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Copyright © 1999-2008 by Joyce J. Diwan. All rights reserved.
Carbohydrates (glycans) have the following
(CH2O)n I or H - C - OH I
Monosaccharides - simple sugars with multiple OH groups. Based on number of carbons (3, 4, 5, 6), a monosaccharide is a triose, tetrose, pentose or hexose. Disaccharides - 2 monosaccharides covalently linked. Oligosaccharides - a few monosaccharides covalently linked. Polysaccharides - polymers consisting of chains of monosaccharide or disaccharide units.
Aldoses (e.g., glucose) have Ketoses (e.g., fructose) have an aldehyde group at one end. a keto group, usually at C2.
H C H HO H H C C C C OH H OH OH
HO H H
CH2OH C C C C O H OH OH
H C OH CH2OH CH2OH D-glyceraldehyde CHO H C OH L-glyceraldehyde CHO HO C H CH2OH CH2OH D-glyceraldehyde L-glyceraldehyde .D vs L Designation CHO CHO HO C H D & L designations are based on the configuration about the single asymmetric C in glyceraldehyde. The lower representations are Fischer Projections.
Sugar Nomenclature For sugars with more than one chiral center. C H – C – OH HO – C – H H – C – OH H – C – OH CH2OH D-glucose C HO – C – H H – C – OH HO – C – H HO – C – H CH2OH L-glucose . O H O H Most naturally occurring sugars are D isomers. D or L refers to the asymmetric C farthest from the aldehyde or keto group.
e. galactose.g.g. O H O H C H – C – OH HO – C – H H – C – OH H – C – OH CH2OH D-glucose C HO – C – H H – C – OH HO – C – H HO – C – H CH2OH L-glucose The number of stereoisomers is 2n. Other stereoisomers have unique names. The 6-C aldoses have 4 asymmetric centers. Thus there are 16 stereoisomers (8 D-sugars and 8 L-sugars).D & L sugars are mirror images of one another. They have the same name. . etc. D-glucose & L-glucose. mannose. glucose... e. where n is the number of asymmetric centers.
A ketone can react with an alcohol to form a hemiketal. C R + R' OH R' O C R OH aldehyde R C R' O alcohol hemiacetal R + "R OH "R O C R' OH ketone alcohol hemiketal .Hemiacetal & hemiketal formation H H O An aldehyde can react with an alcohol to form a hemiacetal.
Pentoses and hexoses can cyclize as the ketone or aldehyde reacts with a distal OH. to form a 6-member pyranose ring. . 1 CHO C C C C OH H H HO H H 2 3 4 5 6 D-glucose OH (linear form) OH CH2OH 6 CH2OH 6 CH2OH H 4 5 O H 2 H 1 H 4 5 O H 2 OH 1 H OH 3 H OH 3 OH OH OH H H OH H OH -D-glucose -D-glucose These representations of the cyclic sugars are called Haworth projections. as the C1 aldehyde & C5 OH react. Glucose forms an intra-molecular hemiacetal. named after pyran.
or a 5-member furanose ring. . by reaction of the C2 keto group with the OH on C5. by reaction of the C2 keto group with the OH on C6.1 CH2OH O H OH OH HOH2C 6 5 2C HO H H 3 C C C O H HO 3 1 CH2OH 2 4 5 6 H 4 CH2OH OH H OH D-fructose (linear) -D-fructofuranose Fructose forms either a 6-member pyranose ring.
The 2 stereoisomers are called anomers. with the OH at the anomeric C1: (OH below the ring) (OH above the ring). & .6 CH 2OH 6 CH 2OH H 4 5 O H 2 H 1 H 4 5 O H 2 OH 1 H OH 3 H OH 3 OH OH OH H H OH H OH -D-glucose -D-glucose Cyclization of glucose produces a new asymmetric center at C1. Haworth projections represent the cyclic sugars as having essentially planar rings. .
depending on the sugar. . The representation above reflects the chair configuration of the glucopyranose ring more accurately than the Haworth projection. pyranose sugars actually assume a "chair" or "boat" configuration.H OH 4 6 5 3 H OH H O H 2 H O HO H HO H H OH OH H HO HO H OH 1 OH -D-glucopyranose -D-glucopyranose Because of the tetrahedral nature of carbon bonds.
lacks an aldehyde or ketone.g. e.. is oxidized to a carboxylic acid. or OH at C6.the aldehyde at C1. e. gluconic acid. glucuronic acid. ribitol. .g..Sugar derivatives COOH CH2OH H H H C C C OH OH OH CHO H HO H H C C C C OH H OH OH H HO H H C C C C OH H OH OH CH2OH D-ribitol CH2OH COOH D-gluconic acid D-glucuronic acid sugar alcohol . sugar acid .
