Contemporary Biochemistry plays a crucial role in the Medical field, be it A lecture note on Medical biochemistry integrates and summarizes the
I The science of biochemistry The ultimate goal of biochemistry is to explain all life processes in molecular detail Because life processes are performed
These seven volumes of Lecture Notes represent a yearlong effort on the part of the Kaplan Medicalfacultyto update our curriculum to reflectthe
The series consists of 22 multimedia lectures, which can be used together as a complete introductory course, or separately to learn a single topic Below you
Biochemistry, as the name implies, is the chemistry of living organisms It has its origin in chemistry and biology It tries to explain life processes at
Definition The science that is concerned with the structures, interactions, and transformations of biological molecules The chemistry of life
notes the same way For each topic (corresponding to about a chapter in most texts) write down a short summary of the really important concepts
Biochemistry is the study of the chemistry of cells and organisms Thus it is concerned with the types of molecules found in biological systems,
Biochemistry describes in molecular terms the struc- tures, mechanisms, and chemical (Note that the hydrogen atoms are omitted from the ball-and-
Biochemistry pathways: information (molecular biology) versus Structural (chemistry); Living versus nonliving ?Note that the scale is logarithmic
INTRODUCTION TO BIOCHEMISTRYDefinitionThe science that is concerned with the structures, interactions, and transformations ofbiological molecules.The chemistry of lifeBiochemistry can be subdivided three principal areasiStructural chemistryiMetabolismiThe chemistry of processes and substances that store and transmit biological information(molecular genetics)Biochemistry and LifeThe cell is the fundamental unit of lifeiProkaryotes and eukaryotesiEukaryotic cellsianimal cellsiplant cells (chloroplasts and cell walls)Cells are composed of:iSmall moleculesiMacromoleculesiOrganellesExpect for water, most of the molecules found in the cell are macromolecules, can be classifiedinto four different categories:iLipidsiCarbohydratesiProteinsiNucleic acidsLipids are primarily hydrocarbon structures
Carbohydrates, like lipids, contain a carbon backbone, but theyalso contain many polar hydroxyl (-OH) groups and thereforevery soluble in water.
Proteins are the most complex macromolecules in the cell.They are composed of linear polymers called polypeptides, which contain amino acidsconnected by peptide bondsEach amino acid contains a central carbon atom attached to four substituentsoA carboxyl groupoAn amino groupoA hydrogenatomoAn R groupNucleic acids are the large macromolecules in the cells.They are very long linear polymers, called polynucleotides, composed of nucleotidesA nucleotide contains:iA five-carbon sugar moleculesiOne or more phosphate groupsiA nitrogenous baseiDNA: A, T, G, CiRNA: A, U, G,CDNA Contain Four BasesRNA
The Double HelixBiochemical EnergyAll cellular functions re quire energy.The most-important chemical form of energy in most cells is ATP, adenosine 5"-triphosphate.ATP ADP + PiMost ATP synthesis occurs in chloroplasts and mitochondriaADT and ATPStructures
CARBOHYDRATESOccurrencesCarbohydrates are the most abundant organic compounds in the plant world.They act asstorehouses of chemical energy (glucose, starch, glycogen); are the components ofsupportivestructures in plants(cellulose), crustacean shells (chitin) and connective tissues in animals(acidic polysaccharides) and are essential components of nucleic acids (D-ribose and 2-deoxy-D-ribose).Carbohydrates make up about three fourths of the dry weight ofplants.The Nature of CarbohydratesCarbohydrates are compounds of great importance in both the biological and commercial worldThey are used as a source of energy in all organisms and as structural materials in membranes,cell walls and the exoskeletons of many arthropods.Hydrates of carbon.All carbohydratescontain the elements carbon (C), hydrogen (H) and oxygen (O) with the hydrogen and oxygenbeing present in a 2 : 1 ratioCarbohydrates are usually defined asPolyhydroxy aldehydes orketones, or substances that hydrolyze to yieldpolyhydroxyaldehydesor ketones". (0r)Aldehyde or Ketone derivatives of polyhydroxy alcoholsCarbohydrates are aldehyde or ketone compounds with multiple hydroxyl groupsGeneral molecular formula Cn (H2O)nThe term -carbohydrate comes from the observation that when you heat sugars, you getcarbon and water (hence, hydrate of carbon).Functions of carbohydratesMain sources of ENERGY in body (4kcal/g)-RBCs and Brain cells have an absolute requirement ofcarbohydrates-Storage form of energy (starch and glycogen)-Excess carbohydrate is converted to fat.-Glycoproteins and glycolipids are components of cell membranes and receptors.-Structural basis of many organisms.e.g. Cellulose in plants,-exoskeleton of insects, cell wall of microbes,-Mucopolysaccharidesand ground substance in higherorganisms.
