LECTURE 3 -CARBOHYDRATES

CO 2: Describe, Discuss, and compare the classification, structure and function of carbohydrates and its derivatives.

LECTURE 3 -CARBOHYDRATES
TOPICS: 1. Role & Significance of Carbohydrates 2. Monosacharides 3. Oligosacharides 4. Polysacharides 5. Glyconoconjugates

Section

Section Section Section Section

Sect.1. ROLE OF CARBOHYDRATES As a major energy source for living organisms As a means of transporting energy
(glucose is a principal energy source in animal and plants) sucrose in plant tissues)

( exp:

As a structural material . As a precursor for other biomolecules

building blocks of nucleotides) (purine, pyrimide)

( cellulose in plants, chitin in insects,

Sect . SI NI I

Carbohydrates are the most abundant biomolecules in nature, having a direct link between solar energy and the chemical bond energy in living organisms. Source of rapid energy production Structural building blocks of cells Components of several metabolic pathways ecognition of cellular phenomena, such as cell recognition and binding (e.g., by other cells, hormones, and viruses)

CARBOHYDRATES
Carbohydrate : compounds contains H, C & O with the comp : (CH2O)n (Hydrate of carbon) Carbohydrates : Consist of sugar (saccharum) Sugars : compound that contains alcohol & carbonyl functional group

Carbonyl func.group : >C=o Adehyde aldose Ketone ketose

Examples:

Classification

Carbohydrate

Mono saccharide

Oligo saccharide

Poly saccharide

Glyconoconjugates

Glucose, fructose Ribose (aldopentose) Deoxy ribose

disaccharides Glycoproteins (bacterial cell walls

cellulose, chitin, starch, glycogen, glucoaminoglycans

glycoproteins and proteoglycans

Sect2.
MO OSACHARIDES

Sect. 2. Monosacharides
Sub sections : 2.1 Properties & classification 2.2 Stereoisomers 2.3 Cyclic structure 2.4 Important Reactions 2.5 Important monosach 2.6 glycoproteins and proteoglycans 2.7 Monosaccharide derivatives

2.1 Monosach Properties& classification

Colorless, crystalline solids Soluble in water but insoluble in nonpolar solvents One of the carbon atoms is double-bonded to an oxygen atom to form a carbonyl group; each of the other carbon atoms has a hydroxyl group.
Carbohydrates with an aldehyde (-CHO) functional (group are called aldoses e.g. glyceraldehyde (CH OH-CHOH-CHO) OH-CHOH-CHO) Those with a keto group (-C=O) are ketoses (2

e.g.dihydroxyacetone (CH2OH-C=O-CH2OH) (CH2OH-C=O-

Classified according to the number of carbon atoms they contain

Monosacharides : Exp. aldoses & ketoses

Aldotriose

Aldotetrose

Aldopentoses

Aldohexose

Ketotriose

Ketotetrose

Ketopentose

Ketohexose

2.2. MO OSACCHARIDES STEREOISOMERS

Isomers: same chemical formulas, different structures Conformation : the spatial arrangement of substituent groups chiral centers: asymmetric carbons, i.e carbon atom with four different substituents Enantiomers : mirror images Stereoisomers The simplest aldose, glyceraldehyde, contains one chiral center (the middle carbon atom) and has two different optical isomers, or enantiomers

the projection in which the carbohydrate backbone is drawn vertically with the carbonyl shown on the top.

D- and L- enantiomers L-

2.3 Cyclic structure of monosacharides

in aqueous solution, monosaccharides with five or more carbon atoms in the backbone occur predominantly as cyclic (ring) structures in which the carbonyl group has formed a covalent bond with the oxygen of a hydroxyl group along the chain.

The new chiral center in cyclic (c1) is called anomeric carbon

Pyranoses& Furanoses
Pyranoses: six-membered ring compounds ( resemble pyran ) Furanoses : fivemembered rings, (resemble furan)

The structure systematic names glucose & fructose become HAWORTH STRUCTURES An English chemist W. . Haworth gave a more accurate picture of carbohydrate structure. (Ref. P.205 of textbook)

