15.

BIOMOLECULES

Synopsis: Biochemistry :
• The branch of science that deals with the study of the chemical composition and structure of living
organisms and also various changes taking place within them.
• Biomolecules : The complex organic molecules which form the basis of life.
• Biomolecules build up living organisms and are also required for their growth and maintenances.
• The sequence that relates biomolecules to living organisms is
Biomolecules → Organelles → Cells → Tissues → Organs → Living organism
• Biomolecules which form the basis of life are
(i) Carbohydrates, (ii) Proteins, (iii) Nucleic acids (iv) Lipids, (v) Vitamins and Hormones.
• Most of the biochemical reactions takes in dilute neutral solutions (pH = 7) at bodytemperature and 1
atmosphere pressure involving complex mechanisms.
• The basic structural and function unit of living organisms is the “cell”.
• Glucose molecules supply energy to the cells by undergoing complex and controlled oxidation in
presence of biocatalyst known as enzymes.
• In exergonic reactions Gibbs free energy change ΔG is negative. These reactions are spontaneous (ΔG
< 0 spontaneous).
• In endergonic reactions Gibbs free energy change ΔG is positive these reactions are non spontaneous
(ΔG > 0 non spontaneous).
• Endergonic reactions are made spontaneous by coupling it with exergonic reactions.
Metalbolic process A→B ΔG>0 Endergonic nonfeasible
Conversion of S → P ΔG < 0 Exergonic feasible
A B
ΔG < 0, feasible
S P

• 6CO2 + 6H2O ⎯⎯⎯⎯

sun light
→ C6H12O6 + 6O2 ΔG = +2880 kJ. It is a light reaction, it follows a dark reaction
ATP hydrolysis.
ATP ⎯⎯⎯⎯⎯⎯⎯
−H PO
⎯
→ ADP ⎯⎯⎯⎯⎯⎯⎯
−H PO
⎯
→ AMP ⎯⎯⎯⎯⎯⎯⎯⎯
−H PO
→ Adinocine
Adinosin 3 4 Adinocine 3 4 Adinocine 3 4
−1 −1
Triphosphate ΔG°=−31 kJ mole diphosphate ΔG°=−31 kJ mole monophosphate ΔG°=−14 kJ mole−1

• Glucose can be converted into disaccharide, polysaccharides like starch, cellulose or proteins or oils
depending on the nature of plants and the reaction type.
C6H12O6+6O2→6CO2+6H2O ΔH = –2880 kJ mole–1

i) CARBOHYDRATES
• In the beginning carbohydrates are considered as hydrates of carbon because of general formula
Cn(H2O)m.
• Rhamnose (C6H12O5) and deoxyribose (C5H10O4) are carbohydrates but not represents the formula
Cn(H2O)m.
• They are also called Saccharides due to similar taste like sugar derived from Latin word for sugar
“Saccharum”.

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• Formaldehyde (CH2O), Acetic acid (C2(H2O)2 will not behave like carbohydrates but represents the
formula Cn(H2O)m.
• Based on structural evidence and chemical reactivity. They are defined as polyhydroxy aldehydes and
polyhydroxy ketones.
• Depending upon their behaviour towards hydrolysis carbohydrates are divided into mono di and
polysaccharides.
• Monosaccharides are simple carbohydrates which cannot behydrolysed to simpler carbohydrates.
Ex. (CH2O)n where n = 3 → 7 (glucose, fructose, ribose, galactose)
• Disaccharides give two units of monosaccharides on hydrolysis.
Ex. Sucrose and maltose both have molecular formula C12H22O11.
• Oligosaccharides on hydrolysis give 3 to 10 simple monosaccharides disaccarides also can be
considered as oligosaccharides.
Ex. Trisaccharides – raffinose ⎯⎯⎯
H2O
→ Glucose + fructose + galactose.
Stachycose (C24H42O21) ⎯⎯⎯
H2O
→ Glucose + fructose + 2 Galactose
• Polysaccharides carbohydrates which upon hydrolysis give (more than 10) many monosaccharide
units.
Ex. Starch, cellulose and glycogen (CnH10O5)n.
n = 100 to 3000.
• More than 200 monosaccharides are known they are grouped as polyhydroxy aldehydes called
Aldoses and polyhydroxy ketons called as ketoses.
Aldotriose CH2OH – CHOH – CHO Glyceraldehyde

