BIOMOLECULES

Carbohydrate

Amino acid &

Protein
Biomolecules
Nucleic Acid

Vitamin
 CARBOHYDRATES
Old definition ❖ Carbo-hydrates:
Compound Cx(H2O)y Carbohydrate

C6H12O6
C2H4O2
(CH3COOH)
C6H12O5
(Rhamnose)
New definition Carbohydrates
optically active polyhydroxy aldehydes or ketones or the compounds which
produce such units on hydrolysis.
Carbohydrates, which are sweet in taste, are also called sugars.
The most common sugar, used in our homes is named as
sucrose whereas the sugar present in milk is known as lactose.
 Ketohexose
Aldopentose Aldohexose

Different Types of Monosaccharides

Carbon atoms General term Aldehyde Ketone

3 Triose Aldotriose Ketotriose

4 Tetrose Aldotetrose Ketotetrose
5 Pentose Aldopentose Ketopentose
6 Hexose Aldohexose Ketohexose
7 Heptose Aldoheptose Ketoheptose
Configuration of sugar
Chemical reaction of glucose :-

Reduction:
Aldehyde group
Oxidation:

Fructose does
not react with
Br2 water
Reaction with hydroxyl amine and hydrogen cyanide:
 Biomolecules
ALLEN
* Starch, cellulose are Polymers of Glucose
* Lactose and sucrose are disaccharides
* Sucrose is a non reducing sugar, gives negative test for Benedict and tollen's reagent, they do not
form osazone and do not show mutarotation.
* Acetals of carbohydrates are called as GLYCOSIDE
Formation of Glycosides
Glucose reacts with methyl alcohol in presence of dry HCl to form  and -methyl glycoside of
glucose. The reaction takes place only on OH of hemi-acetylic carbon. Other hydroxyl groups are
unreactive.
H OCH3 CH3O H
C C
(CHOH)3 O (CHOH)3 O
CH CH
CH2OH CH2OH
 –Methyl glucose  –Methyl glucose

To methylate all the OH groups, methylating agent used is dimethyl sulphate.

+ CH3OH HCl


Such compounds are called glucoside (cyclic acetals). They are special type of acetals in which one
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of the oxygen of the acetal linkage is the ring oxygen of the pyranose or furanose.
Ring structure of glucose :
H–C
(i) Glucose does not give pink colour with schief reagent. H–C–OH
(ii) Does not form adduct with NaHSO3, NH3 HO–C–H O

(iii) Glucose exist in two isomeric form H–C–OH

H–C
(iv) It show mutarotation CH2OH

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JEE-Chemistry
ALLEN
Since there is no free aldehyde group, so it does not react with weak reagent
(NH3, NaHSO3) but strong reagent (HCN, NH2OH, C6H5NH – NH2) break up ring

Hydrolysis
  
H 2O


REACTIONS OF GLUCOSE

COOH
(CHOH)4 Br2 / H2 O Red P / HI n Hexane
CH2OH or Alkaline
Gluconic acid solution of I2 CH3COCl
Pentaacetate
+
COONH4 (5-OH group)
(CHOH)4 Tollen’s NH2–OH (1 eq)
C6H12O6 Oxime
Salts of CH2OH
gluconic acids HCN
COONa Glucose cyanohydrin
Fehling’s
(CHOH)4
5HIO4
CH 2OH HCHO + 5HCOOH

COOH Schief's reagent, NaHSO3

HNO3 No reaction
(CHOH)4 NH3
COOH
(Saccharic acid)

These reactions indicate that glucose has 6-C straight chain with one –CHO group & 5-OH group.
General reactions of monosaccharies
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 Biomolecules
ALLEN
1. Acetylation :

+ 5CH3COCl / (CH3CO)2O  + 5HCl

This reaction suggests presence of 5( OH ) group.

Q. The penta acetate of glucose give –ve test with Tollen’s reagent & Fehling solution, explain?

No hemiacetal linkage, So no
H
CHO group in aq.
H OH
alkane solution –ve test
H
Sol. HO H
5
AcCl
 H Tollen's –ve
H OH H Fehling
H –ve
Benedict
–ve
Shifts –ve
NaHSO3
–ve

2. Red by HI / Red P :

Re
dP / HI
 n-Hexane Re
dP / HI
 n-Hexane

3. Reaction with HCN:

+ HCN  + HCN 

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4. Reaction with NH2–OH (hydroxyl amine):

+ NH2–OH  + NH2OH 

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JEE-Chemistry
ALLEN
5. Reaction with phenyl hydrazine: Both glucose and fructose give “osazone”.
Reaction with glucose :

