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Sources of Carbohydrates
Photosynthesis
6CO2 + 6H2O + 673 Kcal C6H12O6 + 6O2
Water 54% Fat 26% Protein 15% Ash 4.6% Carbohydrate <1%
Carbohydrates (CHO)
Sources
Sugars, starch, cellulose, gums
Carbohydrates
Aldehyde
Ketone
Classification
Monosaccharides (CnH2nOn)
Classified by the number of carbon atoms: 3-C triose 4-C tetrose nutritionally 5-C pentose important 6-C hexose
Sugars that contain four or more carbons exist primarily in cyclic form
Monosaccharides
Pentoses (5C)
Component in hemicellulose, glycoproteins Found in every living cell Found in compounds involved in metabolism:
Ribose
Monosaccharides
Hexoses (6c)
Glucose
Component of starch, cellulose, and glycogen Major end-product of carbohydrate digestion in monogastrics Primary form of sugar used for energy
Glucose, fructose, and galactose are among the most important monosaccharides in living organisms
Monosaccharides
Hexoses (6c)
Fructose
75% of sugars in honey Found in fruits and cane sugar Component of milk sugar (lactose) May be metabolized to glucose
Found after hydrolysis of plant mannosans and gums; legumes
Galactose
Mannose
Disaccharides
Disaccharides
Common table sugar Produced in leaves and stems of plants Found in sugar cane and sugar beets
Disaccharides
Oligosaccharide
Polysaccharide
Polysaccharides
Starch
Starch granules
Starch
Apha 1-4 linkages Straight chain 14-30% of total plant starch Water soluble
Starch
2. Amylopectin Alpha 1-4 linkages with alpha 1-6 linkage at branch points 70-85% total plant starch Not water soluble
Starch
3. Glycogen Animal starch Small amounts in liver and muscle Highly branched Water soluble
Carbohydrates
General characteristics
the term carbohydrate is derived from the french: hydrate de carbone compounds composed of C, H, and O (CH2O)n when n = 5 then C5H10O5 not all carbohydrates have this empirical formula: deoxysugars, aminosugars carbohydrates are the most abundant compounds found in nature (cellulose: 100 billion tons annually)
General characteristics
Most carbohydrates are found naturally in bound form rather than as simple sugars
Polysaccharides (starch, cellulose, inulin, gums) Glycoproteins and proteoglycans (hormones, blood group substances, antibodies) Glycolipids (cerebrosides, gangliosides) Glycosides Mucopolysaccharides (hyaluronic acid) Nucleic acids
Functions
sources of energy intermediates in the biosynthesis of other basic biochemical entities (fats and proteins) associated with other entities such as glycosides, vitamins and antibiotics) form structural tissues in plants and in microorganisms (cellulose, lignin, murein) participate in biological transport, cell-cell recognition, activation of growth factors, modulation of the immune system
Classification of carbohydrates
Trioses, tetroses, pentoses, hexoses Di, tri, tetra, penta, up to 9 or 10 Most important are the disaccharides Homopolysaccharides Heteropolysaccharides Complex carbohydrates
Oligosaccharides
Polysaccharides or glycans
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.
Monosaccharides
Aldoses (e.g., glucose) have an aldehyde group at one end.
H C H HO H H C C C C OH H OH OH
HO H H
CH2OH
CH2OH
D-glucose
D-fructose
D vs L Designation
D & L designations are based on the configuration about the single asymmetric C in glyceraldehyde. The lower representations are Fischer Projections.
CHO H C OH HO CHO C H
CH2OH
CH2OH
D-glyceraldehyde
CHO H C OH
L-glyceraldehyde
CHO HO C H
CH2OH
CH2OH
D-glyceraldehyde
L-glyceraldehyde
Sugar Nomenclature
For sugars with more than one chiral center, D or L refers to the asymmetric C farthest from the aldehyde or keto group.
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
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, where n is the number of asymmetric centers. The 6-C aldoses have 4 asymmetric centers. Thus there are 16 stereoisomers (8 D-sugars and 8 Lsugars).
R'
OH
R'
C R
OH
aldehyde
R
alcohol
hemiacetal
R
C R'
"R
OH
"R
C R'
OH
ketone
alcohol
hemiketal
Pentoses and H C OH 2 hexoses can HO C H D-glucose cyclize as the 3 H C OH (linear form) ketone or 4 aldehyde reacts H C OH 5 with a distal OH. CH2OH 6 Glucose forms an 6 CH2OH 6 CH2OH intra-molecular 5 5 O O H H H hemiacetal, as H H 4 1 4 H H OH OH the C1 aldehyde OH OH 2 & C5 OH react, OH 3 2 3 H OH H OH to form a 6-D-glucose -D-glucose member pyranose ring, named after of the cyclic sugars are called These representations pyran. projections. Haworth
1
CHO
OH
1
CH2OH O H OH OH HOH2C 6
5
2C
HO H H
C C C
O H HO
3
1 CH2OH 2
4 5 6
CH2OH
OH
OH
D-fructose (linear)
-D-fructofuranose
Fructose forms either 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.
6 CH 2OH
6 CH 2OH
H
4
O H
2
H
1
H
4
O H
2
OH
1
H OH
3
H OH
3
OH
OH
OH
OH
OH
-D-glucose
-D-glucose
Cyclization of glucose produces a new asymmetric center at C1. The 2 stereoisomers are called anomers, & . Haworth projections represent the cyclic sugars as having essentially planar rings, with the OH at the anomeric C1: (OH below the ring)
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, 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.
