Biomolecules
Biomolecules
Biochemistry is the branch of chemistry concerned withthe chemical reactions occurringin living organism. Thes
     chemical reactions in living organism involve chemical compoundscalled biomolecules. They are theibuilding blcck
                                  (CçHË00s)n +nH,0           H*
                                    Starch                 393 K,
                                                           2-3 atm
                                                                     nCgH1206
                                                                       Glucose
Physical Properties
   1. White crystalline solid
   2. Its M.P. is 419 K.
                              soluble in water.
hemical Properties
   1.   Reaction with HI :0n prolonged heating with HI, glucose gives
        atoms in a straight chain.                                    n-hexane indicating the presence of six carbon
                                                            Heat
                          CH,OH-(CHOH),CHO+14HI.                     CH3(CH,)4  CH3+ 6H,0+712
                                                                       n-Hexane
   2. Reaction with Hydroxyl Amine (NH2OH) : This
                                                  reaction shows the presence of one carbonyl group to form
        glucoxime.
                       CH,OH(CHOH),CHO + NH,OH                 ’     CH,OHCHOH)4CH =            NOH + H,0
                                                                        Glucoxime
  3. Oxidation with Conc. HNO3 :Glucose gives sacchric acid by oxidising primary alcoholic group
                                                                                                 (-CH,OH) and
        aldehydic group (CHO) both into -COOH group.
                                               Conc. HNO3
                            CH,OH- (CHOH),CHO             COOH(CHOH), COOH
                                                  3[0]                    Sacchric acid
  4. With Phenyl Hydrazine (CçHçNHNH2) :With smallamount of the reagent, glucose phenyl hydrazone is formed
                 CH,OH(CHOH),CHO + H,NNHçHs                ’ CH=NNHCGH^ +H,0
                                                              (CHOH)4
                                                               CH,OH
                                                 formed.
        With excess of reagent, glucosazone is
                                                Of CHEMISTRY Clas0 XII
                                          CHO                          CH= NNHC,H5
                                                     3cEH_NHNH,
                                          CHOH                          = NNHC,H5 + 2H,0 + NH + CoH5NH
                                         (CHOH),                       (CHOH)3
                                         CH,0H                          CH,OH
                                                                     Glucosazone
      5. With Br, Water : Glucose gets oxidised to form gluconic acld on
         the red colour of bromine water. It indicates the presence of an reaction with Br2 water. lt readily decolourises
         bromine water.                                                   aldehydic group. Pructose does not react with
                                            CHO                        COOH
                                                        Br, Water
                                           (HOH)4                     (CHOH)4
                                             CH,OH                     CH,OH
                                                                     Gluconic acld
      6. Acetylation :Glucose on acetylation with acetic anhydride gives
                                                                         glucose pentaacetate           confirming the presence of
         five-0H groups.
                             CHO                                        CHO
HO
H OH
                                                               -OH
                                                           CH,OH
                                                        D+}-Glucose
Dand L Designations of Monosaccharides
 The letters 'D' and '= before the name of any compound indicates the relative configuration of a particular stereoisomer.
 This refers to their relation with a particular isomer of gtyceraldehyde.
                                                        CHO                             CHO
                                                  H4 OH                        HO-H
                                                   CH,OH                                CH,OH
                                                (+}-Glyceraldehyde             (--Glyceraldehyde
  All those compounds which can be chemkcally correlated to (+) isomer of glyceraldehyde are said to have D-configuration
  whereas those which can be correlated to (-) isomer of glyceraldehyde are said to have L-configuration.
                                                                         CHO
                                                                                     H         -OH
                                                                                   HO          -H
                                                   CHO
                                                                                     H-oH
                                                   CH,OH                                  CH,OH
                                            D-{"}-Glyceraldehyde
                                                                                        D-(+}-Glucose
  It maybe remembered that 'D' and 'L have no relation with the optical activity of the compound.
                                                                                                        BIOMOLECULES     335
bjectionsAgainst Open Chain Structure of Glucose
   1. Glucoseeven though contains -CHO group but does not react                  with NaHSO3, ammonia and Schiff's reagent.
      The pentaacetate of glucose does not react with hydroxyl amine indicating the absence of
   3. Glucose exists in two stereoisomeric forms, a-D-glucose and p-D- glucose with different free-CHO
                                                                                               melting pointsgroup.