The amino group may be acetylated. as in N-acetylglucosamine. An example is glucosamine.an amino group substitutes for a hydroxyl.Sugar derivatives CH2OH H H OH OH H NH2 O H OH OH H N H H H H OH CH2OH O H O OH C CH3 H -D-glucosamine -D-N-acetylglucosamine amino sugar . .
Sialic acid imparts negative charge to glycoproteins. as shown here. because its carboxyl group tends to dissociate a proton at physiological pH.O H3C C NH H O R H H OH H H OH COO HC R= HC OH OH CH2OH N-acetylneuraminate (sialic acid) N-acetylneuraminate (N-acetylneuraminic acid. also called sialic acid) is often found as a terminal residue of oligosaccharide chains of glycoproteins. .
. splitting out water to form a glycosidic bond: R-OH + HO-R' R-O-R' + H2O E. methanol reacts with the anomeric OH on glucose to form methyl glucoside (methyl-glucopyranose).Glycosidic Bonds The anomeric hydroxyl and a hydroxyl of another sugar or some other compound can join together.g. H OH H O HO HO H H H OH OH H H2O H OH H O HO HO H H OH OCH3 + CH3-OH -D-glucopyranose methanol methyl--D-glucopyranose .
a product of cellulose breakdown. a cleavage product of starch (e.C4 OH of 2 glucoses.g. .. The (1 4) glycosidic linkage is represented as a zig-zag. It is the anomer (C1 O points down). is the otherwise equivalent anomer (O on C1 points up). but one glucose is actually flipped over relative to the other. amylose). is a disaccharide with an (1 4) glycosidic link between C1 .Disaccharides: Maltose. 6 CH2OH 6 CH2OH H 4 5 O H 2 1 H H 4 5 O H 2 1 H H OH 3 H OH 3 OH O OH H 6 CH 2OH OH maltose H OH 6 CH 2OH H 4 5 O H 2 1 H O H 4 5 O H 2 1 OH H OH 3 H OH 3 OH H H OH cellobiose H OH Cellobiose.
the linkage is (12). milk sugar. is composed of galactose & glucose.) Lactose. Its full name is -D-galactopyranosyl-(1 4)-D-glucopyranose . has a glycosidic bond linking the anomeric hydroxyls of glucose & fructose. with (14) linkage from the anomeric OH of galactose.Other disaccharides include: Sucrose. Because the configuration at the anomeric C of glucose is (O points down from ring). common table sugar. The full name of sucrose is -D-glucopyranosyl-(12)-D-fructopyranose.
CH2OH H OH H OH O H OH H 1 H O H 6CH OH 2 5 O 4 OH 3 CH2OH H O H O H OH H H O OH H H CH2OH O H OH H H OH H O H CH2OH O H OH H H OH OH H H H 1 2 H OH amylose Polysaccharides: Plants store glucose as amylose or amylopectin. . Glucose storage in polymeric form minimizes osmotic effects. The end of the polysaccharide with an anomeric C1 not involved in a glycosidic bond is called the reducing end. glucose polymers collectively called starch. Amylose is a glucose polymer with (14) linkages.
. but it also has branches formed by (16) linkages. Branches are generally longer than shown above.CH 2OH H H OH OH H CH 2OH H OH H OH O H OH H H O H OH CH 2OH O H OH H H O H H O H CH 2OH O H OH H H OH H 1 O 6 CH 2 5 H OH 3 H CH 2OH O H 2 OH 1 O H H O H 4 OH H H amylopectin CH 2OH H O OH H O H OH H H OH OH H H O H 4 OH Amylopectin is a glucose polymer with mainly (14) linkages. The branches produce a compact structure & provide multiple chain ends at which enzymatic cleavage can occur.
the glucose storage polymer in animals. is similar in structure to amylopectin.. . e. The highly branched structure permits rapid glucose release from glycogen stores.g. in muscle during exercise.CH2OH H H OH OH H CH2OH H OH H OH O H OH H H O H OH CH2OH O H OH H H O H H O H CH2OH O H OH H H OH H 1 O 6 CH2 5 H OH 3 H CH2OH O H 2 OH 1 O H H O H 4 OH H H O OH H H glycogen CH2OH O H OH H H OH OH H H O H 4 OH Glycogen. But glycogen has more (16) branches. The ability to rapidly mobilize glucose is more essential to animals than to plants.
