CARBOHYDRATES

Objectives:
Define and understand the characteristics of carbohydrate Compare and contrast the different types of carbohydrates Enumerate the functions of carbohydrates

Carbohydrates
These are compounds generally composed of carbon, hydrogen and oxygen. Compounds that contain large quantities of hydroxyl groups It contains either an aldehyde moiety (polyhydroxyaldehydes) or a ketone moiety (polyhydroxy ketones)

Carbohydrates

Carbohydrates, along with lipids, proteins, nucleic acids, and other compounds are known as biomolecules because they are closely associated with living organisms

Carbohydrates
The most abundant organic compounds in the plant world. Has very important functions in both animals and plants Act as storehouses of chemical energy (glucose, starch, glycogen)

provide energy through oxidation

Carbohydrates

Components of supportive structures in plants (cellulose), crustacean shells (chitin) and connective tissues in animals (acidic polysaccharides)
supply carbon for the synthesis of cell components

Carbohydrates

Essential components of nucleic acid (D-ribose and 2-deoxy-D-ribose).

Carbohydrates
Also called as saccharide (from the Latin, saccharum, meaning sugar) Single units of sugar are called monosaccharide. Sugars can readily be linked together to form disaccharides (contains two sugars), oligosaccharides (contains several sugars) and polysaccharides (contains many sugars)

Types of Carbohydrates

Monosaccharide simple carbohydrate

Cannot be split or hydrolyzed into smaller carbohydrate Glucose, the most common carbohydrate, is an example

Monosaccharides

Are simple sugar with an unbranched chain of 3 to 8 carbon atoms, one of them in a carbonyl group and the rest attached to hydroxyl groups

Monosaccharides

There are two types of monosaccharide structure:

An ALDOSE the carbonyl group is on the first carbon (-CHO) A KETOSE contains the carbonyl group on the second carbon atom as a ketone (C=O)

Monosaccharides
The suffix ose indicates that the molecule is a carbohydrate The prefix tri-, tetra-, pent-, and so forth indicate the number of carbon atoms in the chain The designation aldo- and keto- are use to identify if the monosaccharide is an aldose or a ketose.

Monosaccharides

The simplest aldose is glyceraldehyde or an aldotriose

The simplest ketoseone is dihydroxyacetone or a ketotriose

Types of Carbohydrates

Disaccharide consist of two monosaccharide units joined together

Can be split into two monosaccharides Table sugar, sucrose (C12H22O12) is an example which can be hydrolyzed to form glucose and fructose

Types of Carbohydrates

Polysaccharide
Naturally occurring polymers containing many monosaccharide units. It can be hydrolyzed to give many molecules of monosaccharide.

Role of Carbohydrates (Plants)

Carbohydrates: synthesized during the process of photosynthesis

Plants

Use them as a source of energy Store them in the cells.

Role of Carbohydrates (Animals)

Carbohydrates: consumed as sugars, starches, and fiber When complex carbohydrates are consumed, digestion breaks the bonds between the larger carbohydrate molecules so that individual simple sugars can be absorbed into the bloodstream through the walls of the intestines.

Role of Carbohydrates (Animals)

The bloodstream carries the simple sugars to cells throughout the body where they cross into the cells through the cell membrane. Once inside the cells, simple sugars are used as fuel in the process of cellular respiration, releasing energy which is stored as ATP.

Role of Carbohydrates (Animals)

If an organism has a greater supply of carbohydrates than needed for its energy requirements, the extra energy is converted to fats and stored by the body.

Functions of Carbohydrates

Energy Source
Glucose in cells is the primary source of energy -fuel for cellular respiration

Energy Storage (short term)

Glycogen in the liver of animals Starch in the structures of plants

Structural Support
Cellulose forms cell walls in plants Also an important source of fiber for animals to stimulate the digestive system

Occurrence
Cell walls of bacteria and plants Membranes Nucleotides sugar components Nucleic acids DNA and RNA Coenzymes

Physical Properties

Most monosaccharides have a sweet taste (fructose is sweetest; 73% sweeter than sucrose). They are solids at room temperature. They are extremely soluble in water:
Despite their high molecular weights, the presence of large numbers of OH groups make the monosaccharides much more water soluble than most molecules of similar MW.

Glucose can dissolve in minute amounts of water to make a syrup (1 g / 1 ml H O).

Stereochemistry of Carbohydrates

Carbohydrate exists in two isomeric forms that are mirror images of each other:

These forms are stereoisomers of each other.

Stereochemistry of Carbohydrates
Glyceraldehyde is a chiral molecule it cannot be superimposed on its mirror image. The two mirror image forms of glyceraldehyde are enantiomers of each other.