                                                                                                               and their
     methods of preparation.
       It does not give 2, 4-DNP dertvative.
                     Glucose
clic Structure of
 Theabove obbjections have been explained by the ring (cyclic) structure öf glucose. In the cyclic structure of glucose,
  -OHgroup at Cg and -CHO group at C combine to give a 6-membered ring (pyranose structure). These are called
scher Projection Formulae.
                         Hç-OH                              HC
                         HC-OH                              H2-OH                            H -0H
                                           H           HO
                                                              OH                                         HO
                                                                                          H
                                               ÖH         H
                                                                                               OH
                                    a-D-{-)-Fructofuranose                                B-D---Fructofuranose
sacharides
                        C1zHz20,,)
Lose (Cane Sugar,
   obtainedI commercially from         cane sugar or sugar beets.
  ts
                gives equimolar mixture of            D-(+)-glucose and D-(-)-fructose.
                                           C2H2011 +H,0                  ’ CçHi20% + CçHy206
                                           Sucrose                            D{+)-Glucose          D-{-}Fructose
  Thesetwo monosaccharides are held together by gycosidic linkage.
                                           °CH,OH
                                               15
                                   H
                                               H
                                                                   H         HOH,Ç
                                                                                     2
                                               OH                                          H                 OH,
                                   OH
                                               3                                                         4
                                                                                                                 cH,OH
                                                                Glycosidic
                                               H          OH       linkage                OH
                                            a-D-(+)-Glucose                       B-D{--Fructose
                                                           Haworth projection formula of sucrose
nvert Sugar                                                                                                                        of
                 sucrose    upon   hydrolysis  yields dextrorotatory  glucose and laevorotatory fructose. The dextrorotation
 Dextrorotatory                                                                                                      hydrolysis, the
             52.59) is less  than the laevorotation   of fructose (-92.4°) so the mixture is laevorotatory. Upon
 glucose (+
                                                        (-). Hence, the product is known as invert sugar.
 sign of rotation changes from dextro (+) to laevo
Maltose (Malt Sugar, C12Hz2011)                                           unit (1) is linked to C, of another glucose unit
                                                                                                                           (II). It is
                         a-D-glucose    units in which   C of one glucose
 Itis composed oftwo                                       produced   at C of the second glucose unit in
                                                                                                           solution.
                            free aldehydic  group   can be
 areducing sugar as the
                                   SCH,OH                                        SCH,OH
                                                                             H                               H
                              H                                                      H
                                                                                     OH
                                       OH                                                                    OH
                                                                                  N3
                              OH
                                                                                     H              OH
                                       H             OH
                                                                                  (1)
                                        (0                               a-D-Glucose (Reducing glucose unit)
                                                         glucose unit)
                               a-D-Glucose (Non-reducing
                                                  Haworth projection formula
  Polysaccharides
     Polysaccharides are composed of large number of monosaccharide units joined together by glycosidic linkages.
  Starch [Amylum, (CçHo0s)n
    It occurs as microscopic granules in the roots, tubers and seeds of plants.
    ltis dietary source for human beings. It is a polymer of a-glucose and consists of amylose and amylopectin.
                                             CH,OH                                             cH,OH
                                                                           H                                              H
                                                                                                  H
                                                 OH                                               OH
                                                  3                2                                3           2
                                                 H             OH
                                                                           Bycosidiclinkage
                                                                                                                OH
                                                                               Amylose
   Amylose is water soluble component and makes 15-20% of starch. It consists of 200-1000 a-D-(+)glucose units held by
   C-C4 glycosidic linkage. It is a long unbranched chain.
