carbohydrates = polyhydroxyaldehyde or polyhydroxyketones

(CnH2O)n=6 = Carbohydrate / C6H12O6 - glucose and fructose

polyhydric alcohols = many OH in their structure
CARBOHYDRATES ketoses
aldoses
● Are aldehyde or ketone derivatives of polyhydric
alcohols consisting of carbon, hydrogen, and oxygen.
● Empiric formula for many simpler carbohydrates is
(CH2O)n, hence the name “hydrate of carbon”.
● called sugars and starches
● synthesized in green plants through photosynthesis,
whereby energy from the sun is stored as chemical
energy in carbohydrates.
■
Galactose – in lactose of milk, in glycolipids,
and in combination with protein in
glycoproteins and proteoglycans
Disease associated with Carbohydrate Metabolism
● Diabetes mellitus Lifestyle disease / Hereditary disease
Galactose in the bloodstream / metabolic disorder - lens
● Galactosemia opacity and catarac formation
● Glycogen storage disease look for the chapter -search for the table
● Lactose intolerance cannot metabolize lactose - vomiting, bloating, GI
discomfort / cannot digest Beta 1-4
Classes of Carbohydrates
● The empiric formula for many simpler carbohydrates is
(CH2O)n , hence the name “hydrate of carbon”.

I. MONOSACCHARIDE
● “simple sugars”
● Are sweet tasting, but their relative sweetness varies
greatly.
● Are polar compounds with high melting points.
● Cannot be hydrolyzed into simpler carbohydrates;
● Contains a single polyhydroxy aldehyde or ketone unit
● Classification is based on:
○ the number of carbon atoms
○ whether they have an aldehyde or ketone
group (as aldoses and ketoses)
● Examples includes: glucose, fructose
● Presence of so many polar functional groups capable of
hydrogen bonding makes the monosaccharides very
water soluble.
● the simplest carbohydrates, generally have 3 to 6 C
atoms in a chain with an aldehyde or ketone ending
Importance of Carbohydrates and many –OH groups.
● Provide a significant fraction of the energy in the diet of ● those sugars that cannot be hydrolyzed into simpler
most organisms; plants = starch carbohydrates.
humans/ animals =
● Storage form of energy in the body; glycogen = liver or muscle ● They may be classified as trioses (3C), tetroses (4C),
● Cell membrane components that mediate some forms of pentoses (5C), hexoses (6C), or heptoses (7C),
intercellular communication; and depending upon the number of carbon atoms, and as
● Serves as structural component of many organisms: aldoses or ketoses, depending on whether they have an
○ Cell walls of bacteria peptidoglycan aldehyde or ketone group.
○ Exoskeleton of many insects chitin ● In addition to aldehydes and ketones, the polyhydric
○ Fibrous cellulose of plants cellulose = structural polysaccharide alcohols (sugar alcohols or polyols), in which the
glycoside = ● Plant metabolites contains sugar as an essential aldehyde or ketone group has been reduced to an
beside a sugar
features of their structure; alcohol group, also occur naturally in foods.
a. Agyclone =
non sugar ● Play an ecological role in plant-animal interaction, ● They are synthesized by reduction of monosaccharides
b. Glycone =
protection from wound and infection and detoxification for use in the manufacture of foods for weight
sugar
of foreign substances; and reduction and for diabetics.
● Sugar and starch are used as food and ● They are poorly absorbed, and have about half the
pharmaceuticals. energy yield of sugars.
● Primarily produced by plants and form a very large
group of naturally occurring organic
SImplest
substances;common examples are cane sugar, glucose,
starch, etc. Simplest
aldohexose
BIOMEDICAL IMPORTANCE
● GLUCOSE
○ The most important carbohydrate (monosaccharide);
○ Dietary carbohydrate absorbed into the bloodstream;
○ Major metabolic fuel of mammals and universal fuel
of the fetus.
○ Precursor for the synthesis of:
DNA and RNA =
■ Glycogen – for storage
Example of Pentose (5) ■ DNA and RNA – in nucleic acids
 R-C=O-H R-C=O-R'

C=O-H

R
O-R C=O as we
increased the
C no. of sugar
R unit or
saccharide unit
R = increases
R
MW = increase
in structure /
ALDEHYDE KETONE molecule - less caramelized sugar (taho, leche flan)
ALDEHYDE KETONE soluble
fruit sugar

