with
alcohols to form acetals (also called glycosides)
● A glycoside is an acetal formed
from a cyclic monosaccharide by replacement of
the hemiacetal carbon —OH group with an —OR group to form a double ether
● A glycoside produced from glucose – glucoside
● from galactose – galactoside

​DISACCHARIDES

● The two monosaccharides are linked together by acetal formation to form disaccharide
● One monosaccharide act as a hemiacetal and other as alcohol and the resulting ether bond is a
glycosidic linkage.
● Condensation of the hydroxyl function of the hemiacetal group of one monosaccharide with
the hydroxyl group of another monosaccharide forms the bond, called a glycosidic bond,
joining the 2 saccharide units.

➢ Maltose
(reducing sugar)
● Malt sugar,
found in corn syrup, malt,
and germinating seeds
● consists of
two molecules of glucose
joined by -1,4-glycosidic bond
● -1,4-glycosidic bond means that the first sugar is in -configuration and its C#1 is linked
to C#4 of the second sugar component
● the second sugar may be either an α- or a β-anomer.

➢ Cellobiose (reducing
disaccharide)
● one of the major
fragments isolated after extensive
hydrolysis of cellulose
 ● Maltose is digested easily by humans because we have enzymes that can break α-(14)
linkages but not β-(14) linkages of cellobiose
● The 2 glucose units are joined by a -1,4-glycosidic linkage

➢ Lactose (reducing disaccharide)

● Milk sugar
- human - 7%–8% lactose
- cow’s milk - 4%–5% lactose
● consists of -galactose with a -1,4-glycosidic linkage to -glucose (or -glucose)
● Lactose intolerance: a condition in which people lack the enzyme lactase needed to hydrolyze
lactose to galactose and glucose.
● Lactose intolerance is unpleasant, but its effects can be avoided by a diet that rigorously
excluded milk and milk products.

➢ Lactose intolerance vs
Galactosemia
● When
undigested, lactose attracts
water causing fullness,
discomfort, cramping, nausea,
and diarrhea.
● Bacterial fermentation of lactose along the
intestinal tract produces acid (lactic acid) and gas, adding to the
discomfort.
● Galactosemia: the genetic disease caused by the absence of the enzymes needed for
conversion of galactose to glucose.
● A reduced form of galactose, called dulcitol (galactitol), a toxic metabolite, is produced and
accumulates.
 ● If galactosemia is not treated, it leads to severe mental retardation, cataracts, and early deaths

➢ Sucrose (nonreducing disaccharide)

● The common table sugar & the most abundant of all disaccharides found in plants.
● Produced commercially from the juice of sugar cane and sugar beets.
● The -anomeric carbon 1 of glucose joins the -anomeric carbon 2 of fructose
(-1,2-glycosidic bond)
●

➢ Invert sugar
● Optical activities:
- Sucrose : +66.5
- Glucose : +53
- Fructose : -92
- Invert sugar : -39
● invert sugar has a much greater
tendency to remain in solution.
● In the manufacture of jelly and
candy and in the canning of fruit, crystallization
of the sugar is undesirable, therefore conditions leading to the hydrolysis of sucrose are
employed in these processes; in addition, fructose is sweeter than sucrose
● Honeybees and many other insects possess an enzyme called invertase that hydrolyzes
sucrose to invert sugar.
 ● Thus honey is predominantly a mixture of D-glucose and D-fructose with some unhydrolyzed
sucrose.

Practice Exercise

Which of these disaccharides, i.e., maltose, cellobiose, lactose, and sucrose, have the following structural or
reaction characteristics? (There may be more than one correct answer for a given characteristic)

A. Two different monosaccharide units are present.

b. Hydrolysis produces only monosaccharides.

c. Its glycosidic linkage is a “head-to-head” linkage.

d. It is not a reducing sugar.

Answers​: A. Lactose, sucrose; B. Maltose, cellobiose, lactose, sucrose; C. Sucrose D. Sucrose

➢ Artificial sweeteners
OLIGOSACCHARIDES

● Commonly found in onions, cabbage, broccoli and wheat

● In humans, intestinal bacteria action on the undigestable raffinose and stachyose present in
beans produces gaseous products that can cause discomfort and flatulence.