FISHER A D HAWORTH FORMS OF SUGAR

SUMMARY OF SUGAR STRUCTURES

ISOMERSISOMERS- compounds that have the same chemical formula e.g. fructose, glucose, mannose, and galactose are isomers of each other having formula C6H12O6. EPIMERSEPIMERS- refer to sugars whose configuration differ around one specific carbon atom e.g. glucose and galactose are C-4 epimers Cand glucose and mannose are C-2 epimers. CE A TIOMERS- a special type of isomerism found in pairs of TIOMERSstructures that are mirror images of each other. The mirror images are termed as enantiomers and the two members are designated as D- and L- sugar. The vast majority of sugars in humans are DLDsugars. CYCLIZATIO OF SUGARS- most monosaccharides with 5 or more SUGARScarbon atoms are predominately found in a ring form, where the aldehyde or ketone group has reacted with an alcoholic group on the same sugar group to form a hemiacetal or hemiketal ring. Pyranose ring- if the ring has 5 carbons and 1 oxygen. ringFuranose ring- if the ring is 5-membered (4 carbons and 1 oxygen ring5-

2.4.IMPORTA T REACTIO S I MO OSACCHARIDES

Monosaccharides undergo the following reactions :

1. 2. 3. 4. 5. 6.

Mutarotation Oxidation Reduction Isomerization Esterification Glycoside formation

IMPORTA T REACTIO S I MO OSACCHARIDES Details 1. Mutarotation alfa and beta forms of sugars are readily interconverted when dissolved in water 2 Oxidation and reduction in presence of oxidising agents, metal ions (Cu2+) and enzymes, monosacchs undergo several oxidation reactions e.g. Oxidation of acid; aldehyde group (R-CHO) yields aldonic acid; of terminal CH2OH (Racid; (alcohol) yields uronic acid; and of both the aldehyde and CH2OH gives aldaric acid. The carbonyl groups in both aldonic and uronic acid. can react with an OH group in the same molecule to form a cyclic lactone. ester lactone. REDUCTIO reduction of the aldehyde and ketone groups of monosacchs yield sugar alcohols (alditols) Sugar alcohols e.g.sorbitol, are used (alditols) commercially in processing foods and pharmaceuticals.

IMPORTA T REACTIO S (Cont)

4.

ISOMERIZATIO Monosaccharides undergo several types of isomerization e.g. D-glucose in Dalkaline solution for several hours contain D-mannose and D-fructose. The DDconversion of glucose to mannose is termed s epimerization. (p.208-9 of epimerization. (p.208Textbook). ESTERIFICATIO Free OH groups of carbohydrates react with acids to form esters. This esters. reaction can change the physical and chemical propteries of sugar. Phosphate and sulfate esters of carbohydrates [carbos] are common in nature. Phosphorylated derivatives of some carbos, formed during reactions with ATP, are important metabolic components of living cells GLYCOSIDE FORMATIO Hemiacetals and hemiketals reaction with alcohols to form the corressponding acetal or ketal (p.210 of Text).On the contrary when a cyclic hemiacetal or hemiketal form of monosaccharide reacts with alcohol, the new linkage is called glycosidic linkage and the compound glycoside [e.g. glucosides, frutosides, pyranosides]

6.

Alfa & beta GLYCOCIDIC BO D

REDUCI G SUGARS All monosacchs are reducing sugars. They can be oxidised by weak oxidising agent such as Benedicts reagent Benedict's reagent is a solution of copper sulfate, sodium hydroxide, and tartaric acid.
Aqueous glucose is mixed with Benedict's reagent and heated. The reaction reduces the blue copper (II) ion to form a brick red precipitate of copper (I) oxide. Because of this, glucose is classified as a reducing sugar.

2.5 IMPORTA T MO OSACCHARIDES GLUCOSE FRUCTOSE GALACTOSE

D-Glucose:
D-glucose (dextrose) is the primary fuel in living cells especially in brain cells that have few or no mitochondria. Cells such as eyeballs have limited oxygen supply and use large amount of glucose to generate energy Dietary sources include plant starch, and the disaccharides lactose, maltose, and sucrose

DIABETES (diabetes mellitus)

Characterized by high blood glucose levels that splills over into the urine These high glucose levels impairs the insulin-stimulated insulinglucose entry into cells and starve the cells of insulin. This leads to ketosis or high levels of ketone bodies (acids) that hinders the buffering capacity of the blood in the kidney, which controls blood pH (by excreting excess H+ ions into the urine). The H+ excretion is accompanied by the excretion ammonia, sodium,potassium, and phosphate ions causing severe dehydration This leads to excessive thirst symptom of diabetes and lifelife-threatening decrease in blood volume.

Important monosaccharides. Cont

FRUCTOSE
D-fructose (levulose) is often referred as fruit sugar and is found in some vegetables and honey This molecule is an important member of ketose member of sugars It is twice as sweet as sucrose (per gram basis) and is used as sweeting agent in processed food products It is present in large amounts in male reproductive tract and is synthesised in the seminal vesicles.

