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Carbohydrates 2011
Carbohydrates 2011
Carbohydrates 2011
Roles of Carbohydrates
Storage of metabolic fuel Structural framework of nucleic acids Structural elements in the cell walls of bacteria and plants Linked to proteins and lipids which are involved in cell recognition
Monosaccharides Stereoisomers
OPTICAL ISOMERS
Stereosiomers can be distinguished using plane of polarized light
Naming stereoisomers
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
D- sugars are the most common carbohydrates. D-refers to the right hand orientation of the OH on the chiral carbon farthest from the carbonyl carbon L-sugars: L refers to the left hand orientation of the OH on the chiral carbon farthest from the carbonyl carbon
EXERCISE
Draw the possible structure(s) of 1. aldotetrose 2. ketotetrose
Glucose
H O C H HO H H C C C C OH H OH OH
The most common sugar Known as dextrose Also known as blood sugar
CH2OH
D-glucose
Galactose
One of the monosaccharides in the disaccharide lactose Found in plant gums and pectins polysaccharides An epimer of glucose at C4 Converted to glucose during metabolism
Fructose
One monosaccharide in the disaccharide sucrose (table sugar). Called levulose or fruit sugar Found in honey and fruits Sweeter than sucrose and glucose Commercially prepared as highfructose sugars from corn starch for sweetness An epimer of glucose at C2 Readily converted to glucose in metabolism by isomerization
CH2OH C O HO H H C C C H OH OH
CH2OH
D-fructose
Because of the tetrahedral nature of carbon bonds, pyranose sugars actually assume a "chair" or "boat" configuration, depending on the sugar. The representation above reflects the chair configuration of the glucopyranose ring more accurately than the Haworth projection.
CH2OH O H HOH2C 6 OH
5
2C
HO H H
C C C
O H HO
3
1 CH2OH 2
4 5 6
OH
OH
OH
CH2OH
D-fructose (linear)
E-D-fructofuranose
a 6-member pyranose ring, by reaction of the C2 keto group with the OH on C6, or a 5-member furanose ring, by reaction of the C2 keto group with the OH on C5.
The formation of hemiketals and hemiacetals results in an asymmetric carbon atom. Isomers that differ only in their configuration about the new asymmetric carbon are called anomers, the new assymetric carbon is called anomeric carbon. a-anomer has the hydroxyl group at the right side of the anomeric carbon F-anomer has the hydroxyl group at the left side of the anomeric carbon
Anomers in aqueous solution freely interconvert between the E and F forms, unless the hydroxyl group attached to the anomeric carbon is linked to another molecule. This process of interconvertion is called MUTAROTATION
EXERCISE
D-Mannose exists in aqueous solution as a mixture of E and F forms. Draw the Haworth projection formula of the two anomers.
Reactions of Monosaccharides
Oxidation-Reduction
Oxidation
H HO H H
COOH HO HO
O OH OH
Reduction to alditol
Esterification
Amino Derivatives
Formation of Glycosides
Treatment of a monosaccharide, all of which exist almost exclusively in a cyclic hemiacetal form, with an alcohol gives an acetal
CH 2 OH O OH H + H H + CH3 OH OH H -H2 O HO H glycos idic H OH CH2 OH bond F-D -Glu copyran os e O OCH 3 H (F-D -Glu cose) H + OH H H HO anomeric carbon
CH2 OH OH H H OH H HO OCH 3
H OH H OH Methyl F-D -glu copyran os ide Methyl E-D -glu copyran os ide (Methyl F-D -glu coside) (Methyl E-D -glucos ide)
Disaccharides
Maltose present in malt, the juice from sprouted barley and other cereal grains maltose consists of two units of Dglucopyranose joined by an E-1,4glycosidic bond maltose is a reducing sugar
Lactose
lactose is the principal sugar present in milk; it makes up about 5 to 8 percent of human milk and 4 to 6 percent of cow's milk it consists of D-galactopyranose bonded by a F -1,4-glycosidic bond to carbon 4 of Dglucopyranose lactose is a reducing sugar
Sucrose
is the most abundant disaccharide in the biological world; it is obtained principally from the juice of sugar cane and sugar beets sucrose is a nonreducing sugar
N-Glycosides
EXERCISE
A. Draw the chair conformations for E-D mannopyranose and F-D-mannopyranose B. Draw the chair conformation of 1. methyl E- and F-D-mannopyranoside 2. E-D-mannopyranosyl-(1-4)- F-Dglucopyranoside
Polysaccharides
Storage Polysaccharides
Glycogen
is the energy-reserve carbohydrate for animals glycogen is a branched polysaccharide of approximately 106 glucose units joined by E-1,4- and E-1,6-glycosidic bonds the total amount of glycogen in the body of a well-nourished adult human is about 350 g, divided almost equally between liver and muscle
Starch
starch can be separated into amylose and amylopectin amylose is composed of unbranched chains of up to 4000 D-glucose units joined by E-1,4-glycosidic bonds amylopectin contains chains up to 10,000 Dglucose units also joined by E-1,4-glycosidic bonds; at branch points, new chains of 24 to 30 units are started by E-1,6-glycosidic bonds
Structural Polysaccharides
Cellulose
is a linear polysaccharide of D-glucose units joined by F-1,4-glycosidic bonds it has an average molecular weight of 400,000 g/mol, corresponding to approximately 2200 glucose units per molecule cellulose molecules act like stiff rods and align themselves side by side into well-organized waterinsoluble fibers in which the OH groups form numerous intermolecular hydrogen bonds this arrangement of parallel chains in bundles gives cellulose fibers their high mechanical strength it is also the reason why cellulose is insoluble in water
Plant Polysaccharides
Pectin
Is a heteropolymer containing galacturonate and rhamnose residues Used a gelling agent in the preparation of jams and jellies
Chitin
Present in exoskeletons of arthropods Composed of N-acetylglucosamine, linked in F(1-4)
Peptidoglycan
is composed of an alternating sequence of Nacetyl-muraminic acid (NAM) and Nacetylglucosamine (NAG) joined by F-1,4glycosidic bonds.
CH 2 OH O O O H 3 C CH C= O NH L A la D Gln NH O= C CH 3 O HO
CH 2 OH O O N O= C CH 3
D A la O N H-( Gly) 5 C- - --
Glycoproteins
Components of the cell membrane, where they play variety of roles in cell adhesion
Glycoprotein Functions
Glycoproptein and Cancer Protein Turnover Viral Growth Antifreeze Glycoprotein
Protein glycosylation takes part in the lumen of the endoplasmic reticulum and in the golgi complex
Glycosaminoglycans (GAGs) are anionic polyanionic polysaccharides chains made of repeating disaccharide units
play important roles in the structure and function of connective tissues polysaccharides based on a repeating disaccharide where one of the monomers is an amino sugar and the other has a negative charge due to a sulfate or carboxylate group Glycosaminoglycans tend to be negatively charged, because of the prevalence of acidic groups. GAGs are usually attached to proteins to form proteoglycans
Common GAGs
heparin: natural anticoagulant hyaluronic acid: a component of the vitreous humor of the eye and the lubricating fluid of joints chondroitin sulfate and keratan sulfate: : components of connective tissue
Chondroitin 6-sulfate
The repeating disaccharide units of Nacetylgalactosamine ang glucoronic acid can be sulfated in either 4 or 6 position of GalNAc They are prominent components of cartilage tendons, ligaments and aorta Palate is made from chondroitin sulfate
LECTINS
Proteins that bind specific carbohydrate structures Are ubiquitous, being found in plants, animals and microorganisms