MONOSACCHARIDESDef : They are the simplest carbohydrate unites which cannot be hydrolysed to a simpler formThey are classified into a) simplemonosaccharides b) derivedmonosaccharidesSimple monosaccharidessub classified according to1-The number of carbon atoms present in their molecule and,2-The type of carbonyl group they contain.Derived monosaccharidesinclude the derivatives of simplemonosaccharides such asoxidation products, reduction products, substitution products and esters
Accordingtothenumberofcarbonatoms(n):Ifsugarcontains3carbons→ it'scalledtriose,4c→tetroses5c→ pentose6c→ hexose7c→heptoses
MONOSACCHARIDE STRUCTURESThe simplest monosaccharide that possesses a hydroxyl group and a carbonyl group with anasymmetric carbon atom is the aldotriose-glyceraldehyde.( Referenc e carbohydrate)(Acarbon is said to be asymmetric if four different groups or atoms are attached to it. The carbonis also called as a chiral center).Glyceraldehyde is considered as a reference compound and itexists in two optically active forms, D and L.A chiral object cannot be superimposed on itsmirror image.A chiral carbon (Asymmetric carbon) is one that has four different groupsattached to it.
An aldehyde or ketone can react with an alcohol in a 1:1 ratio to yield a hemiacetalor hemiketal, respectively, creating a new chiral center at the carbonyl carbonTwo types of ring structures are possible, the five-membered furanose and the six memberedpyranose ring if the carbonyl group interact with hydroxyl group. These names are derivedfrom the parent compounds 'furan' and 'pyran'.The most common ring structure foraldohexoses is the pyranose ring structure that involves the first carbonyl carbon and thehydroxyl group attached to the fifth carbon.The furanose ring structure is formed by interactionof carbonyl carbon with the hydroxyl group attached to the fourth carbon.This furanose formis less stable than the pyranose structure and is not very common among Aldohexose
Six membered pyranose ringFive membered furanose ringIsomerismIsomers are different compounds that have the same molecularformula. Different compoundsmeans that they have different physical properties (melting point, boiling point etc.). They mayalso have very different chemical properties depending on the type of isomerism present.It wascoined by J.J. Berzelius for different compounds with same molecular formula
Structural isomers, in which the atoms are joined in a different order, so that they havedifferent structural formulaeTypes of structural isomerismChain isomerismThese isomers arise because ofthe possibility of branching in carbon chains. For example,there are two isomers of butane, C4H10. In one of them, the carbon atoms lie in a "straightchain" whereas in the other the chain is branched.
Position isomerismIn position isomerism,the basic carbon skeleton remains unchanged, but important groups aremoved around on that skeleton.
Functional IsomersD-glucose and D-fructose differ in the position of carbonyl group (aldehyde and ketone group).These two compounds are functionalisomer
Stereoisomerism or constitutional isomersAnother type of isomerism exhibited by compounds possessing asymmetric carbon atom likemonosaccharides, is stereoisomerism. These stereoisomers differ in the spatial arrangement ofatoms or groups.There are two types of stereoisomerisms-geometrical and optical isomerism.
Geometric IsomerismGeometric isomers(also calledcis/trans isomers) are a type of stereoisomer resulting from adouble bond or a ring structure. The double bond or ringin the structure means that not allbonds are free to rotate, giving rise to geometric isomers whose shapes cannot interconvert.Geometrical isomerism is not noticed among carbohydrates.Optical isomerismOptical isomers differ in the arrangement of atomsaround anasymmetric carbon atom. The number of possible opticalisomers can be calculated using the formula 2n wheren=number of asymmetric carbon atoms. For example,glucose contains four asymmetric carbon atoms and thepossible optical isomers of glucose are 24 = 16. Opticalisomers are named like this because of their effect on planepolarised light.EnantiomersEnantiomers are non-superimposable mirror images of each other.They differ in the ability torotate the plane polarized light.A solution of one enantiomer rotates the plane of such light tothe right, and a solution of the other to the left.D-glucose and L-glucose are examples ofenantiomers.
EpimersEpimers are monosaccharides differing inconfiguration around a single carbon atom other thanthe carbonyl carbon. e.g. Mannose and glucose are epimers with respect to carbon 2. Galactoseand glucose are epimers with respect to carbon 4.