Important monosaccharides. Cont....

GALACTOSE
is necessary to synthesize a variety of biomolecules glycolipids, (lactose-in mammalary glands, glycolipids, certain lactosephospholipids, proteoglycans, phospholipids, proteoglycans, and glycoproteins) glycoproteins) Galactose and glucose are epimers at carbon 4 and interconversion is catalysed by enzyme epimerase. epimerase. Medical problems galactosemia (genetic disorder) where enzyme to metabolize galactose is missing; accumulation of galactose in the body can cause liver damage, cataracts, damage, cataracts, and severe mental retardation

2.7.MO OSACCHARIDE DERVATIVES URO IC ACIDS formed when terminal CH2OH group of a mono sugar is oxidised
Important acids in animals D-glucuronic acid and its epimer L-iduronic acid L In liver cells glucuronic acid combines with steroids, certain drugs, and bilirubin to improve water solubility therby helping the removal of waste products from the body These acids are abundant in the connective tissue carbohydrate components.

Mono sugar derivatives AMI O SUGARS

Sugars in which a hydroxyl group (common on carbon 2) is replaced by an amino group e.g. D-glucosamine and D-galactosamine DD common constituents of complex carbohydrate molecule found attached to cellular proteins and lipids Amino acids are often acetylated e.g. acetylacetyl-glucosamine.

Mono sugar derivatives

DEOXYSUGARS
monosaccharides in which an - H has replaced an OH group Important sugars: L-fucose (formed from D-mannose LDby reduction reactions) and 2-deoxy-D-ribose 2-deoxy L-fucose found among carbohydrate components of glycoproteins, such as those of the ABO blood group determinates on the surface of red blood cells 2-deoxyribose is the pentose sugar component of D A.

GLYCOSIDES
Monosaccharides can be linked by glycosidic bonds

(joining of 2 hydroxyl groups of sugars by splitting out water molecule) to create larger structures. Disaccharides contain 2 monosaccharides e.g. lactose (galactose+glucose); maltose (glucose+glucose); sucrose (glucose+fructose) Oligosaccharides 3 to 12 monosaccharides units e.g. glycoproteins Polysaccharides more than 12 monosaccharides units e.g. glycogen (homopolysaccharide) having (homopolysaccharide) hundreds of sugar units; glycosaminoglycans (heteropolysaccharides) containing a number of different heteropolysaccharides) monosaccharides species.

Section 3 DISACCHARIDES A D OLIGOSACCHARIDES

DISACCHARIDES A D OLIGOSACCHARIDES Cnfigurations: alfa or beta ( 1,4, glycosidic bonds or linkages; other linkages 1,1; 1,2; 1,3; 1,6) Digestion aided by enzymes. Defficiency of any one enzyme causes unpleasant symptoms (fermentation) in colon (fermentation) produces gas [bloating of cramps]. Most common defficiency, an ancestoral disorder, lactose intolerance caused by reduced synthesis of lactase

Important sugars of Disaccharides

LACTOSE
(milk sugar) disaccharide found in milk; composed of one molecule of galactose and glucose linked through beta(1,4) beta(1,4) glycosidic linkage; because of the hemiacetal group of the glucose component, lactose is a reducing sugar

Lactose intolerance
Lactose (milk sugar) in infants is hydrolyzed by intestinal enzyme lactase to its component monosacch for absorption into the bloodstream (galactose epimerized to glucose). Most adult mammals have low levels of betabetagalactosidase. Hence, much of the lactose they ingest moves to the colon, where bacterial fermentation generates large quantities of CO2, H2 and irritating organic acids. These products cause painful digestive upset known as lactose intolerance and is common in the African and Asian decent.

MALTOSE ( malt sugar) An intermediate product of starch hydrolysis; it is a disaccharide with an alfa(1,4) alfa(1,4) glycosidic linkage between two D-glucose molecules; in solution the free Danomeric carbon undergoes mutarotation resulting in an equilibrium mixture of alfa and beta maltoses; it does not occur freely in nature

SUCROSE common table sugar: cane sugar or beet sugar produced in the leaves and stems of plants; it is a disaccharide containing both alfa-glucose and beta-fructose residues alfabetalinked by alfa,beta(1,2)glycosidic bond. alfa,beta(1,2)glycosidic

CELLOBIOSE degradation product of cellulose containing two molecules of glucose linked by a beta (1,4) glycosidic bond; it does not occur freely in nature

