Biomolecules INTRODUCTION A polyhydroxy compound that has an aldehyde or a ketone functional group, present either in free state or as a hemiacetal or hemiketal are called carbohydrate. Carbohydrates are substances having general formula C,(H,0),. PSA ACO Mel Nite ghd) UL Sd (i) Monosaccharides + A carbohydrate that cannot be hydrolysed to simpler compounds is called monosaccharide, 4 Monosaccharides which have six carbons are either aldohexoses or ketohexoses. Ex. Glucose, Fructose, Galactose ete. Aldoses: Monosaccharides containing aldehyde group are called aldoses. Ketoses: Monosaccharides containing ketonic group are called ketoses. i) Oligosaccharides 4 Carbohydrates that yield 2 to 10 monosaccharide units, on hydrolysis, are called oligosaccharides. % They are further classified as disaccharides, trisaccharides, tetrasaccharides, etc., depending upon the number of monosaccharides, they provide on hydrolysis. The two monosaccharides units obtained by hydrolysis ofa disaccharide may be same or different. Ex. Sucrose on hydrolysis gives one molecule each of glucose and fructose (iii) Polysaccharides © A carbohydrate that can be hydrolyzed to many monosaccharide units is called a polysaccharide. Ex: Starch, Cellulose, ete. Sugars and Non Sugars Both monosaccharides and oligosaccharides are crystalline solids, soluble in water and sweet in taste. These are collectively known as sugars, 4 Polysaccharides are amorphous, sparingly soluble in water and tasteless and are known as non-sugars. Reducing and Non Reducing Sugars ‘© The saccharides, that reduce Febling’s reagent, Tollen’s reagent, are called as reducing sugars ‘ All monosaccharides, whether aldose(or) ketose, are reducing sugars, Ex: Glucose, fructose, galactose MONOSACCHARIDES (1) Glucose (C,H,,0,) mannose, It acts as a reducing agent (reduces both Febling’s solution and ammonical silver nitrate solution). Physical properties + Glucose is sweet in taste and also optically active (dextro + Glucose shows mutarotation. Structure a n ony i ne NZ r noo) ron), Hor neon uf con chon CHOH Glucose aeD-Blucopyranose —p-D-elucopyranose 66%) (6%)Chemical Reactions of Glucose scncoa, I veal Grocock, Geom pea cee Ho l ae TEES? CHOMCHON.CHOH 1 Gon sort [222+ crromcnor,coon + C40 | sloconi aid red pot 10, ‘COOHKCHON, COOH + 0 SPT char cid slucosnone Cyclic Structure of Glucose The open chain structure of glucose proposed by Baeyer explained most of its properties, but it could not explain the following:- (@ Glucose does not give schiffs test and does not react with NaHSO, and, give hydrogensulphite addition product inspite of presence of -CHO group (ii) Pentaacetate of glucose does not react with NH,OH ‘group indicating absence of - CHO group 4 The glucose forms a six-membered ring in which -OH at C-5 is involved in ring formation. This explains the absence of -CHO group and also existence of glucose in two forms ie., a-D-(+)-Glucose and B-D-(+)-Glucose. These two cyclic forms exist in equilibrium with open chain structure. I ntc-on ntc_on u—}—on n—}—on HO}—H 0 = Ho}—8 41 on nt —on aH iH ‘OH 6 6 CH,on CH,0H c-D-(4)-Glucose Ho 3¢-0H = ttion = pot—n 0 u—44+—on ae CH,0H B-D-(+)-Glucose © The spontaneous change in specific rotations of an optically active compound is called mutarotation Mutarotation of Glucose G_ D(+)Glucose = eg. mix = P-D{+)glucose ) [eben ‘os a 4 Equilibrium mixture consists of 36% a-D(+) Glucose and 64% B-D(+) Glucose, this behaviour couldnt he explained by open chain stactre. ) Epimers & Epimers are a pair of diastereomers that differ only inthe configuration about a single carbon atom. Ex: Glucose and Mannose are C, epimers cHo cHo u—t—on o—{—# HO—,— H HO Salaam ton = Hn H—t—on =9—}—08 CHO CHLOH D-Glucose —Fig.: D-Mannose Anomers Anomers are epimers whose conformations differ only about cr For example, a-D(+) and p-D(+) glucose are anomers. a-D(-) and f-D() fructose are anomers. In glucose C, carbon is anomeric carbon and in fructose C, carbon is anomeric carbon. (2) Fructose % Ibis also known as a-Laevulose i.e. natural occurring compound is Iaevorotatory. $ It is pentahydroxy ketone and shows mutarotation like lucose. + Itis a reducing sugar, Structure cH,- on, | S20 