● Solanin - a potato toxin,

is a oligosaccharide found in
association with an alkaloid
● Bitter taste of potatoes is
due to relatively higher levels of
solanin.

Reactions of Monosaccharides

➢ Antigens used in the ABO

blood group classification

General Characteristics of Polysaccharides

➢ The Polymer Chain

● many monosaccharide units
bonded with glycosidic linkages
● branched or unbranched
● homopolysaccharide or
heteropolysaccharides
 ● alternate name is glycan
● not sweet and don’t show positive tests with Tollen’s and Benedict’s solutions
● limited water solubility
● Storage polysaccharides
- Starch
- Glycogen
● Structural polysaccharides
- Cellulose
- Chitin
● Acidic polysaccharides
- Heparin
- hyaluronic acid
● Homopolysaccharides
- Starch
- Glycogen
- Cellulose
- Chitin
- Carrageenan
● Heteropolysaccharides
- hyaluronic acid
- heparin
- chondroitin sulfate
- alginic acid

Storage Polysaccharides

➢ Starch
● the chief caloric distributor in the diet; the reserve carbohydrates for plants
● Amylose​ - straight chain polymer; 15 - 20% of the starch; water-soluble fraction; 60 – 300
glucose units joined by -1,4-glycosidic bonds
● Experimental evidence indicates that the molecule is actually coiled like a spring and is not a
straight chain of glucose units.
● When coiled in this fashion the molecule has just enough room in its core to accommodate an
iodine molecule.
● The characteristic blue color that starch gives when treated with iodine is due to the
formation of the amylose-I2 complex.

● Amylopectin
 - branched chain polymer
- 80 - 85 % of the starch
- the water-insoluble fraction
- composed of 300 – 6000 glucose units joined primarily by -1,4-glucosidic bonds
and occasionally by -1,6-glucosidic bonds
- -1,6 bonds are responsible for branching which occurs about once every 25-30
units.

➢ Glycogen
● the animal starch
● glucose storage molecule of animals
● stored in granules in liver and muscle cells
● like amylopectin, is a nonlinear polymer of glucose units joined by -1,4- and
-1,6-glycosidic bonds but has lower molecular weight
● more highly branched structure
● its branches are shorter
● gives red-brown color with I2

➢ Cellulose
● a fibrous
carbohydrate found in all
plants where it serves as the
structural component of the
plant’s cell wall
● a linear
polymer of glucose units
joined by -1,4-glucosidic
bonds
● linear nature
of chains allows close
packing into fibers, making
it difficult for solvent molecules to pull the chains apart, thus cellulose is inert towards most
solvents
 ● Cotton ~95% cellulose and wood ~50% cellulose
● It serves as dietary fiber in food-- readily absorbs water and results in softer stools
● 20 - 35 g of dietary fiber is desired everyday

● yields D-glucose upon hydrolysis yet man & the carnivorous animals can’t utilize cellulose as
a source of glucose.human‘s digestive juices lack the enzyme cellulase that hydrolyze
-1,4-glucosidic linkages.
● ruminants (cows, goats) and termites have, within their digestive tracts, microorganisms that
produce cellulase

➢ Chitin
● Similar to cellulose in both function and structure
● polymer of N-acetyl-D-glucosamine bound by β-1  4 glycosidic linkages (has a linear
extended structure like cellulose)
● Function is to give rigidity to the exoskeletons of crabs, lobsters, shrimp, insects, and other
arthropods
● itself is inert and practically insoluble in most solvents. Its derivative, chitosan, can be
prepared by simple alkali-catalyzed deacylation. Chitosan derivatives are commercially used
as films, fibers, surface coatings and ultrafiltration membranes
 ➢ Carageenan
● occurs as hydrocolloid extracted from selected species of red algae
● locally obtained from Eucheuma
● Striatum, Eucheuma spinosum and Acanthapora
● Sulphated polysaccharides, consisting of polymers of sulphated D-galactopyranose bonded
through alternating α- 13 and β-14 glycosidic linkages
● widely used in food industry
● its gelling property is used in enhancing the texture of various dairy products and in
preventing oiling off in caramel and toffee during hot weather
● also serve as coating to retard moisture loss from foods and fresh produce like fruits and
vegetables