Schematic of arrangement of cellulose chains in a microfibril. website at Georgia Tech. See: Botany online website. a major constituent of plant cell walls. Every other glucose is flipped over. due to linkages. and pack with a crystalline arrangement in thick bundles .microfibrils. This promotes intra-chain and inter-chain H-bonds and van der Waals interactions. that cause cellulose chains to be straight & rigid.CH2OH H OH H OH O H OH H 1 H O H 6CH OH 2 5 O 4 OH 3 CH2OH H O H H OH O H OH H H O H CH2OH O H OH H H H OH O H CH2OH O H OH H H H OH OH H H 1 2 H OH cellulose Cellulose. . consists of long linear chains of glucose with (14) linkages.
which can withstand high hydrostatic pressure gradients. These microfibrils are very strong. . Osmotic swelling is prevented. Explore and compare structures of amylose & cellulose using Chime.CH2OH H OH H OH O H OH H 1 H O H 6CH OH 2 5 O 4 OH 3 CH2OH H O H H OH O H OH H H O H CH2OH O H OH H H H OH O H CH2OH O H OH H H H OH OH H H 1 2 H OH cellulose Multisubunit Cellulose Synthase complexes in the plasma membrane spin out from the cell surface microfibrils consisting of 36 parallel. interacting cellulose chains. The role of cellulose is to impart strength and rigidity to plant cell walls.
Glycosaminoglycans tend to be negatively charged. The constituent monosaccharides tend to be modified. with acidic groups.D-glucuronate 6COO 6 CH2OH 5 H O H 2 1 4 O H 1 O H H 4 5 H OH 3 OH O 3 2 H H H NHCOCH3 H OH N-acetyl-D-glucosamine hyaluronate Glycosaminoglycans (mucopolysaccharides) are linear polymers of repeating disaccharides. because of the prevalence of acidic groups. etc. sulfated hydroxyl and amino groups. . amino groups.
D-glucuronate 6COO 6 CH2OH 5 H O H 2 1 4 O H 1 O H H 4 5 H OH 3 OH O 3 2 H H H NHCOCH3 H OH N-acetyl-D-glucosamine hyaluronate Hyaluronate (hyaluronan) is a glycosaminoglycan with a repeating disaccharide consisting of 2 glucose derivatives. . The glycosidic linkages are (13) & (14). glucuronate (glucuronic acid) & N-acetyl-glucosamine.
core protein heparan sulfate glycosaminoglycan transmembrane -helix cytosol Proteoglycans are glycosaminoglycans that are covalently linked to serine residues of specific core proteins. The glycosaminoglycan chain is synthesized by sequential addition of sugar residues to the core protein. .
D-glucuronate 6 CH2OH 5 Websites on: Aggrecan Aggrecan & versican.Some proteoglycans of the extracellular matrix bind non-covalently to hyaluronate via protein domains called link modules.: • Multiple copies of the aggrecan proteoglycan associate with hyaluronate in cartilage to form large complexes. E. H 4 6COO H O H 2 1 4 O H 1 O H 5 H OH 3 OH O 3 2 H H H NHCOCH3 H OH N-acetyl-D-glucosamine hyaluronate . another proteoglycan.g. binds hyaluronate in the extracellular matrix of loose connective tissues. • Versican.
. in segments of the polymer.iduronate-2-sulfate H H COO OH O H H H OSO3 N-sulfo-glucosamine-6-sulfate CH2OSO3 H O H OH O H O H NHSO3 H heparin or heparan sulfate . Later.examples of residues Heparan sulfate is initially synthesized on a membraneembedded core protein as a polymer of alternating N-acetylglucosamine and glucuronate residues. while N-acetylglucosamine residues may be deacetylated and/or sulfated. glucuronate residues may be converted to the sulfated sugar iduronic acid.
but is more highly sulfated. When released into the blood.PDB 1RID Heparin. . Heparin has an extended helical conformation. Heparin shown has 10 residues. has a structure similar to that of heparan sulfates. heparin: (IDS-SGN)5 C O N S Charge repulsion by the many negatively charged groups may contribute to this conformation. a soluble glycosaminoglycan found in granules of mast cells. it inhibits clot formation by interacting with the protein antithrombin. alternating IDS (iduronate2-sulfate) & SGN (N-sulfo-glucosamine-6-sulfate).