OLIGOSACCHARIDE SUGARS
Oligosaccharides are small polymers often found attached to polypeptides in glycoproteins and some glycolipids. glycolipids. They are attached to membrane and secretory proteins found in endoplasmic reticulum and Golgi complex of various cells Two classes: -linked and O-linked O-

Section 4 POLYSACCHARIDES
4.1. Intro to Polysaccharides 4.2. Classification of Polisacharides 4.2.1. Homosacharides 4.2.2. Heteropolysacharides

4.1. Intro to Polysaccharides

Composed of large number of monosaccharide units connected by glycosidic linkages Classified on the basis of their main monosaccharide components and the sequences and linkages between them, as well as the anomeric configuration of linkages, the ring size (furanose or pyranose), the absolute configuration (D- or L-) and any other substituents (D- Lpresent. (http://www.lsbu.ac.uk/water/hypol.html) Polysaccharides are more hydrophobic if they have a greater number of internal hydrogen bonds, and as their hydrophobicity increases there is less direct interaction with water Divided into homopolysaccharides (e.g.Starch, glycogen, cellulose, and chitin) & heteropolysaccharides (glycoaminoglycans or GAGs, murein).

4.2. Classification of Polisacharides

4.2.1.HOMOSACCHARIDES
Found in abundance in nature Important examples: starch, glycogen, cellulose, and chitin Starch, glycogen, and cellulose all yield DDglucose when they are hydrolyzed Cellulose - primary component of plant cells Chitin principal structural component of exoskeletons of arthropods and cell walls of many fungi; yield glucose derivative -acetyl glucosamine when it is hydrolyzed.

STARCH (Homosaccharide)
A naturally abundant nutrient carbohydrate, (C6H10O5)n, found chiefly in the seeds, fruits, tubers, roots, and stem pith of plants, notably in corn, potatoes, wheat, and rice, and varying widely in appearance according to source but commonly prepared as a white amorphous tasteless powder. Any of various substances, such as natural starch, used to stiffen cloth, as in laundering. Two polysaccharides occur together in starch: amylose and amylopectin Amylose unbranched chains of D-glucose residues linked with Dalfa(1,4,)glycosidic alfa(1,4,)glycosidic bonds Amylopectin a branched polymer containing both alfa(1,4,) and alfa(1,4,) alfa(1,6) glcosidic linkages; the alfa(1,6) branch points may occur alfa(1,6) every 20-25 glucose residues to prevent helix formation 20Starch digestion begins in the mouth; alfa-amylase in the saliva alfainitiates hydrolysis of the gycosidic linkages

GLYCOGE

(Homosaccharide)

Glycogen is the storage form of glucose in animals and humans which is analogous to the starch in plants. Glycogen is synthesized and stored mainly in the liver and the muscles. Structurally, glycogen is very similar to amylopectin with alpha acetal linkages, however, it has even more branching and more glucose units are present than in amylopectin. Various samples of glycogen have been measured at 1,7001,700600,000 units of glucose. The structure of glycogen consists of long polymer chains of glucose units connected by an alpha acetal linkage. The branches are formed by linking C # 1 to a C # 6 through an acetal linkages. In glycogen, the branches occur at intervals of 8-10 glucose units, 8while in amylopectin the branches are separated by 12-20 glucose 12units.

STRUCTURE OF GLYCOGE

CELLULOSE (Homosaccharide)
Cellulose is found in plants as microfibrils (2-20 nm diameter and (2100 - 40 000 nm long). These form the structurally strong framework in the cell walls. Cellulose is mostly prepared from wood pulp Cellulose is a linear polymer of -(1 4)-D-glucopyranose units in 4C1 4)conformation. The fully equatorial conformation of -linked glucopyranose residues stabilizes the chair structure, minimizing its flexibility Cellulose has many uses as an anticake agent, emulsifier, stabilizer, dispersing agent, thickener, and gelling agent but these are generally subsidiary to its most important use of holding on to water. Water cannot penetrate crystalline cellulose but dry amorphous cellulose absorbs water becoming soft and flexible. Purified cellulose is used as the base material for a number of waterwater-soluble derivatives e.g. Methyl cellulose, carbomethycellulose

Cellulose as polymer of -D-glucose

Cellulose in 3D

CELLULOSE

CHITI (Homosaccharide)
Chitin is a polymer that can be found in anything from the shells of beetlesto webs of spiders. It is present all around us, in plant and animal creatures. It is sometimes considered to be a spinoff of cellulose, cellulose, because the two are very molecularly similar. Cellulose contains a hydroxy group, and chitin contains acetamide. Chitin is unusual because it is a "natural polymer," or a combination of elements that exists naturally on earth. Usually, polymers are man-made. Crabs, beetles, worms manand mushrooms contain large amount of chitin. Chitin is a very firm material, and it help protect an insect against harm and pressure

Structure of the chitin molecule, showing two of the acetylglucosamine units that repeat to form long chains in betabeta-1,4 linkage.

