CARBOHYDRATES

Prepared by Mrs. Roselita O. Natividad and Dr. Teresita G. Montaño

Natural Science Department – Ateneo de Zamboanga University

Objectives:
At the end of this chapter, you should be able to answer the following questions:
1. How are carbohydrates classified?
2. What are optical isomers and why are they important in living organisms?
3. What information do Fischer projection and Haworth conformation models provide?
4. What structural properties of cellulose account for its widespread occurrence in plants?
5. What are the functions of carbohydrates?
6. Describe the properties of carbohydrates and explain.
7. Show the chemical equations of the common reactions that monosaccharides undergo.
8. Show the glycosidic linkages between monosaccharide molecules in disaccharides

Carbohydrates are class of organic compounds that includes sugar, starches, and cellulose. They make up
most of the organic matter on Earth because of their extensive roles in all forms of life. Originally,
carbohydrates were considered to be hydrates of carbon because they contain hydrogen and oxygen in the
ratio of 2 is to 1 just as in water. Based on experiments though, not all carbohydrates contain the ratio of 2:1
for H:O and there are also compounds with 2:1 ratio for H:O but do not belong to carbohydrates, thus today,
carbohydrates are defines as polyhydroxyaldehydes or polyhydroxyketones or substances that yield these
compounds on hydrolysis

Questions:
1. What are the elements found in all carbohydrates?
2. How are carbohydrates defined?
3. What are the functional groups present in carbohydrates?

FUNCTIONS
Carbohydrates act as storehouses of chemical energy (glucose, starch, glycogen), components of
supportive structures in plants (cellulose), shells (chitin), and connective tissues in animals (acidic
polysaccharides), and essential components of nucleic acids (DNA and RNA) and is linked to many proteins and
lipids where they play key roles in mediating interactions among cells and interactions between cells and other
elements in the cellular environment.

ORIGIN
Carbohydrates are being produced in nature through the process called photosynthesis.

Sunlight

CO2 + H2O  C6H12O6 + O2

Chlorophyll

CLASSIFICATION:
Carbohydrates are classified into three major categories:
1. Monosaccharides 2. Disaccharides 3. Polysaccharides

Monosaccharides
Monosaccharides are simple sugars and are categorized further according to the number of carbon
atoms they contain. They have the general formula of C nH2nOn with one carbon being the carbonyl group either
that of the aldehyde or ketone. The “ose” ending indicates that a molecule is a carbohydrate, those with the
aldehyde group are called aldoses and those with the ketone group are called ketoses. Most common of the
monosaccharides contain 3 to 8 carbon atoms.
 Trioses
 A three-carbon simple sugar
 Formed during the metabolic breakdown of hexoses in muscle metabolism
 There are only two trioses: glyceraldehyde and dihydroxyacetone

H–C=O CH 2OH
H – C – OH C=O
CH2OH CH2OH
Glyceraldehyde Dihydroxyacetone

 Glyceraldehyde and dihydroxyacetone are common names, the common names are the ones being
used because these names are firmly rooted in the literatures
 Glyceraldehyde contains a stereocenter and therefore exists as a pair of enantiomers (mirror image)
 These pair of enantiomeric isomers of glyceraldehyde differ only in one physical property; they rotate
the plane-polarized light in opposite direction, thus, are called optical isomers
 Optical isomers are often designated as D and L

H–C=O H–C=O
H – C – OH OH – C – H
CH2OH CH 2OH
D-glyceraldehyde L-glyceraldehyde

 The D and L glyceraldehydes serve as reference points for assigning relative configuration to all other
aldoses and ketoses
 The reference point is the stereocenter (chiral carbon) farthest from the carbonyl group and this is
called penultimate carbon
 Because most carbohydrates have two or more chiral centers, the letter D and L refer only to a
molecule’s structural relationship to the glyceraldehyde isomers and not to the direction in which it
rotates plane-polarized light

Questions:
1. Define/describe the following terms:
Stereo center Enantiomer Chiral center

2. What are the letters D and L stands for?

3. Describe a penultimate carbon.

Cyclic Structure of Monosaccharides

 Ordinarily, aldehydes and ketones react with alcohols to form hemiacetals, such as