● Most monosaccharides have a sweet taste;

● Solid at room temperature; and
● Very soluble in water

C1 applicable
to glucose
only

Physical Properties of Monosaccharides

 ● PENTOSES – are important in nucleotides, nucleic
acids and several coenzymes
● HEXOSES - glucose, galactose, fructose, and mannose
● KETOSES & ALDOSES
● Carboxylic acid derivatives of glucose
○ D - glucuronate – for glucuronide formation
and in glycosaminoglycans
○ L - iduronate (in glycosaminoglycans) and
Lgulonate (an intermediate in the uronic acid
pathway) – metabolic derivatives of
D-Glucuronate
STRUCTURE OF MONOSACCHARIDES
● Aldehyde monosaccharides are aldoses; ketone
anomeric carbon = C2 monosaccharides are ketoses. The simplest aldose is
glyceraldehyde. The simplest ketose is
dihydroxyacetone. They are constitutional isomers of
each other, sharing the formula C3H6O3.

Benedict's
reagent = reducing sugar =
blue monosaccharide

Positive =
red-orange or cupric to cuprous
brick red ppt = reducing sugar

● Glyceraldehyde is an aldotriose. Dihydroxyacetone is a

ketotriose.
● Monosaccharides Fischer Projection Formula
● All carbohydrates have 1 or more chirality centers.
Glyceraldehyde, the simplest aldose, has one chirality
center, and has two possible enantiomers.

● The prefix D is used when the –OH group is drawn on

the right side of the carbon chain. The prefix L is used
when the –OH group is drawn on the left side of the
carbon chain. The wedged and dashed lines can be
re-drawn in a Fischer projection formula:

PHYSIOLOGICALLY IMPORTANT MONOSACCHARIDES

● Derivatives of trioses, tetroses, and pentoses and of
seven-carbon sugar (sedoheptulose)
○ Formed as metabolic intermediates in
glycolysis and pentose phosphate pathway
glycolysis = breakdown of sugar pentose phosphate pathway = important on the
synthesis of ribose phosphates (DNA/ RNA)
Common Monosaccharides

● Glucose (dextrose) is blood sugar and the most

abundant monosaccharide. Normal blood glucose levels
are 70-110 mg/dL.
● Galactose is one of the components of the disaccharide
lactose.
● Fructose is one of the components of the disaccharide To cyclize D-glucose, first we must determine which alcohol to
sucrose. use to make a six-membered ring.

The Cyclic Forms of Monosaccharides

When an aldehyde reacts with an alcohol, a hemiacetal is

formed:

When the aldehyde and alcohol are on the same molecule, a

As the reaction occurs, there are two cyclic forms of D-glucose,
stable cyclic hemiacetal is formed:
an alpha (α) anomer and a beta (β) anomer.

These rings are called Haworth projections.

Ketohexoses like fructose form five-membered rings with two

anomers.

The C atom that is part of the hemiacetal is a new chirality center,

called the anomer carbon.
 II. DISACCHARIDES
● Meaning "two sugars“
● Are commonly found in nature as sucrose, lactose and
maltose
● Formed by a condensation reaction where one molecule
of water condenses or is released during the joining of
two monosaccharides
● Are condensation products of two monosaccharide
units.
● The type of bond that is formed between the two sugars
is called a glycosidic bond
● They link together by forming an acetal

● When this reaction occurs between two

monosaccharides, the bond that joins them together is
called a glycosidic linkage.

Reduction and Oxidation

Reduction of the Aldehyde Carbonyl Group

The carbonyl group of an aldose is reduced to a 1o alcohol

using H2 with Pd. The glycosidic linkage joining the two rings can be alpha (α) or
beta (β).

If the bond is alpha (α)

If the bond is beta (β).

Oxidation of the Aldehyde Carbonyl Group

The aldehyde group is easily oxidized to a carboxylic acid

using Benedict’s reagent. Aldoses can be oxized, while
ketones cannot.
 MALTOSE
● Disaccharide consists of two glucose molecules joined
by an alpha (α) glycosidic bond.
● Hydrolysis of maltose yields 2 glucose molecules.

● Hydrolysis cleaves the C—O glycosidic linkage and

forms two monosaccharides.