                          CH,OH                    CH,OH
                          H                           H
                                                          H
                              OH                          OH
                                                                                     -a-link
                              H    OH                     H            OH
                                                                                     -C-çlink
                                        CH,OH                                  CH                                 CH,OH
                                                                       H
                                                                               H
                                        OH                                                                        H
                                                     H                         OH                                                  1
                                                                                                                  OH          H
                                        H            OH                        H         OH
                                                          a-link                                                  H           OH
                                                                                                a-link
    Water insoluble amylopectin has a                         Amylopectin
                                      structure similar to that of amylose with the
  are branched. It constitutes about 80-85%   of starch.                           eexception that in amylopectin thechains
Cellulose
  It is astraight chain polysaccharidee
   by glycosidic linkage between C of exclusively occursin
                                       one glucose unit and plants. It is composed only of                                             whicharejoined
                                                             C, of the next
                                                                                                glucose unit. B-D-glucose units
                                                                            HOH,
                                                                            H
                                                                                    OH         H
                                                    HOH,C
                                                    H
                                                                                    H          OH
OH H
                                 HOH,C
                                                            H          OH
                                                                                          B-linkage
OH H
                                               OH
                                                           Cellulose
Giycogen
                                                          starch. It occurs in liver. muscles and brain and is broken down
 tis an energy storage molecule and is also called animal
 into glucose. It is also found in yeast and fungi.
Inportance of Carbohydrates
                                                     the        functioning of living organisms.
   1. They act as store house of chemical energy for
                                               acids.
   2. They are essential components of nucleic
                                          cells and   are essential component of ATP.
    3. They form structural materials for
                                                          PROTEINS
                                                                                                                             15% of
                                                 acids with molar mass ranging           up to more than 50 million. About
 Chemically   proteins are the polymers of amino
                                                                                                         on
 the human body weight is protein.              (-CO0H) function groups. Only a-amino acids are obtained
                                   and carboxyl
 Amino acids contain amino (-NH,)
 hydrolysis of proteins.                         R-CH-C0OH
                                                                 NH2
                                                      a-amino acid (R=side chain)
                                             pENH                                   ONH
                                                                                 Zwitter ion
    This structure is also known as internal salt. In this form, amino acids show amphoteric behaviour. At a
    dipolar ion does not migrate to any electrodes passing electric current through their solution. This is called              certain pH
    point ofthat amino acid. Each amino acid has acharacteristicisoelectric point. For neutralamino
                                                                                                                 acids.isoeleIcsotreileandcptrpioeint
    is slightly lessthan pH7(Glycine =6.1). For acidic amino acids, it lies between pH 3.0-5.4 (aspartic acid =3.0)
     basic amino acid, it lies between pH 7.6-10.8 (lysine =9.7). At isoelectric point, an amino acid has the least
    water and this property is used in the separation of different amino acids obtained from the hydrolysis of protein. in           solublity
Peptides and Proteins
    a-amino acids are connected to each other by peptide bond or peptide linkage ( CONHH. TheNH, groun af.
    amino acid molecule combines with the-cóoH group of another amino acid molecule to form a peptide bondne
    water molecule is given out.
                   H,NCH, -C0OH + H,N-CH-C0OH
                           Glycine                                    -H,0
                                                                             H,N -CH, co-NH CH-coOH
                                                       Alanine                               Peptide linkage
                                                                                             (Glycylalanine)
   The above peptide linkage is dipeptide.
   When a large number of amino acids (more than ten) are combined, the products are called polypeptides. Apolypeptide
   with more than hundred amino acid residues having molecular mass higher than 10000 u is called a protein.
Classification of Proteins
On the Basis of Molecular Structure
  It is of two types:
1. Fibrous Proteins
   These types of proteins consist of linear thread like molecules which
   tend to li side by side to form fibres. The molecules are held together
   at many points by hydrogen bonds or disulphide bonds. They are
   usually insoluble in water. For example, keratin in skin, hair, nails and
   wool; collagen in tendons; fibroin in silk; myosin in muscles etc.
2. Globular Proteins
   In thistype of proteins, the molecules are folded together into compact                                         H
                                                                                           (a)
                                                                                                                                 (b)
Structure of Proteins                                                                Fig. 10.1. a-helix
                                                                                                        structure of proteins
   The protein's structure and shape can be usually studied at four different levels:
1. Primary Structure
   The sequence of amino acid residues in polypeptide or protein, is called primary structure. Any change in the primary
   structure creates a different protein.