Aldotetrose CH2OH – (CHOH)2 – CHO Erythrose, threose

Arabinose, ribose,
Aldopentose CH2OH – (CHOH)3 – CHO
xylose, lyxose

Glucose, mannose,

galactose, gulose,
Aldohexose CH2OH – (CHOH)4 – CHO
talose, lolose, allose,

altrose
O
Ketotriose || Dihydroxyacetone
CH2OH − C − CH2OH
O
Ketoterose || Erytrulose
CH2OH − C − CHOH − CH2OH
O
Ketopentose || Ribulose, Xylulose
CH2OH − C − (CHOH)2 CH2OH
O
|| Fructose, surbose,
Ketohexose
CH2OH − C − (CHOH)3 CH2OH tagatoce

• Sugars monosaccharides and oligosaccharides are crystalline solids soluble in water and sweet in taste
are called sugars.

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• Nonsugars polysaccharides are amorphous solids insoluble in water and taste less called reducing
sugars while others which do not reduced.
• Reducing sugar carbohydrates which contain aldehyde or keto group in hemiacetal form reduce
Tollens and Fehlings solution are these reagents are called nonreducing sugars.
• Glucose (Dextrose : Grape sugar) 20% in fruits and grapes.
• Sucrose and starch on boiling with dil H2SO4 in alcoholic solution undergoes hydrolysis to give glucose.
+
C12H12O11 + H2O ⎯⎯⎯
H
→ C6H12O6 + C6H12O6
sucrose glu cos e fructose
+
H 2 −3atm
C12H22O11 + nH2O ⎯⎯⎯⎯⎯
393
→ nC6H12O6
glu cos e

• The molecular formula of the glucose is C6H12O6.

• Glucose has 5 – OH group is conformed by the acylation of glucose.
• Acylation of glucose with acetic anhydride or with acylchloride give glucose pentacetate.
CHO − (CHOH)4 − CH2OH ⎯⎯⎯⎯⎯
(CH3 CO)O
→
CHO − (CHOCOCH3 )4 − CH2 OCOCH3
• Glucose has one carbonyl group. Presence of carbonyl group can be conformed by the reaction with
hydroxylamine or with a molecule of hydrogen cyanide.
CH2OH − (CHOH)4 CHO + H2N − NHC6H5 ⎯⎯→
D − glu cos e phynyl hydroxylamin

HOCH2 − (CHOH)4 − CH = N − NHC6H5

D − glu cos e phenyl hydrazone

CH2 OH − (CHOH)4 CHO + HCN ⎯⎯→

D − glu cos e

HOCH2 − (CHOH)4 − CHOHCN

D − glu cos e cyanohydrin

• Glucose reduces ammonical silver nitrate (Tollen’s reagent) to metallic silver.

CH2OH(CHOH)4 − CHO + Ag2O ⎯⎯→
CH2OH − (CHOH)4 − COOH
Gluconic acid

• Glucose reduces Fehlings solution to reddish brown cuprous oxide.

CH2OH − (CHOH)4 − CHO + 2CuO ⎯⎯→
CH2OH − (CHOH)4 − COOH + Cu2O
Gluconic acid

• Tollens test, Fehlings test confirms that the carbonyl group is –CHO aldehyde group.
• Bromin water or an alkaline solution of iodine oxidises only the aldehyde group of glucose to gluconic
acid.
• Glucose molecule has one primary alcoholic group (CH2OH).
• Presence of CH2OH group can be known with nitric acid test.
• Glucose with nitric acid gives saccharic acid.
CH2OH − (CHOH)4 − CHO ⎯⎯⎯⎯
HNO3
→
HOOC − (CHOH)4 − COOH
Saccharic acid