Chiral Carbon
Chiral molecules have the same relationship to each other that your left and right hands have when reflected in a mirror. Achiral objects can be superimposed on the mirror images for example, drinking glasses, spheres, and cubes.

Chiral Carbon

Any carbon atom which is connected to four different groups will be chiral, and will have two nonsuperimposable mirror images; it is a chiral carbon or a center of chirality.
if any of the two groups on the carbon are the same, the carbon atom cannot be chiral.

Many organic compounds, including carbohydrates, contain more than one chiral carbon.

2n Rule

When a molecule has more than one chiral carbon, each carbon can possibly be arranged in either the right-hand or left-hand form, thus if there are n chiral carbons, there are 2n possible stereoisomers.

2n Rule

Fischer Projection Formula

A two-dimensional representation showing the configuration of a stereocenter, horizontal lines represent bonds projecting forward from the stereocenter, and vertical lines represent bonds projecting toward the rear. Place the carbonyl group at or near the top and the last achiral CH2OH at the bottom.

Fischer Projection

Naming Stereoisomers

When there is more than one chiral center in a carbohydrate, look at the chiral carbon farthest from the carbonyl group: if the hydroxy group points to right when the carbonyl is up it is the D-isomer, and when the hydroxy group points to the left, it is the L-isomer.

D- and L- configuration
D dextrorotatory, (+) clockwise rotation, position of the hydroxyl group on the reference carbon is on the right of the projection formula L levorotatory, (-) counterclockwise rotation, position of the hydroxyl group on the reference carbon is on the left of the projection formula

Naming Stereoisomers

Naming Stereoisomers

Identify the following compounds as D or L isomers, and draw their mirror images.

Whats so Great about Chiral Molecules?

Molecules which are enantiomers of each other have exactly the same physical properties (melting point, boiling point, index of refraction, etc.) but not their interaction with polarized light. Polarized light vibrates only in one plane; it results from passing light through a polarizing filter.

Whats so Great about Chiral Molecules?

Whats so Great about Chiral Molecules? (Optical Activity)

A levorotatory () substance rotates polarized light to the left. [E.g., lglucose; (-)-glucose] A dextrorotatory (+) substance rotates polarized light to the right. [E.g., dglucose; (+)-glucose] Molecules which rotate the plane of polarized light are optically active.

Whats so Great about Chiral Molecules? (Optical Activity)

Most biologically important molecules are chiral, and hence are optically active. Often, living systems contain only one of all of the possible stereochemical forms of a compound. In some cases, one form of a molecule is beneficial, and the enantiomer is a poison (e.g., thalidomide).

Diastereomers
Chiral carbon give rise to stereoisomers and that they are nonsuperimposable. Common sugars typically have not one, but multiple chiral carbons. Glucose has 16 possible stereoisomers

Diastereomers
D-glucose has only one mirror image and in fact, any stereoisomer has only one mirror image. For glucose, the other 14 stereoisomers are not mirror image; thus, are called diastereomers

Amino Sugars
Amino sugars contain an NH2 group in place of an OH group. Only three amino sugars are common in nature:

D-glucosamine D-mannosamine D-galactosamine

D-glucose

Common Names
Glucose dextrose

Natural Source
Fruits, vegetables, corn syrup and honey

D-glucose

Importance
Building block for disaccharides (such as sucrose, lactose and maltose) and polysaccharides (starch, cellulose and glycogen)

Disease
Hypoglycemia/hyperglycemia

D-galactose

Natural Source
None for free form Formed by hydrolysis of milk lactose

Importance
Cellular membranes of brain and nervous system

D-galactose

Disease
Galactosemia Enzyme to digest galactose missing and levels build in blood cause mental retardation, cataracts and cirrhosis

D-fructose

Common names
Levulose Fruit sugar

Natural source
Fruit juice and honey Hydrolysis of sugar

Importance
Due to sweetness, used as sugar

Sugar Ring Structures

Sugar can exist as linear structures but mostly exist as cyclic structures. The linear form mutates into the cyclic form thru mutarotation. When sugars cyclize, they typically form furanose (five-membered) or pyranose (six-membered) ring structures. (hemiacetal or hemiketal).

Sugar Ring Structures

Cyclization creates a carbon with two possible orientations of the hydroxyl around it. This carbon is referred as the anomeric carbon and the two possible forms as anomers.

Sugar Ring Structures

The two possible configurations of the hydroxyl group are and .

corresponds to the hydroxyl being in the down position corresponds to the hydroxyl being in the up position

Sugar Ring Structures

Sugar ring structures can be written in a variety of ways. The most common forms are the Haworth projections and the Fischer projections

Haworth Projections
A five or six-membered cyclic sugar compound is represented as a planar pentagon or hexagon lying roughly perpendicular to the plane of the paper. Groups bonded to the carbons of the ring then lie either above of below the plane of the ring.