                                                   R                          R"
                                                       U=0
                                                  H              R
  secondary Structure
             the                                                                                             BIOMOLECULES 341
   trefersto      shape in which along
   structure. a-helix                  polypeptide chain can
                    structure is a right handed helix, with 3.6 exist. They are found to exist in a-helix and B-pleated sheet
  byhydrogen bonding.                                           amino acid residues per turn and a
  inß-structure all peptide                                                                        13 member ring is formed
                            chains  are stretched out to
                                                         nearly maximum extension and Ithen laid side by side
  together by intermolecular
                               hydrogen bonds.                                                                 which are held
RH RCH RCH
                                                          HCR
                                                                         HCR             HCR
                                                          C=0-4 =0.4A
                                                          HCR          HCR             HCR
3. Tertiary Structure
 This structure represents overall folding of the polypeptide chains ie, further folding of the secondary structure. Fibrous
 and globular structures arise due to tertiary structure.
 Secondary and tertiary structures of proteins are stabilised by hydrogen bonds, disulphide linkages, van der Waals' and
 electrostatic forces ofattraction. This structure also refers to overall three dimensional shape of a protein.
                                               Tertiary
                                                                                               Quaternary
                        Secondary                                                                structure
            Primary                           structure
            structure    structure
                                                                           (two sub-units of two types in quaternary structure)
                          Diagrammatic representation of protein structure
               Fig. 10.3.
                         1. Primary           2. Secondary
                            structure                                      3. Tertiary                4. Quatermary
                                                  structure                   structure                  structure
                                                         N                      R groups
                                                                                Haeme group
                              Fig. 10.4. Primary, secondary, tertiary and quaternary
                                                                                     structures of haemoglobin
4. Quaternary Structure
   Many proteins exist as stable and
   The overall structure of a proteinordered, non-covalent aggregates of more than one polypeptide chain (called subunits).
                                      arising from the spatial arrangement of these subunits
   called its quaternary structure.                                                          with respect to each other is
Denaturation of Proteins
 The protein with a unique three
                                     dimensional structure found in living system showing biological activity is a
  native protein. When this native protein   is                                                                         called
  are disturbed. So that globules unfold and subjected to physical change like temperature, pH etc., the hydrogen bonds
                                                helix gets uncoiled. Thus, protein loses its
  denaturation of protein. During this, 2° and 3° structures                                 biological activity, This is called
                                                               are destroyed but 1° structure remains
  coagulation of egg while on boiling, curdling of milk.                                                 intact. For example,
                                                               ENZYMES
   Enzymes are biological catalysts and catalyse the
                                                       biochemical reactions. Almost all enzymes are globular proteins
   Enzymes show specificity for both, the reaction and the substrate.
   For example:                               Ci2tlg2011
                                                               Maltose
                                                                           2C,H,206
                                                Maltose                      Glucose
Mechanism
 They act as catalysts by lowering the   activation energy. They are needed
   enzyme, the degree of specificity shown for the substrates can vary widely. only in small quantity. Depending unon the
                                                              HORMONES
  Hormones function as chemical messengers in the body. They are produced in the endocrine glands and
                                                                                                                        tralt the
   organs and tissues inthe bloodstream. Chemicallythey may be steroids,(eg, estrogenand androgen),
                                                                                                                  .polypeptides
   insulin and endorphins) or amino acid derivatives (eg. epinephrine and norepinephrine). Hormones affect growth (eg
                                                                                                                   and
 welopment,   metabolism, sexual functions and                                      BIOMOLECULES 343
     glucosein the
 yelof                blood. Steroid hormones reproduction.  They also affect
                                               regulate tissue growth and moods. Insulin and glucagon  regulate the
        andadrenal cortex.
enads                                                                                 reproductive processes
                                                                                               and are secreted by
                                                             VITAMINS
             compounds are required in small amounts in the diets of
        onganic
 hese
reproduction. Most of them cannot be                                   animals in order to ensure healthy growth and
                                     synthesized in our body but plants can synthesize almost all of them.
assfication of Vitamins
 1.fatsoluble vitamins : Vitamins A, D, Eand Kare fat soluble and water
Jiver.
                                                                        insoluble. They              are stored in adipose tissue and
 2. Water soluble vitamins : Vitamins of Bgroup and vitamin Care water soluble. They cannot be stored in the body
(exceptvitaminB2) anddhence, their in take        be should regular.