D-Galactose is an epimer of D-glucose because the two sugars differ only in the configurationatC-4.D-Mannose is an epimer of D-glucose because the two sugars differ only in theconfiguration atC-2.AnomersWhen a molecule such as glucose converts to a cyclic form, it generates a new chiral centreatC-1.The carbon atom that generates the new chiral centre (C-1) is called the anomeric carbon.Anomers are special cases-they are epimers that differ in configuration only at the anomericcarbonFor example, α-D-glucose and β-D-glucose are AnomersThe α form has the anomericOHgroup atC-1on theopposite side of the ring from theCH2OHgroup atC-5.The β form has the anomericOHgroup on the same sideastheCH2OHDiastereomersDiastereomers are stereoisomers that are not mirror images of each other. D-glucose, D-mannose, D-galactose and other members of aldohexose are diastereoisomers.Stereoisomers with two or more stereocenters can bediastereomers. It is sometimes difficultto determine whether or not two molecules are diastereomers.
Optical activityMolecules that are chiral can rotate the plane of polarized light. The property of rotating theplane of polarized light is called optical activity, A ray of ordinary light vibrates in all directionsat right angles to the direction in which the ray is travelling. When this light is passed througha Nicol prism, the emerged light vibrates in only one direction and such light is called as a'plane polarized lightWhen a beam of plane polarized light is passed through a sugar solution, that is optically active,the plane-polarized light will be rotated either to the right (clockwise ) or t o the left(anticlockwise ). Whe n the plane polar ized light is rotated to the right, the compound isdextrorotatory and is written as (+). If the plane polarized light is rotated to the left, thecompound is levorotatory (-)
MutarotationMutarotation is a term given to thechange in the observed optical rotation of a substance withtime. Glucose, for example, can be obtained in either its a or b-pyranose form. The two formshave different physical properties such as melting point and optical rotation.When either formis dissolved in water, its initial rotation changes with time. Eventually both solutions have thesame rotation.In Glucose solution, 2/3 of sugar exist as β form,& 1/3 as α form.Interconversion of α & β forms is called MUTA ROTATIONMutarotation of D-Glucose
OligosaccharidesThese consist of 2 and up to 10 molecules of simple sugars and are hydrolysable. They are subclassified into di-, tri-andtetrasaccharides etc..., according to the number of molecules ofsimple sugars they yield on hydrolysisDisaccharidesDisaccharides are sugars composed of two monosaccharides covalently bonded together by aglycosidic linkage.Themostabundantdisaccharidesaresucrose,lactoseandmaltose.ThedisaccharidescanbeclassifiedintohomodisaccharidesandheterodisaccharidesA)Homodisaccharides:areformedofthesamemonosaccharideunitsmaltose,isomaltose,cellobiose andtrehaloseB)Heterodisaccharides:areformedofdifferentmonosaccharideandinclude:sucrose,lactoseMaltose, also known as malt sugar, is formed from two glucose moleculesLactose, or milk sugar, is a disaccharide formed when the monosaccharides glucose andgalactose are joinedSucrose is common household sugar and is formed when the monosaccharides glucose andfructose bondMALTOSE = GLUCOSE + GLUCOSELACTOSE = GLUCOSE + GALACTOSESUCROSE = GLUCOSE + FRUCTOSELactose:It is formed ofβ-galactoseandα-glucose linked byβ-1,4-glucosidic linkageContain free anomeric carbon so reducing sugarLactose is a reducing disaccharide found only in milk.It is made up of galactose at the non-reducing end and glucose at the reducing end.
Maltose (malt sugar):Maltose is a disaccharide made up of two glucose residue joined by aglycosidic linkagebetween C-1 of one glucose residue and C-4 of the other.The anomeric carbon atom of thesecond glucose is free and therefore maltose is a reducing sugar.