Haworth Projections

Haworth Projections
When cyclization occurs, the anomeric carbon of an aldose is carbon 1 and for most ketoses is carbon 2. Are most commonly drawn with the anomeric carbon to the right and the hemiacetal oxygen to the back.

Haworth Projections

Hawort Projections

Haworth Projections

Identify the structures below as being the - or - forms, and draw the structure of their anomers:

Haworth Projections

Show the mutarotation of D-xylose and D-tagatose.

Reactions of Monosaccharides
Formation of Glycosides (Acetals) Reduction to Alditols Oxidation to Aldonic Acids (Reducing Sugars) Oxidation to Uronic Acid Formation of Phosphoric Esters

Formation of Glycosides
The hemiacetal and hemiketal forms of monosaccharides (cyclic sugars) can react with alcohols to form cyclic acetal and cyclic ketal structures called glycosides. The new carbon-oxygen bond (from the anomeric carbon to OR) is called the glycosidic bond or linkage.

Formation of Glycosides

Formation of Glycosides
Once the glycoside is formed, the ring can no longer open up to the openchain form. Glycosides, therefore, are not reducing sugars.

Formation of Glycosides

Show the formation of the glycosidic bond of -D-glucopyranose (-Dglucose)

Formation of Glycosides

Identify the glycosidic bond and the anomeric carbon in the following compounds.

Oxidation and Reduction

Oxidation and reduction of monosaccharides in nature are catalyzed by specific enzymes classified as oxidases for example, glucose oxidase.

Reduction to Alditols
The carbonyl group of monosaccharides can be reduced to a hydroxyl group by variety of reducing agents. The reduction products are known as alditols.

Product formed when the CHO group of monosaccharide is reduced to a CH2OH group.

Reduction of Alditols

Reduction of -D-glucose gives Dglucitol, more commonly known as Dsorbitol.

Sorbitol
Sorbitol is found in the plant world in many berries and cherries, plums, pears, apples, seaweed, and algae. It is about 60% as sweet as sucrose (table sugar). Used in the manufacture of candies and as sugar substitute for diabetics

Reduction of Alditols
Common alditols found in the biological world include erythritol, Dmannitol, and xylitol. Xylitol us used as a sweetening agent in sugarless gum, candy and sweet cereals.

Assignment

Research on 15 alditols found in the biological world.

Give the structure using Fischer projection. Identify the parent monosaccharide where it was derived. State the use of the alditol. Give the source where the alditol can be found.

Oxidation to Aldonic Acids (Reducing Sugars)

Aldehyde group of an aldose can be oxidized, under basic conditions, to a carboxylate group. An example is the oxidation of -Dglucose will yield D-gluconate (the anion of D-gluconic acid)

Oxidation to Aldonic Acids (Reducing Sugars)

Any carbohydrate that reacts with an oxidizing agent to form an aldonic acid is classified as a reducing sugar. (it reduces the oxidizing agent) 2-ketoses are also reducing agents but carbon 1 (CH2OH group) of a ketose is not oxidized directly. 2-ketose-enediol-aldose-aldonic acid

Oxidation to Uronic Acids

Enzyme-catalyzed oxidation of the primary alcohol at carbon 6 of a hexose yields a uronic acid. D-glucose enzyme-catalyzed oxidation yields D-glucoronic acid.

D-glucuronic acid
Widely distributed in both the plant and animal worlds. In humans, it serves as an important component of the acidic polysaccharides of connective tissues. The body uses to detoxify foreign phenols and alcohols. In liver, these compounds are converted to glycosides of glucuronic acids (glucuronides) and excreted in the urine.

Formation of Phosphoric Esters

Mono- and diphosphoric esters are important intermediates in the metabolism of monosaccharides. Phosphate esters of monosaccharides are found in the sugar-phosphate backbone of DNA and RNA, and in ATP. Phosphate esters can form at the 6carbon of aldohexoses and aldoketoses.

Formation of Phosphoric Esters

Phosphoric acid is a strong enough so that the pH of cellular and intercellular fluids, both acidic protons of a phosphoric ester are ionized.

Disaccharides and Oligosaccharides

Most carbohydrates in nature contain more than one monosaccharide unit.

Disaccharides (two units) Trisaccharides (three units) and so forth Oligosaccharides ( six to ten units) Polysaccharides (large number of units)

Units are joined by a glycosidic bond or linkage.

Disaccharides

Two monosaccharides units joined together by a glycosidic bond between the anomeric carbon of one unit and an OH group of the other unit.