Acidic Polysaccharides

➢ Hyaluronic acid
● repeating unit is a disaccharide composed of -D-glucuronic acid and
N-acetyl-D-glucosamine in a -(13)-linkage.
● each disaccharide is attached to the next by -(14)-linkage
● alternating -(13) and -(14)-linkages
● highly viscous - serve as lubricants in the fluid of joints and part of vitreous humor of the eye
● when some insects sting,
they inject an enzyme called
hyaluronidase, which breaks hyaluronic
acid linkages and facilitates the spread of
 the venom
➢ Heparin Alginic acid
● consists of repeating units of D-glucuronic acid and D-glucosamine
● an anticoagulant in blood that inhibits blood clot formation
● used in open-heart surgery

➢ Alginic acid
● consists of repeating units of D-glucuronic acid and D-glucosamine
● an anticoagulant in blood that inhibits blood clot formation
● used in open-heart surgery
● locally extracted from Sargassum seaweeds
● consist of repeating units of β-14 bonded mannuronic and α-14 bonded L-guluronic
acid; cell wall material
● serves as base coatings in meats and fish which reduces moisture loss and fat absorption
 ➢ Chondroitin sulfate
● consists of repeating units of D-glucuronic acid-D-glucosamine sulfate
● structural role in cartilage, bone, and cornea of the eye

Dietary Considerations and Carbohydrates

➢ Glycemic Foods
● A developing concern about intake of carbohydrates involves how fast the given dietary
carbohydrates are broken down to glucose within the human body
● Glycemic index refers to:
- how quickly carbohydrates are digested
- how high blood glucose rises
- how quickly blood glucose levels return to normal
- Glycemic index (GI) has been developed for rating foods
- Low-GI foods are desirable

Glycolipids and Glycoproteins: Cell Recognition

● A glycolipid is a lipid molecule that has one or more carbohydrate (or carbohydrate
derivative) units covalently bonded to it.
● A glycoprotein is a protein molecule that has one or more carbohydrate (or carbohydrate
derivative) units covalently bonded to it.
 ● Such carbohydrate complexes are very important in cellular functions such as cell-cell
recognition, cell adhesion and cellular communication.

Dietary Considerations and Carbohydrates

➢ Unavailable carbohydrates
● those not hydrolyzed by digestive enzymes
● they constitute the dietary fiber
● Fiber in the diet aids in the formation of bulk in the intestinal tract, which increases the
absorption of water along the tract.
● Dietary fiber, as it reaches the gut, is intact in structure where they form a meshwork
● The meshwork has spaces where fecal matter and water are trapped
● The effect is soft fecal matter which can be easily removed.
● If absent fecal matter is hard, and has a long transit time.
● Long sojourn will dehydrate it and will make it harder to remove.
● It also increases the rate at which digestive wastes move through the intestinal tract, which
lessens the time the intestine comes in contact with any ingested carcinogens.
● Some forms of diverticulitis (inflammation of the colon) have been relieved by increasing the
quantity of fiber in the diet.
● Straining at stool because of lack of dietary fiber can lead to hemorrhoidsand nervous
disorders
➢ Dietary fiber
● Lack of dietary fiber may also lead to overnutrition.
● When one does not masticate, the secretion of digestive hormones (such as gastrin and
cholecystokinin) is not induced.
● Without these hormones, it takes longer to reach the feeling of satiety.
● Dietary fiber may also be beneficial in weight maintenance.
● Fiber increases the bulk in the stomach and intestines without contributing to the caloric
intake.
● There is also a correlation between ischaemic heart disease and gallstone formation with the
lack of dietary fiber.
● Cholesterol can be trapped in the meshwork reducing the concentration of blood cholesterol.
● With dietary fiber, bile will not be supersaturated with cholesterol.
● In its absence, bile will be supersaturated with cholesterol and gallstone formation results.
● When cholesterol is trapped plaque formation will be reduced.
● In the absence of dietary fiber, excess cholesterol can lead to plaque formation leading to
ischaemic heart disorders.About 20-35 grams of dietary fiber daily is a desirable intake.