Sucrose, a sugar of commercial importance, is widely distributed in higher plants.Sugarcaneand sugar beet are the sole commercial sources.It is made up of glucose and fructose.Theanomeric carbon atom of glucose (C-1) and fructose(C-2) are involved in linkage and istherefore a non-reducing disaccharide.Sucrose is a major intermediate product ofphotosynthesis and it is the principal form in which sugar is transported from the leaves to otherportions of plants via their vascularsystems.Invert sugarThe hydrolysis of sucrose when followed Polarimetrically the optical rotation changes frompositive (dextro-) to negati ve (levo-).The dextrorotatory sucrose on hydrolysis yieldlevorotatory mixture of glucose and fructose.The levorotaion is due to the presence of fructose
which is by itself more levorotatory (-92) t han dextrorototar y gluc ose (+52.2).Thisphenomenon is called inversion and the mixture of glucose and fructose is called invert sugar.This reaction is catalysed by the enzyme invertase.Invert sugar is sweeter than sucrose.Honeycontains plenty of invert sugar and therefore is very sweet.PolysaccharidesPolysaccharides are large polymers of the monosaccharides.Unlike monosaccharides anddisaccharides, polysaccharidesare either insoluble or form colloidal suspensions.Thepolysaccharides found in nature either serve a structural function (structural polysaccharides)or play a role as a stored form of energy (storage polysaccharides).Storage polysaccharides (digestiblepolysaccharides)The principal storage polysaccharides are STARCH AND GLYCOGEN.Starch is a polymerof alpha glucose and is, in fact, a mixture oftwo different polysaccharides-AMYLOSE ANDAMYLOPECTINStarchThe principal food-reserve polysaccharide inthe plant kingdom is starch.It forms the majorsource of carbohydrate in the human diet.Starch has been found in some protozoa, bacteriaand algae. But the major source is plants where it occurs in the seeds, fruits, leaves, tubers andbulbs in varying amount from a few percent to over 74%.Starch is an alpha-glucan that hasstructurally distinct components called amylose and amylopectin.A third component referredas the intermediate fraction has also been identified in some starches.Starch molecules areorganized into quasicrystalline macromolecular aggregates called granules.The shape of thegranules are characteristics of the source of the starch.The two components, amylose andamylopectin, vary in amount among the different sources from less than 2% of amylose inwaxy rice or waxy maize to about 80% amylose in amylomaize.The majority of starchescontain 15 to 35% of amylose.
Amylose is formed by a series of condensation reactions that bond alpha glucose moleculestogether into a long chain forming many glycosidic bondsAmylose is made up of α D-glucose units linked mostly in a linear way by α 1-4 linkages
It has a molecular weight of 150,000 to 1,000,000 depending on itsbiological origin.It consistsof a mixture of linearmolecules with limited, long-chainbranching involving α 1-6 Linkages.Amylose gives a characteristic blue color with iodine due to the ability of the iodine to occupya position in the interior of a helical coil of glucose unitsAmylopectinAmylopectinconsists of a straight chain of alpha glucose units with branch points occurring atapproximately every twelth glucose unit along the straight chain.The branch point"s form whencarbon 6 of a glucose molecule in the straight chain forms a glycosidic bondwith carbon 1 ofa glucose molecule positioned above the chain.
This highly branched amylopectin molecule is wrapped around the amylose to make up thefinal starch molecule.This large insoluble molecule with branch points that allow for easyaccess for enzymes when breaking down the molecule, makes starch an ideal food storagecompound.Amylopectin is a branched, water-insoluble polymer comprised of thousands of D-glucose residues.It contains 94-96% α 1-4 and 4-6% α 1-6 linkages.The molecular weight ofamylopectin is in the order of 107-108.The amylopectin molecule is 100-150 A in diameterand 1200-4000 A long.
InulinInulin is a non-digestible fructosyl oligosaccharide found naturally in more than 36000typesof plants.It is a storage polysaccharide found in onion, garlic, chicory, artichoke, asparagus,banana, wheat and rye.It consists of mainly, if not exclusively, of-2->1 fructosyl-fructoselinks.A starting glucose moiety can be present, but is not necessary.Inulin is a soluble fibrethat helps maintain normal bowel function, decreases constipation, lowers cholesterol andtriglycerides.It is used for fat replacement and fibre enrichment in processed foodsSTRUCTURAL POYSACCHARIDES(indigestible polysaccharides)
