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Important Point:
Polymers / Monomers
Many macromolecules consist of polymers A polymer is a large molecule built up from smaller building block molecules Monomers (a.k.a., subunits) are the building block molecules Small molecules common to all organisms are ordered into unique macromolecules . . . For each class (of compound) we will see that the macromolecules have emergent properties not found in their individual monomers.
carbohydrates monosaccharides
proteins RNA & DNA amino acids nucleotides
Chapter Carbohydrates
Carbohydrates
composition:
have
the
following
basic
(CH2O)n
I or H - C - OH I
Carbohydrates
Carbohydrates are The hydrates of carbon Carbohydrates often written as COH Basic chemical structure consists of sugar units Found as aldehydes or ketones derived from polyhydric alcohols A major source of energy from our diet. Composed of the elements C, H, and O. SARKARA (Sanskrit), SAKCHARON (Greek), SACCHARUM (Latin)
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Carbohydrates
Carbohydrates Also called saccharides, which means sugars. often shown as aliphatic or linear structures, but exist in nature as ringed structures Are produced by photosynthesis in plants. Such as glucose are synthesized in plants from CO2, H2O, and energy from the sun. Are oxidized in living cells (respiration) to produce CO2, H2O, and energy.
7
Types of Carbohydrates
The types of carbohydrates are (Usually by the number of sugar units in the molecule)
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.
Monosaccharides
Monosaccharides (simple sugars) cannot be broken down into simpler sugars under mild conditions, are consist of 3 to 6 carbon atoms, typically. A carbonyl group (aldehyde or ketone). Several hydroxyl groups. Aldoses and ketoses contain aldehyde and ketone functions, respectively. Triose, tetrose, etc. Denotes number of carbons. Aldoses with 3c or more and ketoses with 4c or more are chiral. Most (99%) are straight chain compounds D-glyceraldehyde is the simplest of the aldoses (aldotriose) All other sugars have the ending ose (glucose, galactose, ribose, lactose, etc)
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11
Monosaccharides Nomenclature
Functional group
Ketone
Number of carbons
4 5 6 7 8
Aldoses
Aldoses are monosaccharides O With an aldehyde group at the end. CH aldose With many hydroxyl (OH) groups. H COH triose (3 C atoms) tetrose (4 C atoms) H COH pentose (5 C atoms) CH2OH hexose (6 C atoms) Erythose, an aldotetrose
13
Aldose sugars
H C (H C O OH)n H H C C O OH H H H C C C O OH OH H H H H C C C C O OH OH OH H H H H H C C C C C O OH OH OH OH
CH2OH Aldose
Ketoses
Ketoses are monosaccharides CH2OH With a ketone group, C=O ketose usually at C2. With many hydroxyl (OH) H COH groups. triose (3 C atoms) tetrose (4 C atoms) pentose (5 C atoms) hexose (6 C atoms)
H COH HCOH CH2OH
Fructose, a ketohexose
16
Ketose sugars
CH2OH C (H C O OH)n
CH2OH C O H
CH2OH C C O OH H H
CH2OH C C C O OH OH H H H C CH2OH C C O OH OH OH
CH2OH
Learning Check
Identify each as aldo- or keto- and as tetrose, pentose,
or hexose:
O C H H C OH H C OH H C OH H C OH CH2OH
CH2OH C O HO C H H C OH CH2OH
B
19
Solution
A. aldohexose B. ketopentose
20
Chapter Carbohydrates
Structures of Monosaccharides
Fisher projection: straight chain representation Haworth projection: simple ring in perspective Conformational representation: chair and configurations
boat
21
Some Monosaccharides
Some Monosaccharides
All carbons in a monosaccharide are bonded to a hydroxyl group (-OH) except for one which is bonded to a carbonyl group (=O) (note that this statement is true only for the linear form of monosaccharides)
Chiral Carbons
A carbon is chiral if it has four different groups Chiral compounds have the same composition but are not superimposable Display in Fisher projection
CHO H OH CH2OH
D-glyceraldehyde
ENANTIOMERS
CHO HO H CH2OH
L-glyceraldehyde
Some Monosaccharides
2 | 1C3 | 4
2 | 3C1 | 4
26
Fischer Projections
A Fischer projection Is used to represent carbohydrates. Places the most oxidized group at the top. Shows chiral carbons as the intersection of vertical and horizontal lines.
27
D and L Notations
D & L designations are based on the configuration about the single asymmetric C in glyceraldehyde. For sugars with more than one chiral center, in a Fischer projection, the OH group on the Chiral carbon farthest from the carbonyl group determines an L or D isomer. Left is assigned the letter L for the L-isomer. Right is assigned the letter D for the D-isomer.