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
sugar alcohol - lacks an aldehyde or ketone; e.g., ribitol. sugar acid - the aldehyde at C1, or OH at C6, is oxidized to a carboxylic acid; e.g., gluconic acid,
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 - an amino group substitutes for a hydroxyl. An example is glucosamine. The amino group may be acetylated, as in N-acetylglucosamine.
O H3C C NH
H O R H H OH H H OH COO HC R= HC OH OH
CH2OH
N-acetylneuraminate (N-acetylneuraminic acid, also called sialic acid) is often found as a terminal residue of oligosaccharide chains of glycoproteins. Sialic acid imparts negative charge to glycoproteins, because its carboxyl group tends to dissociate a proton at physiological pH, as shown here.
Glycosidic Bonds
The anomeric hydroxyl and a hydroxyl of another sugar or some other compound can join together, splitting out water to form a glycosidic bond: R-OH + HO-R' R-O-R' + H2O E.g., methanol reacts with the anomeric OH on glucose to form methyl glucoside (methylglucopyranose).
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
Fisher projection: straight chain representation Haworth projection: simple ring in perspective Conformational representation: chair and boat configurations
if the substituent is to the right in the Fisher projection, it will be drawn down in the Haworth projection (Down-Right Rule)
for D-sugars the highest numbered carbon (furthest from the carbonyl) is drawn up. For L-sugars, it is drawn down for D-sugars, the OH group at the anomeric position is drawn down for and up for . For L-sugars is up and is down
Optical isomerism
A property exhibited by any compound whose mirror images are nonsuperimposable Asymmetric compounds rotate plane polarized light
POLARIMETRY
Measurement of optical activity in chiral or asymmetric molecules using plane polarized light Molecules may be chiral because of certain atoms or because of chiral axes or chiral planes
Measurement uses an instrument called a polarimeter (Lippich type) Rotation is either (+) dextrorotatory or (-) levorotatory
polarimetry
Magnitude of rotation depends upon:
1. the nature of the compound
2. the length of the tube (cell or sample container) usually expressed in decimeters (dm) 3. the wavelength of the light source employed; usually either sodium D line at 589.3 nm or mercury vapor lamp at 546.1 nm 4. temperature of sample
[]
D = Na D line T = temperature oC obs : observed rotation in degree (specify solvent) l = length of tube in decimeter c = concentration in grams/100ml [] = specific rotation
D-glucose D-fructose D-galactose L-arabinose D-mannose D-arabinose D-xylose Lactose Sucrose Maltose+ Invert sugar Dextrin
+52.7 -92.4 +80.2 +104.5 +14.2 -105.0 +18.8 +55.4 +66.5 +130.4 -19.8 +195
Disaccharides:
Maltose, a cleavage product of starch (e.g., amylose), is a disaccharide with an (1 4) glycosidic link between C1 - C4 OH of 2 glucoses. It is the anomer (C1 O points down).
6 CH2OH
6 CH2OH
H
4
O H
2 1
H
4
O H
2 1
H OH
3
H OH
3
OH
OH
H
6 CH 2OH
OH
maltose
OH
6 CH 2OH
H
4
O H
2 1
H O H
4
O H
2 1
OH
H OH
3
H OH
3
OH
OH
cellobiose
OH
Cellobiose, a product of cellulose breakdown, is the otherwise equivalent anomer (O on C1 points up). The (1 4) glycosidic linkage is represented as a zigzag, but one glucose is actually flipped over relative
Sucrose, common table sugar, has a glycosidic bond linking the anomeric hydroxyls of glucose & fructose. Because the configuration at the anomeric C of glucose is (O points down from ring), the linkage is (12). The full name of sucrose is -D-glucopyranosyl(12)--D-fructopyranose.)
Lactose, milk sugar, is composed of galactose & glucose, with (14) linkage from the anomeric OH of galactose. Its full name is -D-
CH2OH H OH H OH O H OH H
1
H O
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 1
2
OH
amylose
Polysaccharides:
Plants store glucose as amylose or amylopectin, glucose polymers collectively called starch.
Glucose storage in polymeric form minimizes osmotic effects. Amylose is a glucose polymer with (14) linkages. It adopts a helical conformation.
The end of the polysaccharide with an anomeric C1 not involved in a glycosidic bond is called the
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, but it also has branches formed by (16) linkages. Branches are generally longer than shown above. The branches produce a compact structure & provide multiple chain ends at which enzymatic cleavage can
glycogen
CH2OH O H OH H H OH OH H
H O
H 4
OH
Glycogen, the glucose storage polymer in animals, is similar in structure to amylopectin. But glycogen has more (16) branches. The highly branched structure permits rapid glucose release from glycogen stores, e.g., in muscle during exercise. The ability to rapidly mobilize glucose is more essential to animals than to plants.
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 1
2
OH
cellulose
Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with (14) linkages. Every other glucose is flipped over, due to linkages.Waals interactions, van der that promotes intra-chain This cause cellulose chainsand inter-chain H-bonds to be and straight & rigid, and pack with a crystalline arrangement in thick bundles - microfibrils. Schematic of arrangement of cellulose chains in a microfibril. See: Botany online
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 1
2
OH
cellulose
Multisubunit Cellulose Synthase complexes in the plasma membrane spin out from the cell surface microfibrils consisting of 36 parallel, interacting cellulose chains. These microfibrils are very strong.
The role of cellulose is to impart strength and rigidity to plant cell walls, which can withstand high hydrostatic pressure gradients. Osmotic swelling is prevented.