–Ph–NH2
+ 3 C6H5 NH – NH2 –NH , –2H O Osazone
3 2

Mechanism :

O O H
+ HC– N–NHPh
HC HC–NH2NHPh HC= N–NHPh 
HC–NH–NH–Ph
NH2NHPh IMPE
CHOH CH–OH CH–OH C – OH + +
–H2O –H C O H
R R R R
R
+
–H

HC=NNHPh HC=NH
2PhNHNH2
C NNHPh –NH3 C O

R R

Propose Mechanism for :

CHOH CH=NNHPh
PhNHNH2
C=O C=NNHPh + PhNH2 + NH3
(Excess)

R R
(Osazone)

Reaction with fructose :

Fructose + 3 NH2–NH–C6H5  Osazone

Step (i) + H2N – NH – C6H5 

Step (ii) + H2N – NH – C6H5 

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Step (iii) + H2N – NH – C6H5 

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 Biomolecules
ALLEN
Glucose , Mannose & Fructose give same osazone because structure of last four carbons in these
carbohydrates is same.
Only C-1 and C-2 in glucose and fructose are involved in osazone formation addition reaction do
not run through out the chain.The failure to undergo further reaction has been explained by stabilization
of the osazone by chelation.
6. Catalytic reduction:

CH2–OH CH2–OH
H—C—OH HO—C—H
HO—C—H HO—C—H
H
2 / Ni or
 H—C—OH H
2 / Ni or
 D-sorbital +
NaBH 4 NaBH 4 H—C—OH
H—C—OH H—C—OH
CH2–OH CH2–OH
D-Sorbital D-Manitol

7. Oxidation:

Tollne's reagent
Glucose or Glucose dil
.HNO
3 
Br2 water
or
Fehling solution

Glucose HIO
4  5HCOOH + HCHO + 5HIO3
Oxidation of fructose :
Tollen's, Reagent
Fructose 
Fehling solution
  Gluconic acid

Fructose also reduces tollen’s & fehling reagent because in basic medium fructose isomerises to
glucose.
Br water
Fructose 2  No reaction

Fructose HNO
3  + +
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8. Reaction with enzyme:

Glucose or Fructose Yeast

  2C2H5OH + 2CO2
Zymase enzyme

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ALLEN
9. Reaction with dil NaOH / Ca(OH)2
dil. NaOH
Mannose or Glucose or fructose   Glucose + Fructose + Mannose
Mechanism :
H–C–OH

C–OH l

Glucose

Fructose
Base-catalyzed isomerisation of aldoses and Ketoses:
Although glucose in solution exists mostly in its cyclic hemiacetal forms it is also in equilibrium
with a small amount of it’s acyclic aldehyde form.

0.02 M
Ca ( OH ) 2
  + + + Traces of other compound

Method of ascending the sugar series: An aldose may be converted into it’s next higher
aldose eg. an aldopentose into an aldohexose.
By Kiliani Fischer upgradation:

HCN
 (
i ) H 2 Pd
  
aq. ( ii ) BaSO4 H
3O

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Theoretically two lactones are possible, since two cyanohydrin may be formed when hydrogen
cyanide adds on to the aldopentose (a new assymetrical carbon is produced)

+ HCN  +

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 Biomolecules
ALLEN
Wolfrom reaction : Wolfrom have stepped up an aldose to a ketose with one more carbon atom
by a modified Arndt-Eistere reaction.

Br
2  (
i ) Ac 2O
 CH
2N2
 (
i ) AcOH

H 2O ( ii ) SOCl 2 (ii ) Ba ( OH ) 2

Method of descending the sugar series :

Wohl’s method:

CHO CH=N–OH CN
CH–O–C–CH3 CHO
CHOH CHOH
NH2OH (CH3CO)2O O aq.AgOH
(CHOH)3 + AgCN
(CHOH)3 (CHOH)3 ,excess (CH–O–C–CH3)3
CH2OH
CHOH
2 CH2OH O
CH2–O–C–CH3
O

Ruff’s method:

Br
2 /
H 2O
 Ca
salt
 + CO2
H 2O 2 / Fe 2 
Fenton 's
reagent

Conversion of an aldose into a ketose :

3
C6H5 NHNH2
  HCl

 Zn
/ 
CH3COOH
 

An aldehyde group is reduced more readily than a ketonic group.