Most common disaccharides includes:

1. Lactose - composed of one molecule of glucose and

one molecule of galactose.
2. Maltose - composed of two molecules of glucose
3. Sucrose - composed of one molecule of glucose and
one molecule of fructose.
● The disaccharide bond is cleaved by the enzyme
lactase in the body.
● Individuals who are lactose intolerant no longer produce
this enzyme.
● Without the enzyme, lactose cannot be digested,
causing abdominal cramps and diarrhea.
● Sucrose is very sweet, but contains many calories.
● To reduce caloric intake, many artificial sweeteners
have been developed.

● Use in alcohol production. Although maltose is

uncommon in nature, it can be formed through the
breakdown of starch by the enzymes of the mouth.
SUCROSE
● An excellent preservative because it has no "reducing
end" or reactive group like the other sugars
● Other natural sources of sucrose are found in plants
such as sugar cane, sugar beets, and maple syrup
● Hydrolysis of sucrose yields mixtures of glucose and
fructose called “invert sugars”
● Is found in common table sugar and is composed of
glucose and fructose linked via α 1-2 alpha glycosidic
bond

Do you have lactose intolerance?

● Many people are lactose intolerant and suffer from

intestinal cramping and bloating due to the incomplete
digestion of the substance because they lack lactase
that converts lactose to glucose and galactose, where
glucose eventually becomes ATP (source of energy)

LACTOSE
● beta-glycosidic bonds are unable to be digested by
some people
● Many people are lactose intolerant and suffer from
intestinal cramping and bloating due to the incomplete DISACCHARIDES OF PHYSIOLOGIC IMPORTANCE
digestion of the substance ● Include Isomaltose, maltose, lactose, lactulose, sucrose
● formed through the condensation of glucose and and trehalose
galactose forming a beta glycosidic bond.
● Unlike alpha glycosidic bonds, beta-glycosidic bonds
are unable to be digested by some people
● Lactose is the disaccharide in milk; it consists of 1
galactose ring and 1 glucose ring joined by 1-->
4-β-glycosidic linkages.
III. OLIGOSACCHARIDES
● Important oligosaccharides are raffinose and stachyose
(found in beans and legumes)
● are condensation products of three to ten
monosaccharides.
● Important oligosaccharides are raffinose and stachyose
(found in beans and legumes)
● Raffinose and stachyose, because of their unique
glycosidic bonds, cannot be broken down into their
simple sugars.
● Therefore, they cannot be absorbed by the small
intestine and are often metabolized by bacteria in the
large intestine to form unwanted gaseous by-products.
IV. POLYSACCHARIDES
● condensation products of more than ten
monosaccharide units; examples are the starches and
dextrins, which may be linear or branched polymers.
● sometimes classified as hexosans or pentosans,
depending on the constituent monosaccharides
(hexoses and pentoses, respectively).
● Foods contain a wide variety of other polysaccharides
that are collectively known as nonstarch
polysaccharides; they are not digested by human
enzymes, and are the major component of dietary fiber
(cellulose from plant cell walls - a glucose polymer and
inulin, the storage carbohydrate in some plants - a
fructose polymer.
● Polysaccharides are not reducing sugars, since the
anomeric carbons are connected through glycosidic
linkages;
● Non starch polysaccharides are not digested by human
enzymes, and are major component of dietary fibers:
○ Cellulose (a glucose polymer) and inulin (a
fructose polymer)
● Other polysaccharide of concern is glycogen.
● Cellulose is found in the cell walls of all plants, where it
gives support and rigidity to wood, plant stems, and
grass.
● Humans do not possess the enzyme to hydrolyze
cellulose (b-glycosidase) and cannot digest it.
● Cellulose makes up the insoluble fiber in our diets,
which is important in adding bulk to waste to help
eliminate it more easily.
● Starch is a polymer made up of repeating glucose units
joined by alpha glycosidic linkages.
● When glucose is needed for energy, glucose units are
hydrolyzed from the ends of the glycogen polymer.
Starch
● Homopolymer of D glucose units forming an -glucosidic
chain (called glucosan or glucan);
● Most important dietary source of carbohydrates in
cereals, potatoes, legumes and other vegetables
● Starches (and other glucose polymers) are usually
insoluble in water because of high molecular weight;
● Starch is the major storage form of carbohydrates in
plants and of two different forms: amylose and
amylopectin
Two main constituents
● AMYLOSE (13-20%) non-branching (linear) helical
structure 14-α-glycosidic linkages.
● AMYLOPECTIN (80-85%) branched chains composed
of 24-30 glucose residues united by14-α and
1-->6-α-glycosidic linkages.
● Both starch molecules can be digested by humans
using the enzyme amylase
Starch
● The extent of starch hydrolysis by amylase enzyme is
determined by:
○ Its structure
○ Degree of crystallization or hydration (the result
of cooking)
○ Whether it is enclosed in intact (and
indigestible) plant cell walls