OH
CH3 – C = O + O – CH2 – CH3  CH3 – C – O – CH2 – CH3
CH3 H CH 3

 But this kind of reaction is unstable and easily revert to the aldehyde or ketone forms
 In sugars, however, those that contain 4 or more carbons exist primarily in cyclic forms
 The ring formation occurs in aqueous solution because aldehydes and ketones react reversibly with
hydroxyl groups present in the sugar to form cyclic hemiacetals

H–C=O
H – C – OH
HO – C – H
H – C – OH OR
H – C – OH
CH2OH
  The hemiacetal formation on C1 may occur either above or below the ring
 During the hemiacetal formation, two forms of ring structure can occur: furanose (with 5 membered
ring) and pyranose (with 6 membered ring)

Conformation Representation
 Although Haworth projection formulas often represent carbohydrate structure but they are
oversimplified
 The conformational structures are better because they illustrate the puckered nature of sugar rings
 Pentoses formed a 5-membered ring and this is so close to planar
 Hexoses formed 6-membered ring and they can be represented as a chain or boat conformations

Questions:
1. Write structure of a sugar in the Haworth projection and Fischer projection.

Tetroses
 Are four-carbon sugars
 Some of the examples are tetrose, erythrose.

Question:
1. Write the structure of tetrose and erythrose.

Pentoses
 Are five-carbon sugar molecules
 The most important of these are ribose and deoxyribose, which are found in nucleic acids. Ribose
forms part of ribonucleic acid (RNA), and deoxyribose forms part of deoxyribonucleic acid (DNA).
 Both DNA and RNA are components of every cell nucleus and cytoplasm.

CHO CHO
H – C – OH H–C–H
H – C – OH H – C – OH
H – C – OH H – C – OH
CH2OH CH2OH

Ribose Deoxyribose

 Other pentoses of physiologic importance include

o ribulose, which is an intermediary in the pentose phosphate shunt
o D-lyxose,which is found in the heart muscle, and
o D-xylose and D-arabinose, which are components of glycoproteins.

Question:
1. Write the structure of the following:
Ribulose D-Lyxose
D-Xylose D-Arabinose

Hexoses
 Six-carbon sugars
 Are the most common of all the carbohydrates
 Most important as far as the human body is concerned are glucose, galactose and fructose
 All have the same molecular formula C6H12O6, but with different structural formula, thus, they are
isomers.

Question: Define isomerism.

 Glucose
 An aldohexose and can be represented structurally as:

H H OH
C=O C
H – C – OH H – C – OH
HO – C – H  HO – C – H O or
H – C – OH H – C – OH
H – C – OH H–C
CH2OH CH2OH
Glucose
 Also known as dextrose
 Glucose is the most important monosaccharide
 White crystalline solid
 Soluble in water and insoluble in most organic liquids
 Found along with fructose in many fruit juices
 May be prepared by the hydrolysis of sucrose, starch
 It is normally found in the bloodstream and in the tissue fluids
 Requires no digestion and therefore, can be given intravenously to patients who are unable to take
food by mouth.
 Primary fuel for living cells
 In animals, glucose is the preferred energy source of the brain cells and cells that have few or no
mitochondria, or cells that have limited oxygen supply such as those in the eyeball

Galactose
 An isomer of glucose, also an aldohexose
 The structure can be represented as follows;

H H OH
C=O C
H – C – OH H – C – OH
HO – C – H  HO – C – H O or
HO – C – H HO – C – H
H – C – OH H–C
CH2OH CH2OH
Galactose

 Galactose is present in some glycoproteins and glycolipids

 Also, galactose does not occur free in nature but is found as one of the constituents of the
disaccharide lactose
 Necessary to synthesize a variety of biomolecules
 Fructose
 Is a ketohexose
 Its molecular formula, just like that of glucose and galactose, is C 6H12O6
 Can also be represented as a straight-chain or as a ring structure
 The ring structure is predominant

C H2OH HOH2C OH
C=O C
HO – C – H  HO – C – H O
H – C – OH H – C – OH or
H – C – OH H–C
CH2OH CH2OH

Fructose

 Often called levulose, or fruit sugar.