CHITOSA
A spinoff of chitin that has been discovered by the market is chitosan. This is a man-made molecule that is manoften used to dye shirts and jeans in the clothing industry. Chitosan can be used within the human body to regulate diet programs, and researchers are looking into ways in which it can sure diseases. Chitin, the polysaccharide polymer from which chitosan is derived, is a cellulose-like polymer consisting mainly of celluloseacetylunbranched chains of -acetyl-D-glucosamine. Deacetylated chitin, or chitosan, is comprised of chains of D-glucosamine. When ingested, chitosan can be Dconsidered a dietary fiber.

CHEMICAL STRUCTURE OF CHITOSA

http://www.pdrhealth.com/drug_info/nmdrugprofiles/nutsupdrugs/chi_0067.shtml

4.2.2.HETEROPOLYSACCHARIDES Are high-molecular-weight carbohydrate high-molecularpolymers more than one kind of monosaccharide Important examples include glycosaminoglycans (GAGs) the principle components of proteoglycans and murein, a major component of bacterial cell walls.

GAGs - high-molecular-weight high-molecularcarbohydrate polymers

Glycosaminoglycans forming the proteoglycans are the most abundant heteropolysaccharides in the body. They are long unbranched molecules containing a repeating disaccharide unit. Usually one sugar is unit. an uronic acid (either D-glucuronic or L-iduronic) iduronic) and the other is either GlcNAc or GalNAc. One GalNAc. or both sugars contain sulfate groups (the only exception is hyaluronic acid). GAGs are highly negatively charged what is essential for their function.

THE SPECIFIC GAGs OF PHYSIOLOGICAL SIGNIFICANCE Hyaluronic acid Occurence : synovial fluid, ECM of loose connective tissue Hyaluronic acid is unique among the GAGs because it does not contain any sulfate and is not found covalently attached to proteins. It forms non-covalently linked complexes with nonproteoglycans in the ECM. Hyaluronic acid polymers are very large (100 10,000 kD) and can displace a large volume of water.

Hyaluronic acid (D-glucuronate + Glc Ac) (D-

Dermatan sulfate (L-iduronate + Glc Ac sulfate) (LOccurence : skin, blood vessels, heart valves

Chondroitin sulfate (D-glucuronate + (DGal Ac sulfate) Occurence : cartilage, bone, heart valves ; It is the most abundant GAG.

Heparin and heparan sulfate (D-glucuronate (Dsulfate + -sulfo-D-glucosamine) sulfoHeparans have less sulfate groups than heparins Occurence : Heparin :component of intracellular granules of mast cells lining the arteries of the lungs, liver and skin Heparan sulfate : basement membranes, component of cell surfaces

Keratan sulfate ( Gal + Glc Ac sulfate)

Occurence : cornea, bone, cartilage ; Keratan sulfates are often aggregated with chondroitin sulfates. sulfates.

MUREI (Peptidoglycan)
Peptidoglycan, Peptidoglycan, also known as murein, is a polymer consisting of murein, sugars and amino acids that forms a mesh-like layer outside the meshplasma membrane of eubacteria. eubacteria. The sugar component consists of alternating residues of -(1,4) linked -acetylglucosamine and -acetylmuramic acid residues. Attached to the -acetylmuramic acid is a peptide chain of three to five amino acids. The peptide chain can be cross-linked to the peptide chain of crossanother strand forming the 3D mesh-like layer. meshSome Archaea have a similar layer of pseudopeptidoglycan. pseudopeptidoglycan.

Peptidoglycan serves a structural role in the bacterial cell wall, wall, giving the wall shape and structural strength, as well as counteracting the osmotic pressure of the cytoplasm. cytoplasm. Peptidoglycan is also involved in binary fission during bacterial cell reproduction. The peptidoglycan layer is substantially thicker in GramGrampositive bacteria (20 to 80 nm) than in Gram-negative nm) Grambacteria (7 to 8 nm), with the attachment of the S-layer. layer. Peptidoglycan forms around 90% of the dry weight of GramGram-positive bacteria but only 10% of Gram-negative Gramstrains. In Gram-positive strains, it is important in attachment Gramroles and serotyping purposes.