onen, Ho eon wg-on }> ton eon tt la Gon don Gen ci radars sae Poston ‘traces SpeisHomon Spec Rettion Spi Rotion on ci)an reduce Fehling sol } and Tollen’s reagents, it is probably due to formation of an equilibrium between glucose, mannose and DISACCHARIDES Sucrose (Invert-sugar) C,,H,,0,, att, Aqueous solution of sucrose is dextrorotatory, its specifi rotation being + 66.5 © On hydrolysis with dilute acids sucrose yields an equimolar mixture of D(+)-glucose and D(-)-fructose: CyH a0, HO" 5 C,H 06+ CH i205 ‘Bucose”—fructone Since D(-)-fructose has a greater specific rotation than D(+)-glucose, the resulting mixture is laevorotatory. + Sucrose is not a reducing sugar. It does not form an oxime or an osazone, and does not undergo mutarotation. HOCH, 0 H\W HO/cHOH On Sucrose Fige Sucrose Maltose (Malt sugar) C,,H,,0,, 4 When itis hydrolysed with dilute acids or by the enzyme ‘maltase, maltose yields two molecules of D (+}-glucose. % Maltose is a reducing sugar, it forms an oxime and an osazone, and undergoes mutarotation. Lactose (Milk-sugar) C,,H.,0,, tis hydrolysed by dilute acids or by the enzyme lactase, to an equimolar mixture of D(+}glucose and D(+)-galactose. % Lactose is a redueing sugar. HOH,C D, HAL OH OW Ay HOH Figs Laltose (B-1, 4-glucosidic linkage) La NET Ce U3 Starch (C,H, ,0,) Ht,.0,), = Amylose (20%) (water soluble) Starch > Amylopectin (80%) (water insoluble) % Both amylose and amylopectin are composed of D-glucose units. @ The amylose molecule is made up of D-glucose unit joined by a-glycosidic linkages between C-1 of one glucose unit and C-4 of the next glucose unit. The number ‘of D-glucose units in amylose range from 60-300. ¢u.0n qo, CHon Lk DH fii OH HL 4 ° 04m u bu On a(1+4)Giycosidic linkage Fig.: Amylose + Amylopectin has a branched-chain structure. linkages between C-1 to one glucose unit and C-4 of the next glucose unit, These chains are in turn connected to each other by 1, 6-Linkages. Hon enon Ar it oon | HP as) Hon wow | cram HOH chou eu, Ath H Wi it ‘it mY oH HY OH ° ° ©. Hon On Hon al 4) Fige: Amylopectin Cellulose (C,H,,0,),, + It is a straight chain polysaccharide composed only of f-D-glucose units, which are joined by glycosidic linkage between Cl of one glucose unit and C4 of the next glucose unit, Tollen’s, Fehling’s and Benedict's Reagents: % Sugars which give positive tests with these reagents are known as reducing sugars and all the carbohydrates which contain a hemiacetal group give positive tests. © [ag(at,),J?+O11+(GheoseorFrciese)-+ Ag +Oridation(Gi) Benedict's reagent (they oxidise an aldose or ketose and give brick red precipitates of Cu,O Cu®* (complex )+ (Glucose or Fructose) + Cu,0 4+ Oxidation tone Steele alot Poe _ = Reducing sugar Non-reducing sugar Dis eon gt ofanother OHH 0, /OTR Sigar \p Nw Hemiaceta, RH Acetal R' or CH,OH or CH,OH (Gives(+ve)test) Penn (Gives (-veytest) All monosaccharides are reducing sugars Ex:- Glucose, fructose, triose, tetroses, pentoses & hexose lll the common disaccharides are reducing sugars ‘Table: Some important carbohydrates and their linkages 1 Carbo] Present monosa | Giycosidic Linkage Re hydrate echaride 2 bi T,_ [Glucose — [= 2._[ Fructose 3, [Sucrose [arDglucose & [Between C, of a-D gh Befructose cose 1 C, of :D fructose J [Lactose | BHD glucose & P-D [Between C, of galactose galactose to C, of glucose 3. |Matiose Two a-D glucose | Between C, of first units elucose units 1 C, of second glucose unit % |Swrch [Combination of [Amylose has C-C- JAmylose and | Glycosidic linkage. ‘Amylopectin | Amylopectin has C, - C, and C,-C, linkage 7, [Cellulose [polymer of (a) Bralycosidic B-D-glucose_ linkage Ee CaP EW aio Amino Acid ‘ Thebondbetween two amino acid moleculesis peptide bond ‘or’ amide bond, and the resultant is known as dipeptide’. except sucrose 4 All proteins are polymers of a-amino acids and on partial Ex :- maltose, lactose hydrolysis give peptides of varying molecular masses All polysaccharides are non reducing sugars which upon complete hydrolysis give a-amino acids. Ex:- starch ,glycogen dextrin Proteins #2, Peptides #0 5.4 — aminoacids ‘Table: Some important amino acids S.No |Name ame Amino) Three letter symbol | One letter code