                        Table 10.1 Some important vitamins, their sources and their
                                                                                       deficiency diseases.
 S. No.           Vitamins
                                                         Sources                                   Deficiency Diseases
   1        Vitamin-A               Fish liver oil,carrots, butter and milk          Xerophthalmia (hardening of cornea of eyes).
                                                                                     night blindness
   2        Vitamin-B1              Yeast, milk, green vegetables, cereals           Beri-beri (loss of appetite, retarded growth)
            (Thiamine)
   3        Vitamin-B2              Milk, egg white, liver, kidney                   Cheilosis (fissuring at corners of mouth
            (Riboflavin)                                                             and lips), digestive disorders and burning
                                                                                     sensation of the skin
    8.       Vitamin-E               Vegetable oils like wheat germ oil, sunflower   Sterility, increased fergility of RBCS and
                                     oil, etc.                                       muscular weakness
             (Tocopherol)
       9.    Vitamin-K
                                     Green leafy vegetables, cereals                 Increased blood clotting time haemmorhage
             (Phylloquinone)
    10.      Vitamin-H (Biotin)      Yeast, liver, kidney and milk                   Dermatitis, loss of hair, paralysis
 Avitamingses : Multiple deficiencies caused by lack of more than one vitamin are very common in human beings. This
 Condition of vitamins deficiency is called avitaminoses.
 Hypervitaminoses : The condition of excess intake of vitamins is known as hypervitaminoses
                                                         NUCLEIC ACIDS
  The nuclee of the cell transmits the inherent characters  of an individual from one generation to the next. This transmis
                                                     consists of chromosomes which are made up of
                        called heredity. The nucleus                                                   proteins and nucleic
  sion of characters is
                                                                    and Ribonucleic Acid(BNA)
  acids. Nucleic acids are oftwo types: Deoxyribonucielc Acid (DNA)
       The repeating unit                                                                         they are                         regarded
      tides. A nucleotide (monomeric
                                        unit) of nucleic acids are called nucleotides. Therefore,                                              as
                          is consisted of :
         1. Anitrogenous base (nitrogen containing
                                                       heterocyclic
                                                                                 NH2                                                         NH2
                                                                                                                                                    polynuces.
            base).
         2. Apentose sugar.
        3. Aphosphate group.
     1.A Ntrogenous Base: There are two types of
     base known as purines and pyrimidines.      nitrogenous                                                             ADENINE (A)
                                                                                                                H
     ()) Purines : Two purines found in nucleic acids are
                                                                                      HN                                                HN
     adenine (A) and guanine (G).
     (0) Pyrimidines : Three pyrimidines in nucleic acids are                                                                     HzN
     uracil (U). thymine (T) and cytosine (C).                               HZN                                         GUANINE (G)
                                                                                                                                                          H
      DNAcontains A, G, T and Cbut RNA contains A, G, Uand C.                          Fig.10.5. Structure of purines : adenine and guanine
NH2
                                                                                     CH3
                                  HN                            HN
                                                                       H                                    H
                                   URACIL (U)                     THYMINE (T)                       CrTOSINE (C)
                               (occurs in onty RNA)           (occurs in only DNA)         (ocCurs in both DNA and RNA)
"çH,OHO OH CH,OMO OH
                                                 H
                                                                                           H
2 2
                                                OH                                             OH           OH
                                           B-2-deoxyD-ibose
                                                                                               B{DH-ibose
   2. A
      pentose Sugar :There are two types of sugarspresent in the nucleic acids RNA contains B-D-ribose but in DNA, there
   is B-D-2-deoxyribose.
   3. A
      phosphate Group : They are responsible for the linkage in nucleic acid polymers.
0- P 0
  called melting temperature (Tm).                                     Fig. 10.8. The double a-helix structure of DNA. The two nucleotide
                                                                        strands are held together by specific hydrogen bonding between
   DNA acts as acarrier of genetic information from parents          bases. The numerals 5', 3' indicate that the free hydroxyl groups of the
   to offsprings and is involved in synthesis of RNA.                 terminal deoxyribose units are present at 5', 3' positions respectively