SECTIO 5 GLYCOCO JUGATES

5.1. 5.2. 5.3. 5.4. Intro to glycoconjugates glycoproteins glycosylation proteoglycans

5.1. Intro to glycoconjugates

They are compounds that result from covalent linkages of carbohydrate molecules to both proteins and lipids. They have a profound effects on the functions of individual cells as weell as cell-cell interactions cellof multicellular organisms. Two classes of carbohydrate-protein conjugate: carbohydrateglycoproteins and proteoglycans. The glycolipids (oligosaccharide-containing lipid (oligosaccharidemolecules) are found predominately on the outer surface of plasma membrane.

5.2.glycoproteins
Glycoprotein carbohydrate chains are highly diverse. They are formed by glycosylation and classified into two groups: 1. -linked oligosaccharides 2. O-linked oligosaccharides OThe -linked oligosaccharides have a minimum of 5 sugar residues -linked attached to polypeptides by an N-glycosidic bond with a chain amide group of amino acid and asparagine O-linked oligosaccharides are generally short (1-4 sugar (1residues) O-linked are attached to polypeptides by the side chain hydroxyl group of amino acids serine or threonine in polypeptide chains or hydroxyl groups of membrane lipids

5.3.glycosylation
Glycosylation is the process or result of addition of saccharides to proteins and lipids The process plays an important role in the synthesis of membrane and secreted proteins Majority of proteins synthesized in the rough ER undergo glycosylation It is an enzyme -directed site-specific process. siteTwo types of glycosylation exist: N-linked glycosylation to the amide nitrogen of asparagine side chains and Olinked glycosylation to the hydroxy oxygen of serine and threonine side chains. Glycosylation may play a role in cell-cell adhesion (a cellmechanism employed by cells of the immune system), system), as well.

GLYCOPROTEI FU CTIO S
Types of glycoproteins: asparagine-linked carbohydrate; asparaginemucinmucin-type cabohydrate Examples: glycophorin (membrane protein, source human RBC, % carbohydrate - 60); potato lectin (lectin, carbohydrate binding proteins, source potato, % carbohydrate 50) Functions: Functions: Many glycoproteins have structural functions: constituent of the cell wall; form connective wall; tissues such as collagen; found in gastrointestinal mucus secretions; used as protective agents and lubricants ;found abundantly in the blood plasma. plasma. The human blood groups A, B, AB, and O depend on the oligosaccharide part of the glycoprotein on the surface of erythrocyte cells. The terminal monosaccharide of the glycoprotein at the nonreducing end determines blood group.

BLOOD GROUPS
TYPE A B AB O O AB TERMINAL SUGAR N-acetylgalactosamine E-D-galactose both the above neither of the above is the universal donor is the universal acceptor

Oligosaccharides are antigeneic determinants

Carbohydrates on cell surfaces are immunochemical markers. ABO blood group antigens are oligosaccharide components of glycoproteins and glycolipids on the surfaces of individual cells, besides blood cells. Individuals with type A cells have A antigens on their cell surfaces and carry anti-B antibodies antiThose with type B cells which bear B antigens, carry anti-A antibodies anti-

Those with type AB cells, which have both A and B antigens, carry neither anti-A nor anti-B antiantiantibodies Type O individuals whose cells bear neither antigen, carry both anti-A and anti-B antibodies. antiantiTransfusion of type A blood group into a type B individual, results in an anti-A antibody- A anti- antibodyantigen reaction. This reaction clumps together (agglutinates) the transfused erythrocytes, resulting in an often fatal blockage of blood vessels

Functions of glycoproteins (elaborated)

http://www.cs.stedwards.edu/chem/Chemistry/CHEM43/CHEM43/Glycoproteins/Glycoproteins.HTML

Carbohydrates and proteins by themselves serve in a vast number of biological functions,linking the two together results in a macromolecule with an extremely large number of functions. Structural: Structural: Glycoproteins are found throughout matrices. They act as receptors on cell surfaces that bring other cells and proteins (collagen) together giving strength and support to a matrix. In nerve tissue glycoproteins are abundant in gray matter and appear to be associated with synaptosomes, axons, and microsomes. Protection: Protection: Human lacrimal glands produce a glycoprotein which protects the corneal epithelium from desiccation and foreign particles. Human sweat glands secrete glycoproteins which protect the skin from the other excretory products that could harm the skin