Cellulose is the most abundant organic substance found in nature.It is the principal constituentof cell walls in higher plants. It occurs in almost pure form (98%) in cotton fibres and toalesser extent in flax (80%), jute (60-70%), wood (40-50%) and cereal straws (30-43%).It islinear, unbranched homoglycan of 10,000 to 15,000 D-glucose units joined by β 1-4 linkagesThe structure of cellulose can be represented as a series of glucopyranose rings in the chairconformation.Pectin-It is in fruits of many plants. The constituent monosaccharide is ά-D-galactouronicacidChitin-Most abundant in nature after cellulose, found in fungi and anthropods. The constituentmonosaccharides are N-Acetyl-D-glucosamine. It is non-reducing sugarProperties of carbohydrateMonosaccharides1.Reaction with alcohol-The Glycosidic OH group of mutarotating sugars reacts withalcohol to form ά and β glycosides or acetals. Thus glucose form glucosides and fructosefrom fructosides2.Reaction with acetic anhydride-The Glycosidic and alcoholic OH group ofmonosaccharides and disaccharides react with acetylating agents to form acetate derivativescalled esters3.Oxidation with acids-Only the aldehydes group of sugar is oxidized to producemonocarboxylic acid with bromine water, while with nitric acid both aldoses and ketosesreact to form dicarboxylic acid4.Oxidation with metal hydroxides-Metal hydroxides like copper hydroxide oxidize freealdehydes or keto group of mutarotating monosaccharides and at the same time theythemselves reduce to free metalReducing sugar + Cu2+oxidized sugar + 2 Cu+2Cu++ 2OH-2Cu.OH Cu2O + H2OYellow RedThis sugar is active ingredient in Fehling"s, Benedict"s and Barfoed"s reagent
Reducing property of sugarsSugars are classified as either reducing or non-reducing depending upon the presence ofpotentially free aldehyde or keto groups.The reducing property is mainly due to the ability ofthese sugars to reduce metal ions such as copper or silver to form insoluble cuprous oxide,under alkaline conditionAny carbohydrate which is capable of being oxidized and causes the reduction of othersubstanceswithout having to be hydrolyzed first is known as reducing sugar.The aldehydegroup of aldoses is oxidized to carboxylic acid. This reducing property is the basis forqualitative (Fehling' s, Benedict 's, Barfoed' s test s) and quantita tive reactions.Allmonosaccharides are reducing. In the case of oligosaccharides, if the molecule possesses a freealdehyde or ketone group it belongs to reducing sugar (maltose and lactose).The carbohydrateswhich are unable to be oxidized and do not reduce other substances are known as non-reducingsugars. If the reducing groups are involved in the formation of glycosodic linkage. the sugarbelongs to the non-reducing group (trehalose, sucrose, raffinose and stachyose).The reasonthat sucrose is a non-reducing sugar is that it has no free aldehyde or keto group. Additionally,its anomeric carbon is not free and can"t easily open up its structure to react with othermolecules.Reaction with acidsMonosaccharides are generally stable to hot dilute mineral acids though ketoses are appreciablydecomposed by prolonged action.Heating a solution of hexoses in a strong non-oxidisingacidic conditions, hydroxyl methyl furfural is formed.The hydroxymethyl furfural from hexoseis usually oxidized further to other products.When phenolic compounds such as resorcinol,naphthol or anthroneare added, mixture of coloured compounds are formed.The Molisch testused for detecting carbohydrate in solution is based on this principle.When conc.H2SO4isadded slowly to a carbohydrate solution containing naphthol, a pink color is produced at thejunctureReaction with alkaliDilute alkaliSugars in weak alkaline solutions undergo isomerization to form 1,2-enediols followed by theformation of a mixtureof sugars.Strong alkaliUnder strong alkaline conditions sugar undergo caramelization reactions
CARBOHYDRATEFILL UP THE BLANKS1.Starch is classified under ________2.Isomerism is a common property due to the presence of_______ and structuralarrangement3.Cellulose is a polysaccharide made up of glucose and the linkages are ____4.Plant gums are ___5.Starch is a polymer of ______6.Amylopectin has branched chained ______ units7.