Side chain (R) Isoelectric point Neutral amino acids z Glycine Gy G A 60 2 ‘Alanine Ala A CH, 60 3. Valine* Val Vv (CH)),CH- 60 4 ‘Leucine* Leu L -H,C-CH-(CH,), 6.0 H,C-CH,-CH- 5. Isoleucine* Me 1 1 61 cH, Phenylalanine* Phe Fr =CH-C\H, or CHPh 33 Cysteine Os c ~CH,-SH mn Methionine* Met M ~CH,-CH,-S-CH, 38 “CH: 9. ‘Tryptophan* Tp wv 59 u 10. Serine Ser Ss ‘CHOW 37 1 Asparagine Asn ~CH,-CO-NH, 3A 12. Glutamine Gin ~CH,-CH,-CO-NH, 3.7‘CH-CH, 63 | 13 Threonine* Thr | T | I ee ms i Ol 37 14 | Tyrosine Tyr y cca! La a a 63 Is. Proline Pro Pp ie (tis complete structure) ___| Acidic amino acids - 16. | _ Aspartic a Asp D =CH,-COOH 30 17. | Glutamic acid Glu E i-CH,-COOH 32 Basic amino acids a 18, Lysine Lys K CHACH,,-NH, 98 19, “Arginine* Are R ~CH,-(CH),-NH-C-NH, 108 I | 20. Vistidine™ His W 76 necessarily be present fm our diet are called ‘ssential amin acids. (i) Essential amino acids: eg. (I)Leucine (2)Isoleucine (3) Lysine (ii) Non-essential amino acid () Alanine (2) Asparagine (3) Aspartic acid (4) Cysteine & Somebasicamino acids re lysine arginine andhistamine. 4 Some acidie amino acids are aspartie acid and glutamate Properties 4 Except glycine all other naturally occuring c-amino acids are optically active, since a-carbon is asymmetric. [L-amino acids are represented by writting the -NH, group fon the left hand side. 4 Zwitter ions: Due to the presence of an group in the same molecule, most of the amino-acids ‘are neutral and exist largely as dipolar or zwitter ions or dic and a basic inner salts in which proton from the carboxyl group has ‘been transferred to the amino group and thus a dipolar jon containing both a positive and a negative charge is formed. ve NH R—CH—COOH == R—CH—COO ‘Amino aid ‘iter Peptide linkage “Amino acid units are linked together by peptide —C—NH— linkage and form polypeptides. 4 Ina polypeptide structure free amino group (NHL) ie. N- terminal residue is written on the left hand side and the free carboxyl group on the right hand side ofthe chain. i IL i+ CH—C—NH—CH—COOH U.N—CH cH, 1H, alanine alycine alanine Figs: Alanylglycylalanine In the above structure -COOH group is C- terminal residue and -NH, group is N-terminal residue. Proteins These are high molecular mass complex, biopolymers of ‘amino acids.Classification of Proteins (On the basis of molecular structure: Fibrous Protein Ex. Keratin, myosin, collagen, ular Proteins: E.x. Insulin, albumin, thyog! antibodies, haemoglobin, fibrinogen etc Structure of Proteins Structure and shape of proteins can be studied at 4 different levels e e e e Primaty Secondary Tertiaty)Qiiaterniary Primary Structure * Primary structure is conformed by a single polypeptide chain in a linear manner. 2, Secondary Structure ‘* The conformation in which the polypeptide chains assume a long chain as a result of H-bonding is called secondary structure of protein. ‘© The H-bonds are present between hydrogen of amino group and oxygen atom of carboxylic acid group. © This structure is of two types é ° Helix” pePleated sheet (@ a-Helix: In the a- helix protein, a hydrogen bond is formed between the N-H group to the C=O group of the amino acid. Eg. Myosin, Keratin ete. (i B-Pleated sheet: Intermolecular H-bonds hold together the neighbouring polypeptide chains.Eg. Silk fibres. 3. Tertiary Structure ‘© Tertiary structure refers to its three dimensional structure, ice. folding and bonding of the long peptide chains. ‘© This structure is formed by 4 types of bonds ( Hydrogen bond (i) Hydrophobic bond (iii) lonic bond (iv) Disulphide bonds 4. Quaternary Structure When two or more polypeptide chains units are held together by forces other than covalent bonds (ic., not peptide and disulphide bonds), we get quatemary structure of protein. It is most stable structure. Ex . Haemoglobin, Denaturation of proteins When a protein in its native form is subjected to a physical change like change in temperature or pH, the hydrogen bonds are disturbed. As a result-globules unfold and helices ‘get uncoiled and protein loses its biological activity. This is called denaturation of proteins. During denaturation, 2” and 3° structure are destroyed but 1° structure remains intact, 4 Changing the pH