 Occurs naturally in fruit juices and honey.
 Can be prepared by the hydrolysis of sucrose, a disaccharide, and also by the hydrolysis of inulin, a
polysaccharide found in Jerusalem artichokes.
 Most soluble and also the sweetest of all sugars, being seventy five percent sweeter than glucose
 Because fructose is twice as sweet as sucrose, it is often used as sweetening agent in processed food
products
 Large amounts of fructose are used in the male reproductive tract. It is synthesized in the seminal
vesicles and then incorporated into semen. (Sperm use the sugar as an energy source.)

Physical Properties of Monosaccharides

 Monosaccharides are colorless, crystalline solids
 Very soluble in water, only fairly soluble in ethyl alcohol, and are insoluble in nonpolar solvents, and sweet to the
taste

Reactions of Monosaccharides (Hexoses)

Mutarotation
 The  and  forms are readily interconverted when dissolved in water. The process is called mutarotation
 The open-chain formed during mutarotation can participate in the oxidation – reduction reactions

Oxidation
 Generally, when an aldehyde group is oxidized, it will yield an aldonic acid, while if it is the terminal -CH 2OH , it
will give uronic acid
 If both the aldehyde group and the terminal -CH 2OH group are being oxidized, it will give an aldaric acid

H H OH
C=O C=O C=O
H – C – OH H – C – OH H – C – OH
HO – C – H [O] HO – C – H [O] HO – C – H
H – C – OH H – C – OH H – C – OH
H – C – OH H – C – OH H – C – OH
C=O H – C – OH H – C – OH
OH H H
Glucuronic acid Glucose Gluconic acid

[O]

OH H OH OH
O = C  C  C  C  C  C = O
OH H OH H H OH

Glucaric acid
  The carbonyl groups in both aldonic and uronic acids can react with an -OH group in the same molecule to form a
cyclic ester known as lactone

OH
C=O
H – C – OH
HO – C – H
H – C – OH 
H – C – OH
H – C – OH
H
Lactone

Reduction
 Carbohydrates, specifically the monosaccharides and disaccharides, show reducing properties because
of the functional groups of aldehyde and ketone present in them
 The carbonyl group can be reduced to a hydroxyl group by reducing agents, the reduction product is
known as alditols

H H
C=O H – C – OH
H – C – OH H – C – OH
HO – C – H HO – C – H
H – C – OH + H2  H – C – OH
H – C – OH H – C – OH
H – C – OH H – C – OH
H H
Glucose Glucitol ( Sorbitol)

 Sugar alcohols are used commercially in processing foods and pharmaceuticals

 Sorbitol improves the shelf life of candy because it helps prevent moisture loss. Also, adding sorbitol syrup to
artificially sweetened canned fruit reduces the unpleasant aftertaste of the artificial sweetener saccharine. Once
consumed, sorbitol is converted into fructose in the liver
 In addition, the reducing property of sugars is the basis of the test for sugar in the urine and in the blood
 Laboratory tests for the presence of glucose in urine use Benedict’s reagent, Fehling’s reagent (both contain
cupric hydroxide and positive indication is the presence of a brick- red precipitate)

aldehyde + Cu(OH) 2  acid + Cu2O + H2O

deep blue solution red-orange ppt.
H
C=O COOH
H – C – OH H – C – OH
HO – C – H + 2Cu(OH)2  Cu2O + HO – C – H + H 2O
H – C – OH blue solution red ppt. H – C – OH
H – C – OH H – C – OH
CH2OH CH 2OH
Glucose Gluconic acid

 Another laboratory test for the presence of reducing sugar uses Tollen’s reagent (contains silver hydroxide and
positive indication is the presence of a silvery mirror)
 Molisch test is a general qualitative test for the presence of carbohydrates. When a solution of a carbohydrate is
mixed with alpha-naphthol and then concentrated sulfuric acid is carefully added so as to form a layer below the
mixture, red-violet ring is form at the interface of the two liquids.

H–C=O
H – C – OH CH  CH
HO – C – H  HOCH2 – C C–C=O
H – C – OH O H
H – C – OH hydroxymethyl furfural
CH2OH
Fermentation
 Glucose will ferment in the presence of yeast forming ethyl alcohol and carbon dioxide
 Fuctose will also ferment but galactose will not readily ferment
 Pentoses do not ferment

DISACCHARIDES:

 Most carbohydrates in nature contain more than one monosaccharide units.