GLYCEMIC INDEX
● Measure of digestibility of starchy food;
● Based on the extent to which it raises the blood
concentration of glucose compared with an equivalent
amount of glucose or a reference food such as white
bread or boiled rice.

GLYCOGEN
● Storage polysaccharide in animals and is sometimes
called the animal starch
● stored in the liver and muscle where it is synthesized
and degraded depending upon the energy requirements
of the body.
● the major form of polysaccharide storage in animals,
similar in structure to amylopectin. It is stored mainly in
the liver and in muscle cells.
● When glucose is needed for energy, glucose units are
hydrolyzed from the ends of the glycogen polymer.
● Highly branched 12-14 α-D-glucopyranose. Each
residue is linked by α1→4 linkages with branching by
a1→6 linkage.
Non-starch Polysaccharides - Inulin, Dextrins, Cellulose,
Chitin and Pectins
Inulin
● a polysaccharide of fructose (a fructosan) found in
tubers and roots of dahlias, artichokes, and dandelions.
● It is readily soluble in water and is used to determine the
glomerular filtration rate, but it is not hydrolyzed by
intestinal enzymes, so has no nutritional value.
Dextrins
● are intermediates in the hydrolysis of starch.
Cellulose
● the chief constituent of plant cell walls.
● It is insoluble and consists of β-d-glucopyranose units
linked by β1 → 4 bonds to form long, straight chains
strengthened by cross-linking hydrogen bonds.
● Mammals lack any enzyme that hydrolyzes the β1 → 4
bonds, and so cannot digest cellulose.
● It is an important source of “bulk” in the diet, and the
major component of dietary fiber.
● Microorganisms in the gut of ruminants and other
herbivores can hydrolyze the linkage and ferment the
products to short- chain fatty acids as a major energy
source.
● There is some bacterial metabolism of cellulose in the
human colon.

Chitin
● a structural polysaccharide in the exoskeleton of
crustaceans and insects, and also in mushrooms.
● It consists of N-acetyl-d-glucosamine units joined by β1
→ 4 glycosidic bonds.

Pectin
● occurs in fruits; it is a polymer of galacturonic acid linked
α-1→ 4, with some galactose an/or arabinose branches,
and is partially methylated.

INULIN and DEXTRIN

● Inulin
 ○ A polysaccharide of fructose found in tubers Polysaccharides - Glycoproteins
and roots of dahlias, artichokes, and GLYCOPROTEINS (Mucoproteins)
dandelions ▫ Readily soluble in water ● Proteins containing branched & unbranched
○ Use to determine glomerular filtration oligosaccharide chains;
○ Not hydrolyzed by intestinal enzymes
● Dextrins
○ Intermediates in the hydrolysis of starch

GLYCOSAMINOGLYCANS (Mucopolysaccharides)
● Complex carbohydrates containing amino sugars and
uronic acid;
● Glycosaminoglycans (GAGs) are a group of
unbranched carbohydrates derived from alternating
amino sugar and glucuronate units.
● May be attached in protein molecules to form
proteoglycan.
○ Proteoglycans provide the ground or packing ● They occur in the cell membranes and many other
substance of connective tissues; situations;
○ Hold large quantities & water supply, occupies ● The sialic acids are N- or O-acyl derivatives of
space lubricating other structures. neuraminic acid
○ Examples are hyaluronic acid, chondroitin ● Serum albumin is an example
sulfate, and heparin. ● NEURAMINIC ACID – nine carbon sugar derived from
Hyaluronate, extracellular fluids that lubricate joints and in the mannosamine and pyruvate
vitreous humor of the eye. ● SIALIC ACID – are N- or O-acyl derivatives of
neuraminic acid
○ Constituents of both glycoproteins &
gangliosides (glycolipids)