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• Glucose on prolonged heating with HI gives hexane. It indicates that all six carbons of glucose are Pn
linked linearly.
CH2OH − (CHOH)4 − CHO ⎯⎯→
HI
CH3 − (CH2 )4 − CH3
• Glucose with phenyl hydrazine gives a osazone called glucosagone it is dihydrazone.
• Glucose with concentrated sodium hydroxide first gives a yellow colour and then turns brown and finally
resinifies. This is called is omers action
• Glucose with a dilute solution of sodium hydroxide gives a mixture of D-glucose D-mannose,
D-fructose. This is Lobry de Bruyn Van Ekenstein rearrangement.
• Fructose and mannose also can give Lobry de Bruyn Van Ekenstein rearrangement.
• Due to reversible isomerisation fructose with keto group also can reduce Tollen’s reagent.
• D-glucose and L-glucose differs in the position of –OH group at second carbon.
• Glucose open chain structure proposed by Bayer.
• – CHO group of glucose does not respond to Schiff’s test and sodium bisulphate and ammonia. This
can’t be explained by the open chain structure of glucose.
• Pentacetate of glucose does not react with hydroxy lamine though it contains –CHO group.
• Concentrated solution of glucose at 30°C gives α-D glucose with melting point 146°C and specific
rotation (α)D = +111°.
• Concentrated solution of glucose at above 98°C give B-D glucose with the melting point 150°C and
specific rotation (β)D = +19.2°.
• αD and βD forms of glucose differ from each other in stereochemistry at first carbon.
• The change in specific rotation of ether form of glucose in aqueous solution to that of equilibrium
mixture is called mutarotation.
• ZZZ
X
α-D + glucose YZZ ZZZ
X
Z equilibrium mixture + 52.5° 36% α and 64% β YZZ
Z β-D glucose +19.2°
• αD and βD forms of glucose with methanol and dry HCl gas gives αD glucoside and β-D-glucoside
respectively.
• Glucoside formation involves ring formation with C1 and C5 carbons.
• Glucoside formation makes the C1 carbon (anomeric carbon) asymmetric.
• α-D glucoside and β-D glucoside differs in the configuration at C1 carbon are called anomers.
• In α-D glucoside –OH group is at right and in β-D glucoside –OH grouped left.
• Super imposable mirror images are enantiomers.
• α-D glucoside and β-D glucoside are not mirror images of each other and they are not super imposable,
so they are not enantiomers.
• Pyranose structure (α or β) is a six numbered cyclic configuration of glucose, it is similar to pyran.
O
• Pyran is six numbered ring containing 5 carbons and one oxygen.
• Five membered ring structure of glucose is called furanose structure as it is similar to furan.
• Glucose is found to occur in pyranose structure.
• In Haward structure of glycopyranose the lower thickened edge of the ring is nearest to the viewer.

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• The groups projected to the right in Fisher projection are below the plane of the ring and those on the
left are above the plane of the ring.
β-D glucopyranose

OH H CH2OH
C
H OH H OH
H
HO H O OH H
H OH HO H
H H OH
CH2OH
• The stereochemistry of all sugars is determined with respect to D- or L-glyceraldehyde.
• In Fischer projection OH group on C2 is at right (+) configuration is D and OH is on C2 is at left (–)
configuration is L.
CHO CHO

H OH HO H

CH2OH CH2OH
R(+) Glyceraldehyde S( ) glyceraldehyde

• In tetrose the –OH group at C2 and C3 are on the same side. The consider the highest numbered carbon
atom as stereogenic centre.
CHO CHO

H OH HO H
H OH HO H

CH2OH CH2OH
Analogus to Analogus to
D-glyceraldehyde L-glyceraldehyde
CHO CHO

HO H H OH
H OH HO H

CH2OH CH2OH
D - form L - form

• D form and L-forms are called diasterioisomers or diastereomers.

• Stereoisomers which are not mirror images are called diastereomers.
• Disaccharide on hydrolysis give two monosaccharide units may be same or different.
Sucrose → glucose + fructose
Lactose → glucose + galactose
Maltose → glucose + glucose
• Reducing and nonreducing nature of disaccharide depends on the position of linkages between the two
monosaccharide units.
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 Biomolecules

Sucrose C12H22O11 Cane sugar :

• It is most common disaccharide widely present in plants.
• Sugar cane or beetroot contains sucrose.
• Colourless, crystalline, sweet substance with [α]D = 65.5°.
• Sucrose is dextro-rotatory, on hydrolysis gives dextro-rotatory glycose [α]D = +52.5° and Laevorotatory
fructose [α]D = –92.4°.
• The mixture of glucose and fructose is Laevorotatory.
• Hydrolysis of sucrose involves change in the rotation from D to L, This is called inversion of cane sugar
or mixture is called invert sugar.
• Linkage present in sucrose is C1 – C2 linkage.
Maltose C12H22O11 :
• Maltose is obtained from starch by the hydrolysis process in presence of diastate enzyme produced by
germinated barlyseas.
• (C6H10O5)n + n/2 H2O → n/2 C12H22O11 (maltose).
• Maltose is a reducing sugar contains C-1 to C-4 linkage.