 Those that contain three to ten monosaccharide units are called oligosaccharide
 Disaccharides are double sugars, that on hydrolysis yield two simple sugars.

Disaccharides → 2 monosaccharides

 In disaccharide, the two monosaccharide units are joined together by a glycosidic bond

C12H22O11 + H2O → C6H11O6 + C6H11O6

Sucrose glucose fructose
Maltose glucose glucose
Lactose glucose galactose

 Are white crystalline, sweet solids

 Though they are soluble in water, they are too large to pass through cell membrane.

Sucrose
 The sugar used ordinarily in the home.
 Also known as cane sugar.
 Produced commercially from sugar cane and sugar beets.
 A non-reducing sugar.
 Composed of glucose and fructose
 With general formula of C12H22O11

Maltose
 Commonly known as malt sugar
 Is present in germinating grain
 It consists of two glucose molecules
 A white crystalline solid, sweet to the taste, and only fairly soluble in water
 General formula of C12H22O11 and is
 A reducing sugar
 Lactose
 Commonly known as milk sugar,
 Is present in milk and of an animal origin
 A white crystalline solid, sweet to the taste, slightly soluble in water.
 A reducing sugar
 General formula of C12H22O11

POLYSACCHARIDES

 Are complex sugars, that on hydrolysis yield many simple sugars

 Are polymers of monosaccharide
 Complete hydrolysis of polysaccharides produces many molecules of monosaccharide. When formed from
pentoses, they are called pentosans but when formed from hexoses, they are called hexosans
 The hexosans are the most important in terms of physiology is concerned
 The hexosans have the general formula of (C6H10O5)x

Comparison of Polysaccharides with monosaccharides and disaccharides

Property Monosaccharides and Polysaccharides
Disaccharides
Molecular mass Low Very high

Taste Sweet Tasteless

Solubility in water Soluble Insoluble

Size of particles Pass through a membrane Do not pass through a

membrane
Test with Copper complex Positive (except for sucrose) negative
ions( an oxidizing agent)

Starch:
 Plant store energy primarily in the form of starch granules
 A mixture of the amylopectin and amylose
 Amylopectin is a highly branched polysaccharide present only to a small extend (less than 5%); present in the
covering of the starch granules, contains both α(1,4) and α(1,6) glycocidic linkages. The α(1,6) branch point may
occur every 20 – 25 glucose residues

 Amylosse is a straight-chain polysaccharide present in starch to an extent of about 95%,

  The monosaccharide units are joined together by the  - glycosidic bonding
 Is insoluble in water. When starch is placed in boiling water, the granules rupture, forming a paste that gels on
cooling.
 Gives a characteristic deep blue color with iodine. This test is used to detect the presence of starch
 When hydrolyzed, it forms dextrins (amylodextrin, erythrodextrin, achroodextrin), then maltose and finally
glucose.
 Erythrodextrin turns red in the presence of iodine.
 Both maltose and glucose produce no color in the presence of iodine.

Starch → erythrodextrins → maltose → glucose

Blue red colorless colorless

Cellulose:
 A polysaccharide whose monosaccharides are joined together by  - glycosidic bonding
 Wood, cotton, and paper are composed primarily of cellulose
 Is the supporting and structural substance of plants
 Not affected by any of the enzymes present in the human digestive system and so cannot be digested
 Does not dissolve in water or in most ordinary solvents
 Gives no color test with iodine and gives negative test with Cu 2+ complexions.
 Cotton is nearly pure cellulose

Glycogen
 Is present in the body and is stored in the liver and the muscles, where it serves as a reserve supply of glucose
 Has an animal origin
 The structure is similar to that of amylopectin except that it has more branch points, possibly at every fourth
glucose residue in the core of the molecule. In the outer region, branch points are not so close together
(approximately 8 – 12 residues)

o What effect does the structure of glycogen have on its function as an energy source in animals?

Dextrin
 Is produced during the hydrolysis of starch
 An intermediate between starch and maltose
 Forms sticky colloidal suspensions with water and is used in the preparation of adhesives. The glue on the back of
postage stamps is dextrin
 Also used when digestion of starch might be a problem, as with infants and elderly persons.