Functions of glycoproteins (further elaborated-1) elaboratedProthrombin, thrombin, and fibrinogen are all glycoproteins that play an intricate role in the blood clotting mechanism In certain bacteria the slime layer that surrounds the outermost components of cell walls are made up of glycoproteins of high molecular weight. In addition to forming these s-layers, glycoproteins also function as sbacterial flagella. These are made up of bundles of glycoproteins protruding from the cell's surface. Their rotation provides propulsion. In plants, glycoproteins have roles in cell wall formation, tissue differentiation, & embryogenesis. Reproduction: Glycoproteins found on the surface of spermatozoa appear to increase a sperm cell's attraction for the egg by altering the electrophoretic mobility of the plasma membrane.

Functions of glycoproteins (further elaborated-2) elaborated-

Adhesion: Adhesion: Glycoproteins serve to adhere cells to cells and cells to substratum. Hormones: Hormones: There are many glycoproteins that function as hormones such as human chorionic gonadotropin (HCG) which is present in human pregnancy urine. Another example is erythropoietin which regulates erythrocyte production Enzymes: Glycoprotein enzymes are of three types. These are oxidoreductases, transferases, and hydrolases.

Functions of glycoproteins (further elaborated-3) elaboratedCarriers: Carriers: Glycoproteins can bind to certain molecules and serve as vehicles of transport. They can bind to vitamins, hormones, cations, and other substances. Inhibitors: Inhibitors: Many glycoproteins in blood plasma have shown antiproteolytic activity. For example, the glycoprotein a1-antichymotrypsin inhibits chymotrypsin. a1Immunological: Immunological: The interaction of blood group substances with antibodies is determined by the glycoproteins on erythrocytes. Many immunoglobulins are actually glycoproteins. B and T cells contain surface glycoproteins that attract bacteria to these sites and bind them. In much the same manner, glycoproteins can direct phagocytosis. Because the HIV virus recognizes the receptor protein CD4, it binds to helper T cells which contain it.

CELL MEMBRA E
The cell membrane is a fluid mosaic of lipids, proteins, and carbohydrates. Membrane carbohydrates are usually branched oligosaccharides with fewer than 15 sugar units. Some of these oligosaccharides are covalently bonded to lipids, forming molecules called glycolipids. Most are covalently bonded to proteins, which are thereby glycoproteins. glycoproteins. Plants produce pectin, major component of cell wall. pectin, The oligosaccharides on the external side of the plasma membrane vary from species to species The diversity of the molecules and their location on the cell's surface enable oligosaccharides to function as markers that distinguish one cell from another.

THE MOSAIC OF CELLS MEMBRA E

CELL MEMBRA E MATRIX

The biological membrane is a collage of many different proteins embedded in the fluid matrix of the lipid bilayer. bilayer. The lipid bilayer is the main fabric of the membrane, and its structure creates a semisemipermeable membrane. The hydrophobic core impedes the transport of hydrophilic structures, such as ions and polar molecules but enable hydrophobic molecules, which can dissolve in the membrane, cross it with ease.

Protein layer of cell membrane Proteins determine most of the membrane's specific functions. The plasma membrane and the membranes of the various organelles each have unique collections of proteins. For example, to date more than 50 kinds of proteins have been found in the plasma membrane of red blood cells.

5. . PR TE G Y AN
Proteoglycans represent a special class of glycoproteins that are heavily glycosylated. They consist of a core protein with one or more covalently attached glycosaminoglycan chain(s). These glycosaminoglycan (GAG) chains are long, linear carbohydrate polymers that are negatively charged under physiological conditions, due to the occurrence of sulphate and uronic acid groups. Proteoglycans can be categorised depending upon the nature of their glycosaminoglycan chains. These chains may be: 1. chondroitin sulfate and dematan sulfate 2. heparin and heparin sulfate 3. keratan sulfate

Proteoglycans can also be categorised by size. Example of large proteoglycan is aggrecan. Aggrecan, Aggrecan, is the major proteoglycan in cartilage, present in many adult tissues including blood vessels and skin. The small leucine rich repeat proteoglycans (SLRPs) include decorin, biglycan, fibromodulin and lumican. lumican.

SY THESIS OF PROTEOGLYCA S
The protein component of proteoglycans is synthesized by ribosomes and translocated into the lumen of the rough endoplasmic reticulum. reticulum. Glycosylation of the proteoglycan occurs in the Golgi apparatus in multiple enzymatic steps. First a special link tetrasaccharide is attached to a serine side chain on the core protein to serve as a primer for polysaccharide growth. Then sugars are added one at the time by glycosyl transferase. The completed proteoglycan is then exported in secretory vesicles to the extracellular matrix of the cell.