CH2OH CH2OH
O O
H H H H
H H
OH H O OH H
HO OH

H OH H OH

• Maltose with the enzyme maltose produced by yeast gives two units of glucose both will have pyranose
form.
Lactose C12H22O11 :
• Present in milk and it is known as milk sugar.
• It is a reducing sugar on hydrolysis gives
D-galactose and D-glucose.
• C12H22O11 ⎯⎯⎯⎯→
emulsion
C6O12O6 + C6H12O6.
• Emulsion hydrolyses β-glycosidic linkages.
• Lactose contains C1 – C4 linkage.
CH2OH H OH
O O
HO H
H OH H
OH H H H H
H OH
O
H OH CH2OH

Polysaccharides :

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• Starch, cellulose, dexdrin, glycogen are polysaccharides.

• Monosaccharides are linked through glycoside linkages in polysaccharides.
Starch or Amylum (C6H10O5)n :
• Starch is present in wheat, maize, rice, potatoes, barley, sorghum which are obtained from plants.
• Starch is a amorphous while powder insoluble in cold water soluble in boiling water.
• Starch solution gives blue colour with iodine in cold condition colour disappears on heating.
• Starch on hydrolysis forms D-glucose
n
(C6H10 O5 )n ⎯⎯⎯⎯→
n / 2 H2O
C12H22 O11 ⎯⎯⎯
H2O
→ C6H12O6
2 Maltose D − glucose

• Starch cannot be oxidised by Tollen’s reagent or Fehling’s solution.

• Starch does not forms osazone.
• In starch C1 carbon is in glycoside form.
• Glycosides are acetyls in which anomeric hydroxyl group is replaced by an alkoxy group.
• In glycosides anomeric – OH group is replaced by some other groups connected with O, N, S. They are
respectively called their glycoside.
• Starch contains polysaccharides amylose and amylopectin.
• Natural starch contains 10-20% of amylase and 90-80% of amylopectin.
• Amylase water soluble and it contains only D-glucose units they give blue colour with I2 solution.
• Amylase contains C1 – C4 α-glucosidic linkage.
• Molecular mass of amylase is 10,000 to 50,000.
• Amylopectin branched chain polysaccharide water in soluble.
• Amylopectin doesn’t give blue colour with I2 solution.
• Amylopectin molecule contains 25-30, D-glucose units.
• In amylopectin α-D-glycosidic link between C1 – C4 of the molecule.
• Branched chains in amylopectin are due to C1 – C6 linkages through oxygen.
• Starch a major food material easily hydrolysis in saliva by amylase enzyme to give glucose final
product.
Cellulose (C6H10O5)n :
• This is the structural component of vegetable matter.
• Wood has 40-50% and cotton has upto 90% cellulose.
• It is formed by photosynthesis.
• It contains large number of D-glucose units joined by β-1, 4 glycosidic linkages.
• In the hydrolysis of cellulose gives D-glucose as final product.
• Cellulose is digested in ruminant animals like cattle sheep in presence of enzyme cellulose.
• Cellulose is a colourless amorphous solid.
• Cellulose contains many hydrogen bond which makes the individual stands to align linearly.
• It will not reduce Tollen’s reagent and Fehlings solution.
• It doesn’t form osazone its molecular weight is about 50,000 – 5,00,000 or 300-2500 D-glucose units.

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• Cellulose doesn’t digest in human stomach due to the absence of enzyme cellulose.
• Cellulolytic bacteria present in the stomach (rumen) of ruminant mammals like cattle and sheep gives
cellulose it breakdown the cellulose into glucose during digestion.