Conversion of a Ketose into an aldose :
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[
O]
 Na
/Hg
 
H
2 / Ni
 HNO3 
 HCl

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 Biomolecules
ALLEN
Tests for carbohydrates:
(i) When heated in a dry test tube, it melts, turns brown and finally black, giving a characteristic
smell of burning sugar.
(ii) W hen warmed with a little concentrated H 2SO4, it leaves a charred reside of carbon.
(iii) Molisch’s Test (named after Austrian botanist Hans Molisch) is a sensitive chemical test for
the presence of carbohydrates, based on the dehydration of the carbohydrate by sulfuric acid to produce
an aldehyde, which condenses with two molecules of phenol (usually α-naphthol, though other phenols
(e.g. resorcinol, thymol) also give colored products) resulting in a red- or purple-colored compound.
The test solution is combined with a small amount of Molisch’s reagent (α-naphthol dissolved in ethanol)
in a test tube. After mixing, a small amount of concentrated sulfuric acid is slowly added down the sides
of the sloping test-tube, without mixing, to form a bottom layer. A positive reaction is indicated by
appearance of a purple ring at the interface between the acid and test layers.
All carbohydrates — monosaccharides, disaccharides, and polysaccharides — should give a positive
reaction, and nucleic acids and glycoproteins also give a positive reaction, as all these compounds
are eventually hydrolyzed to monosacharides by strong mineral acids. Pentoses are then dehydrated
to furfural, while hexoses are dehydrated to 5-hydroxymethylfurfural. Either of these aldehydes, if
present, will condense with two molecules of naphthol to form a purple-colored product, as illustrated
below by the example of glucose:

HO
O + HO O
HO H3O
HO –3H2O O
OH OH
5-(hydroxymethyl) furfural
D-glucose

OH OH OH
+
H3O HO [O] , H3O
+ HO
HO O + 2
–H2O O +
–H , –2e
–
O
O
-naphthol
5-(hydroxymethyl) furfural
OH OH
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purple-colored dye

E 37
 DISACCHARIDES
Disaccharides
Sucrose
-D-Glucose

Glycosidic linkage

-D-Fructose

C1 of -D- Glucose + C2 of -D- Fructose Non reducing sugar

-D- Glucopyranose + -D- Fructofuranose
Disaccharides
Sucrose

-D-Glucose

Glycosidic linkage

-D-Fructose

C1 of a-D- Glucose + C2 of b-D- Fructose Non reducing sugar

-D- Glucopyranose + -D- Fructofuranose
 DISACCHARIDES

Invert Sugar

“Hydrolysis of sucrose brings about a change in the sign of rotation, from

dextro (+) to laevo ( ) and the product is named as invert sugar.”

Q. Which of the following statement is not true about sucrose ?

(1) On hydrolysis, it produces glucose and fructose
(2) The glycosidic linkage is present between C1 of - glucose and
C1 of - fructose
(1) It is also named as invert sugar
(2) It is a non reducing sugar
 DISACCHARIDES
Maltose

C1 of -D- Glucose + C4 of -D- Glucose Reducing sugar

Lactose

C1 of b-D- Galactose + C4 of b-D- Glucose Reducing sugar

 POLYSACCHARIDES

Amylose

Amylopectin
(ii) Cellulose: Cellulose occurs exclusively in plants and it is the most
abundant organic substance in plant kingdom. It is a predominant
constituent of cell wall of plant cells. Cellulose is a straight chain
Glycogen: The carbohydrates are stored in animal body as glycogen. It is also known as
animal starch because its structure is similar to amylopectin and is rather more highly
branched. It is present in liver, muscles and brain. When the body needs glucose, enzymes
break the glycogen down to glucose. Glycogen is also found in yeast and fungi
 A-10.@ What is the basic structural difference between starch and cellulose ?

4.@ Which of these are polysaccharides of glucose ?

(A) Starch (B) Cellulose (C) Sucrose (D) Lactose

2. Complete hydrolysis of cellulose gives [AIEEE-2003, 3/225]

(1) D-fructose (2) D-ribose (3) D-glucose (4) L-glucose

7. The incorrect statement among the following is : [JEE(Main) 2017 Online (09-04-17), 4/120]
(1) a-D-glucose and b-D-glucose are anomers.
(2) The penta acetate of glucose does not react with hydroxyl amine.
(3) Cellulose is a straight chain polysaccharide made up of only b-D-glucose units.
(4) a-D-glucose and b-D-glucose are enantiomers.