Disaccharides

Disaccharides

Three physiologically important disaccharides are sucrose, lactose and maltose

Sucrose
Table sugar, is the most abundant disaccharide in the biological world. Prevalent in sugar cane and sugar beets, is composed of glucose and fructose through an -1,2-glycosidic bond. Carbon 1 of -D-glucose bonds to carbon 2 of D-fructose. Non-reducing sugar

Sucrose

Sucrose
Maple syrup contains about 65% sucrose, with glucose and fructose present as well; Caramel is the solid residue formed from heating sucrose.

Sucrose

A flavoring agent called invert sugar is produced by the hydrolysis of sucrose under acidic conditions, which breaks it apart into glucose and fructose; invert sugar is sweeter than sucrose because of the fructose.

Sucrose

Some of the sugar found in honey is formed in this fashion; invert sugar is also produced in jams and jellies prepared from acid-containing fruits.

Lactose
The principal sugar present in milk (milk sugar) Accounts for 5 to 8% of human milk and 4 to 6% of cows milk. Consists of D-galactose bonded by a -1,4-glycosidic bond to carbon 4 of Dglucose.

Lactose
It is digested by the enzyme lactase. Reducing sugar

Maltose
Derives its name from its presence in malt, the juice from sprouted barley and other cereal grains. Consists of two units of D-glucose joined by a glycosidic bond between carbon 1 (the anomeric carbon) of one unit and carbon 4 of the other unit (1,4-glycosidic bond)

Maltose
Also known as malt sugar. It is found in germinating grain (such as barley), and is formed during the hydrolysis of starch to glucose during digestion. Because it has a hemiacetal group, it is a reducing sugar.

Maltose

Oligosaccharides

Oligosaccharides contain from 3 to 10 monosaccharide units.

Raffinose

An oligosaccharide found in peas and beans; largely undigested until reaching the intestinal flora in the large intestine, releasing hydrogen, carbon dioxide, and methane)

Polysaccharides
Polysaccharides contain hundreds or thousands of carbohydrate units. Polysaccharides are not reducing sugars, since the anomeric carbons are connected through glycosidic linkages. We will consider three kinds of polysaccharides, all of which are polymers of glucose: starch, glycogen, and cellulose.

Starch
Starch is a polymer consisting of Dglucose units. Starches (and other glucose polymers) are usually insoluble in water because of the high molecular weight, but they can form thick colloidal suspensions with water. There are two forms of starch: amylose and amylopectin.

Starch - Amylose
Amylose consists of long, unbranched chains of glucose (from 1000 to 2000 molecules) connected by (14) glycosidic linkages. 10%-20% of the starch in plants is in this form.

Starch - Amylose

Starch - Amylose
Amylose forms helices (coils) which can trap molecules of iodine, forming a characteristic deep blue-purple color. (Iodine is often used as a test for the presence of starch.)

Starch - Amylopectin
Amylopectin consists of long chains of glucose (up to 105 molecules) connected by (14) glycosidic linkages, with (16) branches every 24 to 30 glucose units along the chain. 80%-90% of the starch in plants is in this form.

Starch - Amylopectin

Glycogen

Glycogen, also known as animal starch, is structurally similar to amylopectin, containing both (14) glycosidic linkages and (16) branch points. Glycogen is even more highly branched, however, with branches occuring every 8 to 12 glucose units. Glycogen is abundant in the liver and muscles; on hydrolysis it forms glucose, which maintains normal blood sugar level and provides energy.

Cellulose

Cellulose is a polymer consisting of long, unbranched chains of D-glucose connected by (14) glycosidic linkages; it may contain from 300 to 3000 glucose units in one molecule.

Cellulose

Cellulose

Because of the -linkages, cellulose has a different overall shape from amylose, forming extended straight chains which hydrogen bond to each other, resulting in a very rigid structure.

Cellulose

Cellulose is an important structural polysaccharide, and is the single most abundant organic compound on earth. It is the material in plant cell walls that provides strength and rigidity; wood is 50% cellulose.

Cellulose

Most animals lack the enzymes needed to digest cellulose, although it does provide needed roughage (dietary fiber) to stimulate contraction of the intestines and thus help pass food along through the digestive system.

Cellulose

Some animals, such as cows, sheep, and horses, can process cellulose through the use of colonies of bacteria in the digestive system which are capable of breaking cellulose down to glucose; ruminants use a series of stomachs to allow cellulose a longer time to digest.

Cellulose

Some other animals such as rabbits reprocess digested food to allow more time for the breakdown of cellulose to occur.

Cellulose

Cellulose is also important industrially, from its presence in wood, paper, cotton, cellophane, rayon, linen, nitrocellulose (guncotton), photographic films (cellulose acetate), etc.