___ is the sugar present in milk8.The storage polysaccharides of animal tissue is ________9.Isomerism and optical activity property of carbohydrate is due to ______10._____ is a non-reducing sugar11.The change in the optical activity of sugar solution is known as _____12.The carbon atom to which four different atoms or groups are attached is called _____carbon atom13.The plant gums are the Heteropolysaccharides containing several units of ______14.Gluconic acid is a _____ acid15.The group that confers sweet taste to glucose is ______16.Freshly prepared glucose solutionhas a specific rotation of _____17.The sugar used for silvering the mirror is ______18.Fructose is the hydrolytic product of ________19._______ is a non-reducing disaccharide sugar20.The reagent used to form osazone with sugars is __21.Carbohydrates consists of ______ elements in the ratio 1:2:122.The general formula of monosaccharide is _____23.Galactose is ___ type of monosaccharide24.Oligosaccharides on hydrolysis give _____ number of monosaccharides25.The monosaccharide glucose has got __ functional group26.Themonosaccharide having keto group is known as _____27The isomers having similar molecular formula but different structural formula is calledas ___28Stereoisomers are grouped into ______ and _________29Number of optical isomers of the compound depends on number of ________30In a carbohydrate, If H is in the left and OH is on the right, It is designated by_____31Number of optical isomers present in glucose is ______32If the compound causes rotation of the polarized light to the left, it is said to be ______33In a mixture where optical activity is zero, such a mixture is called as _____34Mutarotation is undergone by ______ sugars only35Pyranose rings has got ______ type of linkage by oxygen atom36Hexoses are formed by hydrolysis of _______
DEFINITION1.Carbohydrate:Carbohydrates are chemically defined as polyhydroxy aldehydes orketones, their derivatives and their polymers. (or) Aldehyde or Ketone derivatives ofpolyhydroxy alcohols2.Monosaccharides :They are the simplest carbohydrate unites which cannot behydrolysed to a simpler form3.Oligosaccharides:They contain two to ten monosaccharide units joined by glycosidiclinkages that can be easily hydrolysed.4.Polysaccharides:They are high molecular weight polymers containing more than tenmonosaccharides.5.Chiral or Asymmetric carbon: A chiral carbon (Asymmetric carbon) is one that hasfour different groups attached to it.6.Isomers:Isomers are different compounds that have the same molecular formula7.Structural isomers: The atoms are joined in a different order, so that they have differentstructural formulae8.Functional Isomers: Differ in the position of carbonyl group D-glucose and D-fructose(aldehyde and ketone group). These two compounds are functional isomer9.Stereoisomerism or constitutional isomers:These stereoisomers differ in the spatialarrangement of atoms or groups10.Geometric Isomerism:Geometric isomers(also calledcis/trans isomers) are a type ofstereoisomer resulting from a double bond or a ring structure11.Optical isomerism:Optical isomers differ in the arrangement of atoms around anasymmetric carbon atom.12.Enantiomers:Enantiomers are non-superimposable mirror images of each other. D-glucose and L-glucose are examples of enantiomers.13.Epimers:Epimers are monosaccharides differing in configuration around a singlecarbon atom other than the carbonyl carbon.Mannose and glucose are epimers withrespect to carbon 2. Galactose and glucose are epimers with respect to carbon 414.Anomers:When a molecule such as glucose converts to a cyclic form, it generates a newchiral centre atC-1. The carbon atom that generates the new chiral centre (C-1) is calledthe anomericcarbon15.Homopolysachharides: When made from a single kind of monosaccharide. Eg starch,cellulose, inulin, glycogen, chitin16.Heteropolysaccharides: Theyare made up of more than one type of monosaccharides.Eg. Hemicellulose17.Diastereomers:Diastereomers arestereoisomers that are not mirror images of eachother. D-glucose, D-mannose, D-galactose18.Optical activity:Molecules that are chiral can rotate the plane of polarized light. Theproperty of rotating the plane of polarized light is called optical activity.19.Mutarotation:Mutarotation is the change in the optical rotation because of the changein the equilibrium between two anomers, when the corresponding stereocentersinterconvert.Inter conversion of α & β forms is called MUTA ROTATION
atoms. According to the rule of Le-bell Van"ts Hoff total number of optical isomers of acompound will be equal to 2nwhere n refersto number of asymmetric carbon atoms When abeam of light is allowed to pass through optically active solution, it can be rotated to the rightside ( Dextrorotatory-D( +)) and can be rotated to the left side( Levorotatory L (-)). Whenequal amounts of D and L type of isomers are present, the resulting mixture is optically inactivewhich is called as racemicmixture. When a monosaccharide is dissolved in water, the opticalrotating power of solution gradually changes until reaches a constant value which is referredto as Mutarotation7)Oxidation of hexose sugarMonosaccharides on oxidation under propercondition form different products eg. aldoses mayform monobasic acid or dibasic saccharic acid or monobasic