11. Among the following, the incorrect statement is : [JEE(Main) 2018 Online (16-04-18), 4/120]
(1) Cellulose and amylose has 1,4-glycosidic linkage.
(2) Lactose contains b-D-galactose and b-D-glucose.
(3) Maltose and lactose has 1,4-glycosidic linkage.
(4) Sucrose and amylose has 1,2-glycosidic linkage.
 3. Complex hydrolysis of starch gives : [JEE(Main) 2015 Online (10-04-15), 4/120]
(1) glucose only
(2) glucose and fructose in equimolar amounts
(3) galactose and fructose in equimolar amounts
(4) glucose and galactose in equimolar amounts

1.@ Consider an amylose chain of 4000 glucose unit. At how many cleavage require to lower the average length to 400 units.

4. Accumulation of which of the following molecules in the muscles occurs as a result of vigorous exercise?
[JEE(Main) 2015 Online (11-04-15), 4/120]
(1) Glycogen (2) Glucose (3) Pyruvic acid (4) L-lactic acid

8.* The correct statement(s) about the following sugars X and Y is(are) : [JEE 2009, 4/160]

(A) X is a reducing sugar and Y is a non-reducing sugar.

(B) X is a non-reducing sugar and Y is a reducing sugar.
(C) The glucosidic linkages in X and Y are a and b, respectively.
(D) The glucosidic linkages in X and Y are b and a, respectively.
10. The following carbohydrate is [JEE 2011, 3/180]

(A) a ketohexose (B) an aldose (C) an a-furanose (D) an a-pyranose

Osazone Test

1.Reaction indicate presence of free aldehyde

2.Three mole of PhNHNH2 are consumed
3.If last three chiral c are same then they will produce same osazone

4. D-Glucose , D-Mannose and D-Fructose form same osazone

Q. Which of the following carbohydrate give same osazone :
(1) D-Glucose (2) D-Mannose (3) D-Fructose (4) D-Galactose

D-Glucose D-Mannose D-Fructose D-Galactose

❖ Alkaline solution of fructose contain glucose, fructose and mannose.
Q. Fructose reduces Tollen’s reagent due to :-
(1) Primary alcoholic group
(2) Secondary alcoholic group
(3) Enolisation of fructose followed by conversion to aldehyde by base
(4) Asymmetric carbon
Q. The a- & b- glucose have different specific rotations. When either is
dissolved in water, their specific rotation changes to reach a certain fixed
value. This is called ?
Ans :- Mutarotation

Mutarotation:

❖ All reducing sugar show mutarotation.

Q. Which of the following does not exhibit the phenomenon of
mutarotation ?
(1) (-) Fructose
(2) (+) Sucrose
(3) (+) Lactose
(4) (+) Maltose
Q. Which of the following pairs represents anomer :-
Q. Identify and form of carbohydrate/saccharide :-
Q Which of the following is non-reducing sugar :-
 NUCLEIC ACIDS

Nucleic acids are long chain polymers of nucleotides, so they are also called
polynucleotides.
These are mainly of two types,
Deoxyribonucleic acid (DNA)
Ribonucleic acid (RNA).
DNA (or RNA) Bases + pentose sugar + Phosphoric acid

Nucleotide Base + Sugar + Phosphate

Nucleoside Base + Sugar

 NUCLEIC ACIDS
Nitrogenous Bases:

(a) Purine Nitrogenous Bases:

Pure Ag

Adenine (A) Guanine (G)

(b) Pyrimidine Nitrogenous Bases:

Cut

Cytosine (C) Thymine (T)

Uracil (U)
Q. Which of the following bases is not present in DNA?
(1) Adenine (2) Thymine
(3) Cytosine (4) Uracil

Sugar:

b-D-Ribose b-D-2-Deoxyribose

(RNA) (DNA)
Structure of (a) a nucleoside and (b) a nucleotide
 DNA
James Watson and Francis Crick
Double strand( two nucleic acid chains) helix structure
held together by hydrogen bonds between pairs of complementary bases

two strands are complementary to each

RNA

In secondary structure of RNA single stranded helics is present which sometimes foldsback
on itself.
RNA molecules are of three types and they perform different functions.
They are named as messenger RNA (m-RNA), ribosomal RNA (r-RNA) and transfer RNA
(t-RNA).
What products would be formed when a nucleotide from DNA containing thymine is hydrolysed?

When RNA is hydrolysed, there is no relationship among the quantities of different bases obtained. What
does this fact suggest about the structure of RNA?
 NUCLEIC ACIDS

Q. Find the hydrolysis product when a phosphodiester bonds of nucleotide

breaks :-
3
(1) 3′-OH- deoxyribose-5′- PO4
(2) 5′-OH- deoxyribose-3′- PO43
(3) 2′-OH- deoxyribose-2′- PO43
(4) 4′-OH- deoxyribose-2′- PO43

(Dinucleotide)
H

Me

isobutyl

Sec-butyl