28
D and L Notations
D & L sugars are mirror images of one another. They have the same name, e.g., D-glucose & L-glucose. Other stereoisomers have unique names, e.g., glucose, mannose, galactose, etc. Vant Hoffs Rule: 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 L-sugars).
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
29
O C H O C H H OH H OH H OH CH2OH
D-ribose
OH H OH OH CH2OH
HO H H HO
H OH OH H CH2OH
L-galactose
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Learning Check
Identify each as the D or L isomer. A. B.
O C H HO HO HO H H H CH2OH H HO O C H OH H CH2OH HO H H
C.
CH2OH O H OH OH CH2OH
__-ribose
__- threose
__- fructose
31
Solution
Identify each as the D or L isomer. A. B.
O C H HO HO HO H H H CH2OH H HO O C H OH H CH2OH HO H H
C.
CH2OH O H OH OH CH2OH
L-ribose
L-threose
D-fructose
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More Stereochemistry
Know these definitions Stereoisomers that are mirror images of each other are enantiomers. Pairs of isomers that have opposite configurations at one or more chiral centers but are NOT mirror images are diastereomers. Two sugars that differ in configuration at only one chiral center are epimers.
Epimers
CHO H H H OH OH OH CH 2OH HO H H
CHO H OH OH CH 2OH
HO H H H
CHO OH H OH OH CH 2OH HO HO H H
CHO H H OH OH CH 2OH H HO HO H
CHO OH H H OH CH 2OH
D-arabinose
D-glucose
D-mannose
D-galactose
34
35
36
D-Galactose
D-galactose is
O C H H C OH HO C H HO C H H C OH CH2OH D-Galactose
An aldohexose C6H12O6. Not found free in nature. Obtained from lactose, a disaccharide. A similar structure to glucose except for the OH on C4.
38
Learning Check
Draw the structure and Fischer projection of D-fructose.
39
Solution
CH2OH C O HO C H H C OH H C OH CH2OH D-Fructose
H H OH OH CH2OH Fischer projection HO CH2OH C=O H
40
Chapter Carbohydrates
Cyclic Structures of Monosaccharides
CH2OH O OH OH
OH
OH
PYRAN
FURAN
41
R'
OH
R'
C R
OH
aldehyde
R C R' O
alcohol
hemiacetal
R
"R
OH
"R
C R'
OH
ketone
alcohol
hemiketal
Anomeric Carbon --- The carbon atom which is involved in hemiacetal or acetal formation.
Cyclic Structures
Pentoses and hexoses can cyclize as the ketone or aldehyde reacts with a distal OH. Glucose forms an intramolecular hemiacetal, as the C1 aldehyde & C5 OH react, to form a 6member pyranose ring, named after pyran.
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
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
Cyclic Structures
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.
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
Anomers
Anomers are two sugars that differ in configuration only at the C that was the carbonyl carbon in the open chain form. Ano gr: for upper Anomers like epimers are a kind of diastereomers.
45
Cyclic Structures
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: For D-sugars, has OH down, has OH up. For L-sugars, the reverse is true.
6 CH 2OH 6 CH 2OH 5 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
Optical Isomerism
A property exhibited by any compound whose mirror images are non-superimposable Asymmetric compounds rotate plane polarized light Enantiomers - Optical isomers rotate the beam of plane-polarized light for the same angle, but in opposite direction Rotation is either (+) dextrorotatory or (-) levorotatory Equimolar mixture of optical isomers has no optical activity - racemic mixture Measurement of optical activity in chiral or asymmetric molecules using plane polarized light Molecules may be chiral because of certain atoms 48or because of chiral axes or chiral planes
Mutarotation
Process by which various anomeric forms attain an equilibrium in solution Change in optical activity of a optically active compound in solution.
The optical rotation of glucose solution could change with time. It involves interconversion of - and -D-glucose.
[]D20 = 112.2 for -D-glucose []D20 = 18.7 for -D-glucose - D - glucose -> D glucose <- - D glucose 20D = 113 20D = 52 20D = 19
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Mutarotation
~37%
<<1%
0.0026%
~63%
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Cyclic Structures
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.
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
Cyclic Structures
Cyclic structures Are the prevalent form of monosaccharides with 5 or 6 carbon atoms.
O O
Form when the hydroxyl group on C-5 reacts with the aldehyde group or ketone group.