uronic acid)Production of adonic acids: Aldoses when oxidized in the presence of bromine water, alAldehydegroup is converted into carboxyl groupCHO-(CHOH)4-CH2OH+HoBrCOOH-( CHOH)4-CH2OH + HBrGlucoseBromine waterGluconic acidKetoses are not readily oxidized by bromine waterB)Saccharicacid-The aldoses and ketoses undergo oxidation in the presence ofNitric acid to convert to carbonyl to form saccharic acid or dibasic acid. Eg. D-glucose, D-galactose and D-mannose are converted to D-glucoric acid, D-galactosaccharicacid and D-mannaric acidCHO-(CHOH)4-CH2OH + HNO3COOH-(CHOH)4-COOHGlucoseGlucoric acidWhile fructose is oxidized to tartaric acid, glycolic acid and trihydroxy glutaric acidCH2OH-C= O-(CHOH )3-CH2OH + HNO3 COOH-(CHOH)3-COOHFructoseTrihydroxy glutaric acidCOOH-(CHOH)2-COOHTartaric acidCH2OH-COOHGlycolicacid8)LactoseIt is composed of one molecule of glucose and on molecule of galactose. It is also called asmilk sugar. Lactose in human milk is 60% and in cow"s milk about 4.5%. It is formed inmammary glands. It is dextrorotatory. The ά and β forms has specific rotation of + 90 and+ 35 respectively and equimolar has + 52.5. It is less soluble in water, less sweet thansucrose. Upon the action of lactose, lactose yields glucose and galactose. It is a reducingsugar and has C1-C4Glycosidic linkage.So it reduces Fehling"s solution
sugar will exhibit mutarotation. Reducing sugar will have C1-C4 linkage while non-reducing sugar will have C1-C1 linkage. Reducing sugar are hemiacetal, do form osazoneswith phenyl hydrazines, form oximes with hydroxylamine. But non-reducing sugar areacetal, do not form osazone and oximes13)PolysaccharidesIt is formed by combination of many monosaccharides joined together by Glycosidiclinkages. They are also called as glycans. It is classified into Homoglycans (made up of onekind of monosaccharides) and Heteroglyca ns ( m ade up of diffe re nt kinds ofmonosaccharides) . Polysacchari des ar e gr ouped ba sed on thei r functiona l aspect,polysaccharides are classified into a) Nutrient/ digestible/storage-(Starch, glycogen andinulin) b) Structural/indigest ible (Ce llulose/ pectin/ chit in). The star ch is made up ofamylose and amylopectin and is reserve food materials for higher plants. Glycogen is themajor reserve food in animals and often called as animal starch. Cellulose is a long straightchain polysaccharides consisting of many β-D glucose units joined together by ά-1-4Glycosidic linkage. Hemi cellulose is made up of pentoses and hexoses. It is long chainedbut shorter chains with branched ones.ESSAY TYPES1.What are the main types of carbohydrates found in plants? Add a note on theirimportance in plant metabolismThe main type of carbohydrates found in plants are monosaccharides (triose, tetroses,pentoses, hexoses and heptoses), oligosaccharides (disaccharides and trisaccharides) andpolysaccharides (storage polysaccharides-starch, glycogen) and structural polysaccharides(cellulose, chitin). The metabolism of carbohydrates is of utmost importance to organismsindividually and collectively. Fundamentally all organic food stuffs are ultimately derivedfrom the synthesis of carbohydrates through photosynthesis. The catabolism ofcarbohydrates provides the major share of energy requirements for maintainenance of lifeand work function. Carbohydrates act as an energy reservoirs and serve architecturalfunction and are important constituents of nucleic acids. Plant contains higher amount ofcarbohydrates compared to animals. The carbohydrates present in grains, tubers, roots arereferred to as starch and forms a stable food.2)Describe the mechanism of biosynthesis and degradation of sucroseSynthesis of sucroseSynthesis of sucrose in plants may take place in three different ways1)From glucose-1-phosphate and fructose in the presence of the enzyme Phosphorylase.Eg. In bacteriaGlucose-1-Phosphate + Fructose Sucrose + Pi2)From UDPG (Urdi ne Di-phosphate glucose) and fruct ose in th e presenc e oftheenzyme sucrose synthetase eg. In higher plants
UDPG + Fructose UDP + SucroseSucrose synthetase3)From UDPG and fructose-6-phosphate in the presence of enzyme sucrosePhosphate synthetase. eg, in higher plantsUDPG + fructose-6-phosphate UDP + sucrose phosphateSucrose phosphate synthetaseSucrose phosphate is hydrolysed in the presence of phosphatase enzyme to yield sucroseSucrose PhosphateSucrose + phosphatePhosphataseBreak down of sucroseSucrose is broken down or hydrolysed to yield glucose and fructose in the presence of theenzyme invertase or sucrase. The reaction is irreversibleSucrose + H2OGlucose + FructoseInvertase3)Describe the properties of carbohydrateMonosaccharides1)Reaction with alcohol-The Glycosidic OH group of mutarotating sugars reacts withalcohol