GLYCOSIDES
● Are formed by the condensation between the hydroxyl
group of the anomeric carbon of monosaccharide
(glycone), and a second compound that may not be
another monosaccharide (aglycone)
● O-glycosidic bond – if the second group is a hydroxyl
○ Acetal link (formed from an aldehyde and an –
Another example is chondroitin, a component of cartilage and OH)
tendons. ● N-glycosidic bond – if the second group is amine
○ Ex.: adenine and ribose in ATP
● If the hemiacetal (aldehyde + -OH) portion is glucose,
the resulting compound is Glucoside, if galactose, a
Galactoside;
● The aglycone may be methanol, glycerol, a sterol, a
phenol, or a base such as adenine
MEDICINALLY IMPORTANT GLYCOSIDES
● 1. Cardiac glycosides
○ Contain steroids as aglycone
○ Include derivatives of digitalis (digoxin,
digitoxin) and strophantus (ouabin)
Heparin, stored in the mast cells of the liver, helps prevent blood ● 2. Aminoglycoside Antibiotics
clotting. ○ Streptomycin

DEOXYSUGARS
● Lack an oxygen atom
○ one hydroxyl group has been replaced by
hydrogen
● deoxyribose in DNA
● L-fucose - deoxysugar in glycoproteins
● 2-deoxyglucose – used experimentally as inhibitor of
glucose metabolism
AMINOSUGARS ● The most important types of isomerism are
● Hexosamines ○ D and L isomerism
○ are components of glycoproteins, gangliosides, ○ The presence of asymmetric carbon atoms
& glucosaminoglycosides also confers optical activity on the compound.
● Include: ○ Pyranose and furanose ring structures
○ D-glucosamine – constituent of hyaluronic acid ○ Alpha and beta anomers
○ D-galactosamine (chondrosamine) – ○ Epimers
constituent of chondroitin ○ Aldose-ketose isomerism
○ D-mannosamine
○ Aminoglycosides antibiotics (streptomycin) and D and L isomerism
macrolides (erythromycin) ● Mirror images
● Determined by spatial relationship to the parent
compound of the carbohydrates
● designation of a sugar isomer as the d form or its
mirror image as the l form is determined by its spatial
relationship to the parent compound of the
carbohydrates, the three-carbon sugar glycerose
(glyceraldehyde).

The Stereochemistry of Carbohydrates

● D-isomer = OH group is on the right

● L-isomer = OH group is on the left
● Most monosaccharides in mammals are Dsugars
● Glucose in solution is dextrorotatory, so its solution is
called Dextrose
● The orientation of the —H and —OH groups around the
carbon atom adjacent to the terminal alcohol carbon
(carbon 5 in glucose) determines whether the sugar
belongs to the d or l series.
● When the —OH group on this carbon is on the right (as
seen in Figure 15–2), the sugar is the d isomer; when it
is on the left, it is the l isomer.
● Most of the naturally occurring monosaccharides are d
sugars, and the enzymes responsible for their
metabolism are specific for this configuration.

Forms of Isomerism exhibited by Sugars

Sugars Exhibit Various Forms of Isomerism
● Glucose, with four asymmetric carbon atoms, can form
16 isomers.
Isomers of Glucose
● Glucose can form 16 isomers
 ● The ring structure of an aldose is a hemiacetal, since it
is formed by reaction between an aldehyde and an
alcohol group. Similarly, the ring structure of a ketose
is a hemiketal.
● Crystalline glucose is α-d-glucopyranose.

Pyranose and furanose ring structures:

The ring structures of monosaccharides are similar to the ring

structures of either pyran (a six-membered ring) or furan (a
five- membered ring)

● The cyclic structure is retained in the solution, but

isomer- ism occurs about position 1, the carbonyl or
anomeric carbon atom, to give a mixture of
α-glucopyranose (38%) and β-glucopyranose (62%).
Less than 0.3% is represented by α and β anomers of
glucofuranose.