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CH2OH O
53
drawing
Haworth
drawing
Haworth
If the substituent is to the right in the fisher projection, it will be drawn down in the haworth projection (down-right rule)
drawing
Haworth
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
C
1
H C OH
2
H
6 5
H OH H
4 3 2 1
HO 3 C H H 4 C OH H 5 C OH
6 CH2OH
O H
HOCH2 C C C C C OH OH H OH
57
CH2OH
6 5 4
O
1
OH
OH
3
OH OH
58
O
OH OH OH OH
OH
O OH
OH OH
-D-glucose
-D-glucose
59
60
-Glucose
-Glucose
61
CH2OH O OH
OH
H O C H
CH2OH O OH OH
OH
OH OH
OH
-D-glucose (36%)
OH -D-glucose (64%)
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D-fructose
-D-fructose
-D-fructose
63
Learning Check
Write the cyclic form of -D-galactose
O C H H C OH HO C H HO C H H C OH CH2OH
64
Solution
CH2OH OH OH OH O
OH
-D-galactose
65
Chapter Carbohydrates
Chemical Properties of Monosaccharides
67
Reducing Sugars
Are monosaccharides with a carbonyl group that oxidizes to give a carboxylic acid. Sugars with free anomeric carbons Undergo reaction with benedicts reagent (cu2+) to give the corresponding carboxylic acid. Fehlings reagent: CuSO4 (blue) + RC(=O)H Cu2O (red) + RCO2 Tollens reagent: Ag+ Ag0 Include the monosaccharides glucose, galactose, and fructose.
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Oxidation of D-Glucose
O C H
Benedicts reagent
O C OH H C OH
[O]
H C OH HO C H H C OH H C OH CH2OH D-glucose
+ Cu
2+
+ Cu2O(s)
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Reduction of Monosaccharides
The reduction of monosaccharides Involves the carbonyl group. Produces sugar alcohols called alditols. Such as D-glucose gives D-glucitol also called sorbitol.
D-Glucitol
70
Learning Check
Write the products of the oxidation and reduction of D-mannose.
O C H HO HO H H H H OH OH CH2OH
D-mannose
71
Solution
Write the products of the oxidation and reduction of D-mannose.
O CH2OH HO HO H H H H OH OH CH2OH
D-mannitol
O C OH Oxidation HO HO H H H H OH OH CH2OH
D-mannonic acid
72
C H Reduction HO HO H H H H OH OH CH2OH
D-mannose
Chapter Carbohydrates
Sugar Derivatives
73
Sugar derivatives
COOH
CH2OH H H H C C C OH
CHO H HO H H C C C C OH H OH OH
H HO
C C C C
OH H OH OH
OH
H
OH
H
CH2OH
D-ribitol
CH2OH
COOH
sugar alcohol (alditols) - 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, glucuronic 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 Nacetylglucosamine.
Sugar derivatives
O H3C C NH R H H OH H H O 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.
Sugar derivatives
Deoxy sugars: These are monosaccharides which lack one or more hydroxyl groups on the molecule; example: 2-deoxy ribose - constituents of DNA, 6deoxy-L-mannose (L-rhamnose) is used as a fermentative reagent in bacteriology, etc. Sugar esters: phosphate esters like ATP are important. Acetals, ketals and glycosides: basis for oligo- and poly-saccharides.
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Chapter Carbohydrates
Glycosidic Bonds
78
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 (methyl-glucopyranose).
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
Glycosidic Bonds
with hemiacetal hydroxyl of other saccharide
nonreducing disaccharides
with other then hemiacetal hydroxyl of other saccharide
reducing disaccharides
with nonsugar hydroxyl (alcohol, sterol, heterocycle)
O-glycosides
with amino(imino) group
N-glycosides
80
Glycosidic Bonds
When an anomeric carbon participates in a glycosidic bond, it cannot be oxidized by ferric or cupric ion.