to form ά and β glycosides or acetals. Thus glucose form glucosides andfructose from fructosides2)Reaction with acetic anhydride-The Glycosidic and alcoholic OH group ofmonosaccharides and disaccharides react with acetylating agents to form acetatederivatives called esters3)Oxidation with acids-Only the aldehydes group of sugar is oxidized to producemonocarboxylic acid with bromine water, while with nitric acid both aldoses andketoses react to form dicarboxylic acid4)Oxidation with metal hydroxides-Metal hydroxides like copper hydroxideoxidize free aldehydes or keto group of mutarotating monosaccharides and at thesame time they themselves reduce to free metalReducing sugar + Cu2+oxidized sugar + 2 Cu+2Cu++ 2OH-2Cu.OH Cu2O + H2OYellowRedThis sugar is active ingredient in Fehling"s, Benedict"sand Barfoed"s reagent5)Reduction-The sugars undergo reduction with sodium amalagam to formcorresponding alcohols. Glucose yields sorbitol and fructose yields mixture ofsorbitol and mannitol. With strong acids, it undergo reduction to form levulinicacid.6)Reaction with hydrogen cyanide-(Kilani synthesis). It forms cyanohydrins
Heptoses1)Triose-Glyceraldehydes. The simplest compound having three carbon atoms. It iscolourless, sweet, crystalline and soluble in water, insoluble in ether, cannot behydrolysed and formed in the plants during glycolysis2) Tetroses-Erythroses. This has four carbon atoms, colourless, crystalline, soluble inwater, insoluble in ether. It is produced in plants in photosynthesis in presence oftransketolase from fructose-6-phosphate3)Pentoses-Riboses andRibulose. They have 5 carbon atoms. In plants they are found incombined state. It reduces Fehling"s solution and gives Molisch"s test.They are notfermentable. Ribose is an aldopentosesand ribulose is keto pentoses. It is used in theformation of RNA. Arabinose is colourless, sweet in taste. It can be obtained by thehydrolysis of gum Arabic, peach gum and cherry gum. It reduces Fehling"s solution. Xyloseis aldosugar and xylulose is ketonoic form and is formed in photosynthesis. It is colourless,crystalline, optically inactive. It is also formed by hydrolysis of wood gum or xylose.4)Hexoses-Glucose/ fructose-These sugars are six carbon atoms and cannot be hydrolysed.Glucose is called as dextrose formed by the hydrolysis of cane sugar, glucosides, starch andcellulose etc., It is needle shaped crystals, anhydrous. Fructose is a keto sugar formed inequal quantity with glucose by the hydrolysis of cane sugar, soluble in hot absolutealcoholand ether. Mannose is prepared by hydrolysing mannane found in ivory nuts.5)Heptoses-Glucoheptoses and Sedoheptulose. They are seven sugar carbon atom. It isketosugar and formed in photosynthesis6) Discuss the four important chemical reactions of carbohydrates1)Oxidation with acids:a)Mild oxidizing agent (HOBr). Only the aldehydes group is oxidized by bromine waterto produce monocarboxylic acid. Ketoses do not react with bromine waterCHO-(CHOH)4-CH2OH + HOBrCOOH-(CHOH)4-CH2OH + HBrGlucoseGluconic acidb)Strong acids (HNO3) : B oth al doses a nd ket oses reac t wi th nitri c ac id to formdicarboxylic acidCHO-(CHOH)4-CH2OH + HNO3COOH-(CHOH)4-COOH + H2OGlucose Glucaric acidc)Oxidation with metal hydroxide: Metal hydroxide Cu(OH)2oxidize the free aldehydesand keto group and reduce itself to form free metalReducing sugar + 2 Cu2+Oxidized sugar + 2 Cu2+Blue2 Cu2++ 2OH-2CuOH Cu2O + H2OYellowRed
PROTEINSThe word "Protein" was coined by J.J. Berzelius in 1838 and was derived from the Greek word"Proteios" meaning the 'first rank".Introduction:Most abundant organic molecules ofthe living systemIts fundamental basis of structures and function of life.50 % of dry weight of every cellIt"s a polymer of L α-amino acids.300 different amino acids occur in nature-only 20 as standard amino acids.21st amino acid added-Seleno cysteineDefinitionProteins are organic complex nitrogenous compounds of high molecular weight, formed of C,H, O, N [N= 16%].They are formed of a number of amino acids linked together by peptide linkage [-CO-NH-].The carboxylic group of thefirst amino acid units with the amino group of the second aminoacid and so on.General Properties of ProteinsiProteins are substances of high molecular weight.iProteins form colloidal solution and having its same properties as:Tyndall effect & BrownianmovementiProteins are non-dialyzable due to their large molecules.iProteins are amphoteric which liable to react with acid and alkali.iEach protein has its own isoelectric point.iProtein acts as a buffer solution which resists the change of its pH by addition of acid oralkali.iDenaturationBiological Importance of ProteinsiThey provide the body with nitrogen, sulfur, and some vitamins.iFormation of enzyme