denatures proteins because it changes, side chains. This disrupts the charges on many of electrostatic attractions and hydrogen bonds & The coagulation of egg white on boiling and curdling of milk caused by the bacteria present in milk are common examples of denaturation of protein. Hormones are molecules that act as intercellular messengers, ‘Some hormones are derived from amino acids. e.g thyroxine and adrenaline. Example: (1) Epinephrine or Adrenaline is a hormone that helps to control blood pressure and increases pulse rate. (2) Thyroxine is a hormone secreted by Thyroid. It regulates metabolism of lipids, proteins and carbohydrates. (3) Testosterone Regulates and stimulates male sex organs, Vitamins may be defined as a group of biomolecules which are required in small amounts for normal metabolic process and for the life, growth and health of human beings and animals. Classification of Vitamins The Vitamins are broadly classified into two catagories (® Water soluble vitamins : Vitamin B-complex and vitamin C are water soluble vitamins and must be supplied regularly in diet (i Fat soluble vitamins : These are oily substances and soluble in fats These are A,D,E and K. They are stored in liver and adipose (fat storing) tissues. Biotin (Vitamin H) : It is neither soluble in water nor in fats. Lack of particular vitamin causes a specific deficiency disease. Examples of some important vitamins and deficiency diseases are:- Vitamin A (Retinol): Xerophthalmia (hardening of comea of eye) night blindness and xerosis (drying of skin). ‘Vitamin B, (Thiamine): Beriberi (paralysis of legs and general weakness) loss of appetite * Vitamin D (Ergocaleiferol) (sun shine Vitamin): Rickets (deformation of bones) osteomalacia (soft bones and joint pain), * ‘Vitamin C is chemically known as ascorbic acid- Seurvy-NUCLEIC ACIDS % Nucleic acids are colourless, complex, amorphous compounds made up of three units: bases, sugar and phosphoric acid. Since nucleic acids are long chi polymers of nucleotides, so they are also called polynucleotides. Nucleic acids are of two types: (® Pentose nucleic acids or ribonucleic acids (R.N.A.) (ii) Deoxypentose nucleic acids or deoxyribonucleic acids (DNA) Nucleic acids can be hydrolysed in stages to nucleotides, nucleosides and phosphoric acid and ultimately to base and sugar, Nucleic acid —> Nucleotides -> Nucleosides + H,PO, Base + Sugar ‘Sugar: Two sugars are found to be present in nucleic acids) namely D-ribose in R.N.A. and 2-deoxyribose in D.N. Bases 4 Important purine bases are adenine and guanine; while pyrimidine bases are uracil, thymine and cytosine. 4 Adenine, guanine and cytosine are present in RNA as well as in DNA, while thymine is present only in DNA and uracil only in RNA Nucleoside: Each nucleoside consists of sugar molecule and a nitrogenous base. ‘The relationship can be shown as given below. Nucleic aci Nucleotide = nucleosides + phosphate many nucleotides ‘Nucleoside ~ sugar + nitrogenous base ‘Thus, nucleotide = phosphate + sugar + nitrogenous base Deoxyribose Nucleic-Acid(DNA) (a) Itis found in nucleus. (6) DNA is made up of 3 units- é ° ° Nitrogen base Deoxyribose (sugar) Phosphoric eid (H,PO)) o ° Pyrimidine Purine Structure of DNA Structure of DNA. 4 DNA has a double helix structure and is made up of two chains of polynucleotides. 4 DNA isa polymer of deoxynucteotides. 4 The two strands are joined by 3” > 5° phosphodiester bonds 4 Sugars and phosphates are alternately arranged 4 In both chains, in between A and T, 2 hydrogen bonds a ) are present, while in C and G, 3 H-bonds (C===G) are present. & Aalways attaches with T while C always attaches with G. Functions of DNA (i Self- replication or self - duplication (i) Protein synthesis The specific sequence of base pair in DNA represents coded information for the manufacture of specific proteins. (The major steps in the utilization of the sete) information can be represented as: pwa—2282 5 DNA Ribonucleic Acid (RNA) Ribonucleic acid is a polymer of purine and pyrimidine ribonucleotides linked by 3° > 5° phosphodiester bridges. RNA exists basically as a single-stranded molecule rather than as a double-stranded helical molecule, as does DNA.