The sugar containing that anomeric carbon cannot exist in linear form and can no longer act as a reducing sugar. reducing end: the end of a chain with a free anomeric carbon
81
Chapter Carbohydrates
Disaccharides
82
Important Disaccharides
A disaccharide Consists of two monosaccharides. 2 sugars joined by a condensation reaction to form a glycosidic bond Monosaccharides Disaccharide Glucose + glucose maltose + H2O Glucose + galactose lactose + H2O Glucose + fructose sucrose + H2O
83
Formation of Maltose
Reducing end
85
Cellobiose
Cellobiose is A disaccharide Composed of two D-glucose molecules. Obtained from the hydrolysis of cellulose. Linked by an -1,4-glycosidic bond formed from the OH on C1 of the first glucose and OH on C4 of the second glucose. The -1,4-glycosidic linkage is represented as a zig-zag, but one glucose is actually flipped over relative to the other. Reducing sugar Shows mutarotation Its full name is -D-glucopyranosyl-(14)--D86 glucopyranose
Formation Of Cellobiose
6 CH 2OH
6 CH 2OH
H
4
O H
2 1
H O H
4
O H
2 1
OH
H OH
3
H OH
3
Reducing end
H
OH
OH
cellobiose
OH
Formation of Lactose
Reducing end
Formation of Sucrose
Formation of Sucrose
Note that Fru has been flipped and that it is in the -position
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Trehalose
Trehalose is a disaccharide that occurs naturally in insects, plants, fungi, and bacteria. The major dietary source is mushrooms. Trehalose is used in bakery goods, beverages, confectionery, fruit jam, breakfast cereals, rice, and noodles as a texturizer, stabilizer, humectant, or formulation aid with a low sweetening intensity
CH2OH H O OH H HO H OH O HH H OH H OH H HOH2C O H
OH
93
TREHALOSE
Learning Check
Write the structures and names of the two monosaccharides that form when sucrose is hydrolyzed.
94
Solution
-D-glucose
-D-fructose
95
Learning Check
Identify the monosaccharides in each of the following: A. lactose (1) -D-glucose (2) -D-fructose (3) -D-galactose
B. maltose (1) -D-glucose (2) -D-fructose C. sucrose (1) -D-glucose (2) -D-fructose
(3) -D-galactose
(3) -D-galactose
96
Solution
Identify the monosaccharides in each of the following: A. lactose (1) -D-glucose (3) -D-galactose B. maltose (1) -D-glucose C. sucrose (1) -D-glucose
(2) -D-fructose
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Chapter Carbohydrates
Oligosaccharides
99
Raffinose
(Galactose + Glucose + Fructose)
Melbiose
Sucrose Moiety
100
Stachyose
(Galactose + Galactose + Glucose + Fructose)
Chapter Carbohydrates
Polysaccharides
102
Polysaccharides
Polysaccharides
Polysaccharides are polymers that form from monosaccharides through a condensation reaction between two hydroxyl groups to create a glycosidic linkage.
(1) The monomers joined by glycosidic linkages can be identical or different. (2) The glycosidic linkages can form between any two hydroxyl groups; so the location and geometry of these bonds vary widely. 103
Polysaccharides
characteristics:
polymers (MW from 200,000) White and amorphous products (glassy) not sweet not reducing; do not give the typical aldose or ketose reactions) form colloidal solutions or suspensions
104
Polysaccharides
Functions: storage, structure, recognition Nomenclature: homopolysaccharide vs. heteropolysaccharide. Lower the osmotic pressure. Starch and glycogen are energy storage molecules. Chitin and cellulose are structural molecules. Cell surface polysaccharides are recognition molecules.
105
Starch
Plants store glucose as amylose or amylopectin, glucose polymers collectively called starch. Most starch amylopectin. is 10-30% amylose and 70-90%
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.
Starch is used as an excipient, a binder in medications to aid the formation of tablets. Industrially it has many applications such as in adhesives, paper making, biofuel, textiles. 106
Structures of Amylopectin
Amylose
and
107
Amylose
Amylose is A polymer of -d-glucose molecules. Linked by -1,4 glycosidic bonds. A continuous (unbranched) chain. 200 to 20 000 glucose units helix
108
Amylopectin
Amylopectin Is a polymer of -D-glucose molecules. Is a branched-chain polysaccharide. Has -1,4-glycosidic bonds between the glucose units. Has -1,6 bonds to branches in every 12-30 residues. The branches produce a compact structure & provide multiple chain ends at which enzymatic cleavage can occur.
109
Starch
Amylose and amylopectin are poorly soluble in water, but form micellar suspensions. In these suspensions, amylose is helical and iodine fits into the helices to produce a blue color. Amylopectin produces a red-violet color with I2. Branches provide a mechanism for quickly releasing (or storing) glucose units for (or from) metabolism.
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Glycogen
Glycogen Is the polysaccharide that stores -Dglucose in muscle, the glucose storage polymer in animals. Is similar to amylopectin, but is more highly branched. Glycogen constitutes up to 10% of liver mass and 1-2% of muscle mass. Glycogen is stored energy for the organism. (1,6) branches every 8-12 residues . Like amylopectin, glycogen gives a redviolet color with iodine.
111
Glycogen
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 H OH OH H CH2OH H OH H OH O H OH H H O H OH CH2OH O H OH H H OH H O H 4 O H H O H H OH H CH2OH O 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 CH2OH O H OH H H OH OH
112
glycogen
more branching
Dextrans
A small but significant difference from starch and glycogen. If you change the main linkages between glucose from (1,4) to (1,6), you get a new family of polysaccharides dextrans. Branches can be (1,2), (1,3), or (1,4). Dextrans formed by bacteria are components of dental plaque. Cross-linked dextrans are used as "Sephadex" gels in column chromatography. used as plasma extenders (treatment of shock) 114 These gels are up to 98% water!