Structure of proteoglycans
The GAGs extend perpendicular from the core protein in a bottlebrushbottlebrush- like structure. The linkage of GAGs such as (heparan sulfates and chondroitin (heparan sulfates) sulfates) to the protein core involves a specific trisaccharide linker Some forms of keratan sulfates are linked to the protein core through an N-asparaginyl bond. bond. The protein cores of proteoglycans are rich in Ser and Thr residues which allows multiple GAG attachment.

FU CTIO OF PROTEOGLYCA S
Proteoglycans are a major component of the animal extracellular matrix, the 'filler' substance existing matrix, between cells in an organism. Individual functions of proteoglycans can be attributed to either the protein core or the attached GAG chain. In extracellular matrix, they form large complexes, with other proteoglycans, to hyaluronan and to fibrous matrix collagen). proteins (such as collagen). They are also involved in binding cations (such as sodium, sodium, potassium and calcium) and water, and also calcium) water, regulating the movement of molecules through the matrix. They can affect the activity and stability of proteins and signalling molecules within the matrix.

ROLE OF PROTEOGLYCANS
http://www.cryst.bbk.ac.uk/pps97/assignments/projects/emilia/Proteoglycans.HTM

GAG dependent functions can be divided into two classes: the biophysical and the biochemical. The biophysical functions depend on the unique properties of GAGs : the ability to fill the space, bind and organize water molecules and repel negatively charged molecules. Because of high viscosity and low compressibility they are ideal for a lubricating fluid in the joints. On the other hand their rigidity provides structural integrity to the cells and allows the cell migration due to providing the passageways between cells. For example the large quantities of chondroitin sulfate and keratan sulfate found on aggrecan play an important role in the hydration of cartilage. They give cartilage. the cartilage its gel-like properties and resistance to geldeformation.

Role of proteoglycans contd.

The other, more biochemical functions of GAGs are mediated by specific binding of GAGs to other macromolecules, mostly proteins. Proteoglycans participate in cell and tissue development and physiology. Hurlers syndrome: (refer Text) disease related with proteoglycan metabolism where excessive accumulation of dermatin sulfate due to deficiency of a specific enzyme may cause mental retardation, skeletal deformity ansd death in early childhood.

SUMMARY
Monosaccharides, the simplest carbohydrates, are classified as aldoses or ketoses. The cyclic hemiacetal and hemiketal forms of monosacchs have either alfa or beta configuration at their anomeric carbon. Monosacch derivatives include aldonic acids, uronic acids, deoxy sugars, amino sugars, alfa & beta glycosides. Disaccharides simplest polysaccharides occuring as hydrolysis products of larger molecules e.g. Lactose,sucrose Oligosaccharides play important roles in determining protein structure and in cell-surface recognition cellphenomena. Oligosacchs with 3 or more sugar residues are mostly found in plants.

Summary contd. -1
POLOYSACCHARIDES consist of monosacchs linked by glycosidic bonds. Cellulose and chitin are structural polysacchs with beta(1-4) linkages that adopt rigid and beta(1extended structures. The storage polysacchs starch and glycogen consist of alfa-glycosidically linked glucose alfaresidues Glycosaminoglycans are unbranched polysacchs containing uronic acids and amino sugars that are often sulfated

Summary contd.-2 contd.GLYCOCONJUGATES: Proteoglycans & GLYCOCONJUGATES:

glycoproteins play important roles in information transfer in living organisms. Proteoglycans are enormous molecules consisting of hyaluronate with attached core proteins that bear numerous glycosaminoglycans and oligosaccharides. Found in the extracellular matrix of tissues Bacterial cell walls are made up of peptidoglycan, peptidoglycan, a network of polysaccharide and poypeptide chains.

Summary contd.-3 contd.Glycoproteins or Glycosylated proteins may contain -linked oligosacchs attached to Asn (asparagine) or O-linked oligosacchs attached to OSer or Thr (serine or threonine) or both Different molecules of glycoproteins may contain different sequences and locations of oligosaccharides. Occur in cells in both soluble and membrane bound forms, and in extracellular fluids

E D OTES
The destiny of a nation depends on the manner in which it feeds itself. We eat to live, OT, live to eat. Lower your carbohydrate consumption, but balance it with the right amount of protein and fat.