For glucose in solution, more than 99% is in the pyranose

form.
Alpha and beta anomers
● Two possible structures for the pyranose and furanose
forms of a monosaccharide
● Anomers, and (differing only in configuration at
anomeric C)
Epimers

● Sugars that differ in configuration at ONLY 1 POSITION

● Isomers differing as a result of variations in configuration
of the –OH and –H on carbon atoms 2, 3, and 4 glucose
(epimers of glucose)
● Examples
○ D-glucose & D-galactose (epimeric at C4)
○ D-glucose & D-mannose (epimeric at C2)
○ D-idose & L-glucose (epimeric at C5)
● Biologically, the most important epimers of glucose are
mannose (epimerized at carbon 2) and galactose
(epimerized at carbon 4)

● Chemically, aldoses are reducing compounds, and are

sometimes known as reducing sugars.
● This provides the basis for a simple chemical test for
glucose in urine in poorly controlled diabetes
mellitus, by reduction of an alkaline copper solution.

● Mannose and Galactose

○ The most important epimers of glucose
○ Formed by epimerization at carbon 2 and 4,
respectively

Aldose-ketose isomerism
● Fructose has the same molecular formula as Glucose
but they differ in their structural formula
○ Keto-group at position 2 (anomeric carbon of
fructose)
○ Aldehyde group at position 1 (anomeric carbon
of glucose)

Asymmetric carbon atoms (Optical activity)

The presence of asymmetric carbon atoms also confers

optical activity on the compound.
● When a beam of plane-polarized light is passed through
a solution of an optical isomer, it rotates either to the
right, dextrorotatory (+), or to the left, levorotatory (−).
● The direction of rotation of polarized light is independent
of the stereochemistry of the sugar, so it may be
designated d(−), d(+), l(−), or l(+). For example, the
naturally occurring form of fructose is the d(−) isomer.
● Confusingly, dextrorotatory (+) was at one time called
d-, and levorotatory (−) l-.
● This nomenclature is obsolete, but may sometimes be
found; it is unrelated to d- and l-isomerism.
● In solution, glucose is dextrorotatory, and glucose
solutions are sometimes known as dextrose.
The straight-chain structural formula (aldohexose; Figure 15–1A)
can account for some of the properties of glucose, but a cyclic
structure (a hemiacetal formed by reaction between the aldehyde
group and a hydroxyl group) is thermodynamically favored and
accounts for other properties.
The cyclic structure is normally drawn as shown in Figure 15–1B,
the Haworth projection, in which the molecule is viewed from the
side and above the plane of the ring; the bonds nearest to the
viewer are bold and thickened, and the hydroxyl groups are
above or below the plane of the ring.
The hydrogen atoms attached to each carbon are not shown in
this figure. The ring is actually in the form of a chair.
 ○ Sucralose (sold as Splenda) has a very similar
structure to sucrose.
Physiologically Significant Carbohydrates
POLYSACCHARIDES
MONOSACCHARIDES
● Cellulose is found in the cell walls of all plants, where it
● Glucose (dextrose) is blood sugar and the most gives support and rigidity to wood, plant stems, and
abundant monosaccharide. grass.
● Normal blood glucose levels are 70-110 mg/dL. ● Humans do not posses the enzyme to hydrolyze
● Excess glucose is stored as the polysaccharide cellulose (β-glycosidase) and cannot digest it.
glycogen or as fat. ● Cellulose makes up the insoluble fiber in our diets,
● Insulin regulates blood glucose levels by stimulating which is important in adding bulk to waste to help
the uptake of glucose into tissues of the formation of eliminate it more easily.
glycogen. ● Glycogen storage disease.
● Patients with diabetes produce insufficient insulin to
adequately regulate blood sugar levels, so they must
monitor their diet and/or inject insulin daily.
● Patients with galactosemia lack an enzyme needed to
metabolize galactose, which accumulates and causes
cataracts and cirrhosis.

DISACCHARIDES

● Individuals who are lactose intolerant no longer produce

this enzyme.
● Without the enzyme, lactose cannot be digested,
causing abdominal cramps and diarrhea.
● Sucrose is very sweet, but contains many calories. To
reduce caloric intake, many artificial sweeteners have
been developed.
○ Aspartame (sold as Equal) is hydrolyzed into
phenylalanine, which cannot be processed by
those individuals with the condition
phenylketonuria.

○ Saccharine (sold at Sweet’n Low) was used

extensively during World War I.