Acidic Polysaccharides
 Are a group of polysaccharides that contain carboxyl groups and/or sulfuric ester groups
 Play important roles in the structure and function of connective tissues, the matrix between organs and cells that
provide mechanical strength and also filters the flow of molecular information between cells

Hyaluronic Acid
 The simplest and is present in connective tissue
 Most abundant in embryonic tissues and in specialized connective tissues such as synovial fluid, the lubricant of
joints in the body and also in the vitreous of the eye where it provides a clear, elastic gel that maintains the
retina in its proper position
 Composed of D-glucuronic acid linked by a -1,3-glycosidic bond to N-acetyl-D-glucosamine which in turn linked
to D-glucuronic acid by a -1,4-glycosidic bond

o What is the function of hyaluronic acid?

Heparin
  A polysaccharide used as blood anticoagulant
 It accelerates the inactivation of thrombin and other blood-clotting agents
 The strongest organic acid present in the body
 The repeating units are D-glucosamine, D-glucuronic acid, and L-ioduronic acid bonded by a combination of -
1,4- and -1,4-glycosidic bonds

“What is the function of heparin?”

Dextran
 Dextran ( not the same as dextrin) is a polysaccharide produce by certain bacteria when they are grown on
sucrose
 There are various types of dextrans, differing in chain length and degree of branching
 Medically, dextrans used as blood extenders to hold water in the bloodstream and help prevent drops in blood
volume and blood pressure.

That is, Carbohydrates . . . . . .

 Major function is short-term energy storage
 The term comes from the word carbo meaning carbon and hydrate meaning water
 Often have chemical formula that are multiple of CH2O
 Their structure is related to three classes of organic compounds: aldehydes, ketones, alcohols
 Can undergo intramolecular cyclization to form ring
 The large number of OH in the ring form strong H – bond with each other and with water
 This property is important to the function of glucose as a quick energy source because it must be soluble in
bodily fluids
 When compared to octane or fats, glucose contains more oxygen atoms per carbon; it is also partially oxidized
 The oxidation of glucose evolves less energy per gram than the oxidation of octane or lipids
 While glucose does not store energy as efficiently as gasoline or fats, it stores in a form that is readily transported
 Therefore, the structure can be viewed as a compromise between the need to store energy efficiently and the
need to transport it to cells where it is needed
 For fructose, two of the carbon atoms in the ring have –CH 2OH groups attached
 The difference makes fructose sweeter than glucose and results in an even greater ability to mix with water
 In cellulose, neighboring units form H–bonding between the -OH group. This gives each cellulose molecule a rigid
structure that packs efficiently with its neighbor resulting in the structural strength of cellulose

Questions:

1) How are carbohydrates defined?

2) What are the three major functions of carbohydrates?
3) Define the following terms:
Saccharide Ketose Pyranose
Monosaccharide Aldose Furanose

4) How are carbohydrates produced in nature?

5) What gas is produced by plants during photosynthesis? By animals during metabolism?
6) How are carbohydrates classified?
7) What is the bond that joins together the monosaccharide units to form a more complex polysaccharide?
8) Explain the meaning of the designations D and L as used to specify the configuration of carbohydrates.
9) Which carbon determines whether the sugar has a d or L configuration?
10) Explain the conventions for using  and  to designate the configuration of cyclic forms of monosaccharides.
11) In what form do plants store carbohydrates? Animals?
12) What are the elements found in all carbohydrates?
13) What structural feature does a reducing sugar possesses?
14) What is the difference in meaning between the terms glycosidic bond and glucosidic bond?
15) Compare the structure of cellulose to that of amylose? Glycogen?
16) What is the structural difference between amylose and amylopectine
17) Write ring and opened-chained structure of ribose, deoxyribose, glucose, galactose, fructose?
18) What is the most important monosaccharide in the human body?
19) Draw the structure of the following hexoses in the Haworth and Fischer projection:
a) Mannose b) Galactose
20) Draw the Fischer projection of the following and then encircle the penultimate carbon.
a) Glucose b) Fructose
21) List the functions of hyaluronic acid.
22) Explain mutarotation in reference to glucose. By what means it is detected?