Structural Polysaccharides
Composition similar to storage polysaccharides, but small structural differences greatly influence properties. Cellulose is the most abundant natural polymer on earth. Cellulose is the principal strength and support of trees and plants . Cellulose can also be soft and fuzzy - in cotton.
115
116
Cellulose
Cellulose Is a polysaccharide of glucose units in unbranched chains. Has -1,4-glycosidic bonds. Cannot be digested by humans because humans cannot break down -1,4-glycosidic bonds.
117
Cellulose
Gives no color with iodine. A structural polysaccharide Yields glucose upon complete hydrolysis Partial hydrolysis yields cellobiose
118
Cellulose
Every other glucose is flipped over, due to linkages. This promotes intra-chain and inter-chain H-bonds and van der Waals interactions, that cause cellulose chains to be straight & rigid, and pack with a crystalline arrangement in thick bundles microfibrils. 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.
119
Cellulose
Cellulose
Cellulose is a Structural polysaccharide
Cellulose
Organisms that can digest cellulose include the microorganisms living the gastrointestinal tract of many organisms typified especially by cows and termites and many fungi (i.e., the things that eat the wood of fallen trees)
Chitin
Chitin is the second most abundant carbohydrate polymer Like cellulose, chitin is a structural polymer Present in the cell wall of fungi and in the exoskeletons of crustaceans, insects and spiders Chitin is used commercially in coatings (extends the shelf life of fruits and meats) A chitin derivative binds to iron atoms in meat and slows the rancidity process
123
Chitin
124
Learning Check
Identify the polysaccharides and types of glycosidic bonds in each of the following:
A.
B.
C.
125
Solution
A. Cellulose
B. Amylose Amylopectin C. Glycogen
-1,4-glycosidic bonds
-1,4-glycosidic bonds -1,4-and -1,6-glycosidic bonds -1,4-and -1,6-glycosidic bonds (more branched than amylopectin)
126
Polysaccharides: Unbranched
Branched
and
127
Polysaccharides: Unbranched
Branched
and
128
Polysaccharides: Unbranched
Branched
and
Polysaccharides: Unbranched
Branched
and
Mucopolysaccharides (Glycosaminoglycans)
Glycosaminoglycans (mucopolysaccharides) are linear polymers of repeating disaccharides. The constituent monosaccharides tend to be modified, with acidic groups, amino groups, sulfated hydroxyl and amino groups, etc. Glycosaminoglycans tend to be negatively charged, because of the prevalence of acidic groups.
131
Hyaluronate
Hyaluronate (hyaluronan) is a glycosaminoglycan with a repeating disaccharide consisting of 2 glucose derivatives, glucuronate (glucuronic acid) & N-acetylglucosamine. The glycosidic linkages are b(13) & b(14).
D-glucuronate
6COO
CH2OH
5
H O H
2 1 4
O H
1 O
H
4
H OH
3
OH O
NHCOCH3
OH
N-acetyl-D-glucosamine
132
hyaluronate
Heparan Sulfate
Heparan sulfate is initially synthesized on a membrane-embedded core protein as a polymer of alternating N-acetylglucosamine and glucuronate residues. Later, in segments of the polymer, glucuronate residues may be converted to the sulfated sugar iduronic acid, while N-acetylglucosamine residues may be deacetylated and/or sulfated.
iduronate-2-sulfate
H H COO OH
N-sulfo-glucosamine-6-sulfate
CH2OSO3 H O H H OH O H O H NHSO3
133
O H
OSO3
Heparin
Heparin, a soluble glycosaminoglycan found in granules of mast cells, has a structure similar to that of heparan sulfates, but is more highly sulfated. When released into the blood, it inhibits clot formation by interacting with the protein antithrombin. Heparin has an extended helical conformation.
134
135
136
Importance of carbohydrates
We use them as our major energy source (4 kcal/g)
Humans : starch, sucrose and fructose 80% of our energy intake (average)
We use them for their sweet taste We use them to provide structure and texture in food products
Bread & pudding (starch); Dextrin (soft drinks); Pectin (jellies)
We use them to lower water activity of food products and also influence ice crystallization
Intermediate moist foods; Ice cream
Importance of carbohydrates
We use them as fat substitutes
Modifies starches & celluloses, and gums
We use them to impart desirable flavors and colors for certain food products
Maillard browning