. core protein heparan sulfate glycosaminoglycan transmembrane -helix cytosol The core protein of a syndecan heparan sulfate proteoglycan includes a single transmembrane -helix. as in the simplified diagram above.Some cell surface heparan sulfate glycosaminoglycans remain covalently linked to core proteins embedded in the plasma membrane. The core protein of a glypican heparan sulfate proteoglycan is attached to the outer surface of the plasma membrane via covalent linkage to a modified phosphatidylinositol lipid.
H COO O H Diagram by Kirkpatrick & Selleck..examples of residues .Proteins involved in signaling & adhesion at the cell surface recognize & bind heparan sulfate chains. e. Regulated cell surface Sulf enzymes may remove sulfate groups at particular locations on heparan sulfate chains to alter affinity N-sulfo-glucosamine-6-sulfate iduronate-2-sulfate for signal CH2OSO3 H proteins.g.g. O H H growth factors.. binding of some growth factors (small proteins) to cell surface receptors is enhanced by their binding also to heparan sulfates. E. OH H H H OSO3 H NHSO3 O OH H O heparin or heparan sulfate .
O-linked oligosaccharides have roles in recognition. They link to a protein via a glycosidic bond between a sugar residue & a serine or threonine OH. H H OH OH H H serine residue HN C CH3 -D-N-acetylglucosamine O-linked oligosaccharide chains of glycoproteins vary in complexity.CH2OH C O O CH2 CH NH O H O Oligosaccharides that are covalently attached to proteins or to membrane lipids may be linear or branched chains. interaction. . and enzyme regulation.
with these 2 modifications having opposite regulatory effects (stimulation or inhibition).CH2OH H H OH OH H HN O H O H C CH3 O CH2 C CH NH O serine residue -D-N-acetylglucosamine N-acetylglucosamine (GlcNAc) is a common O-linked glycosylation of protein serine or threonine residues. including enzymes & transcription factors. . Often attachment of GlcNAc to a protein OH alternates with phosphorylation. are regulated by reversible GlcNAc attachment. Many cellular proteins.
. First N-acetylglucosamine is linked to a protein via the side-chain N of an asparagine residue in a particular 3-amino acid sequence.CH2OH H H OH OH H HN C O O H H HN O C CH2 HN CH C HN HC C HN HC C R O R O O Asn CH3 X N-acetylglucosamine Initial sugar in N-linked glycoprotein oligosaccharide Ser or Thr N-linked oligosaccharides of glycoproteins tend to be complex and branched.
to yield a characteristic branched structure. and the N-linked oligosaccharide chain is modified by removal and addition of residues. .NAN Gal NAG Man NAN Gal NAG NAN Gal NAG Man N-linked oligosaccharide Key: NAN = N-acetylneuraminate Gal = galactose NAG = N-acetylglucosamine Man = mannose Fuc = fucose Man NAG NAG Fuc Asn Additional monosaccharides are added.
They have roles in cell-cell interaction and signaling. and in forming a protective layer on the surface of some cells. Such diseases. Carbohydrate chains of plasma membrane glycoproteins and glycolipids usually face the outside of the cell. and gene knockout studies in mice. have been used to define pathways of modification of oligosaccharide chains of glycoproteins and glycolipids.Many proteins secreted by cells have attached N-linked oligosaccharide chains. Genetic diseases have been attributed to deficiency of particular enzymes involved in synthesizing or modifying oligosaccharide chains of these glycoproteins. .
Concanavalin A & wheat germ agglutinin are plant lectins that have been useful research tools. Recognition/binding of CHO moieties of glycoproteins. . glycolipids & proteoglycans by animal lectins is a factor in: • cell-cell recognition • adhesion of cells to the extracellular matrix • interaction of cells with chemokines and growth factors • recognition of disease-causing microorganisms • initiation and control of inflammation.Lectins are glycoproteins that recognize and bind to specific oligosaccharides. The C-type lectin-like domain is a Ca++-binding carbohydrate recognition domain in many animal lectins.
.Examples of animal lectins: Mannan-binding lectin (MBL) is a glycoprotein found in blood plasma. It binds cell surface carbohydrates of disease-causing microorganisms & promotes phagocytosis of these organisms as part of the immune response.
. A cytosolic domain participates in regulated interaction with the actin cytoskeleton. outside The C-type lectin-like domain is at the end of a multi-domain cytosol extracellular segment extending out from the cell surface. selectin lectin domain transmembrane -helix cytoskeleton binding domain A cleavage site just outside the transmembrane -helix provides a mechanism for regulated release of some lectins from the cell surface.Selectins are integral proteins of mammalian cell plasma membranes with roles in cell-cell recognition & binding.
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