chapter 11: carbohydrates copyright © 2007 by w. h. freeman and company berg tymoczko stryer...
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Chapter 11:Carbohydrates
Copyright © 2007 by W. H. Freeman and Company
Berg • Tymoczko • Stryer
BiochemistrySixth Edition
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Carbohydrates
Common termsMonosaccharides: glucose, fructose, mannose, etc.Disaccharides: maltose, cellibiose, sucrose, lactosePolysaccharides: starch, glycogen, chitin,
glycosaminoglycansAldoses, ketoses Pentoses, hexosesPyranose, furanoseAnomeric carbon atom, anomers, D,L isomers, epimers, penultimate carbonGlycosidic bond, hemiacetal, acetalMutarotation Reducing sugar
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Trioses (three carbons)
aldose aldose ketose
* Know
**
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Aldose familyAdlose family
* Know
*
*
* * *
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Ketose familyKetose family *
*
*
* Know
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D-Stereochemistry of Glucose
Convention for the Fischer projection:
Carbonyl (#1C) is at the top.
OH to right = "D"OH to left = "L"
CHO
H C OH
H C OH
H C OH
HO C H
CH2 -OH
Penultimate C
Glucose is assigned the D stereochemistry because the penultimate carbon atom is D.
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Hemiacetal formation
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Pyranose and Furanose forms
Hemiacetal, Haworthstructure
Hemiketal,Haworthstructure
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Haworth Structure of Glucose
-anomer
-anomer
Draw Fischer, rotate 90o, then form the hemiacetal
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Haworth Structure of Fructose
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Ribose and DeoxyribseHaworth structures
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Mutarotation of Fructose
Openchainform
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Mutarotation of Glucose
Open chain Form~0.003%
-D-glucopyranose 36%, D = 112o
-D-glucofuranose~0.5%
-D-glucopyranose 63%, D = 18.7o
-D-glucofuranose~0.5%
Observed rotation = 52.7o
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Glycosidic bond (acetal)
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Three glucose residues
The connections (gycosidic bonds) are ( 1-4)
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Lobry de Bruyn-Alberda von Eckenstein rearrangement
HO C H
H C OH
H C OH
CH2-OH
C O
CH2-OH
HC=O
H C OH
H C OH
H C OH
HO C H
CH2 -OH
CHO
H C OH
H C OH
CH2 -OH
HO C H
HO C H
CH-OH
H C OH
H C OH
CH2 -OH
C OH
HO C H
H-O-
enediol
glucose mannose
fructose
Reactionof a sugarin NaOH.
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Methylation of Glucose
Converting a hemiacetal to an acetal.
HO-CH2
OHHO
O
OH
OH
CH3OH
HO-CH2
OHHO
O
H+
OH
OCH3
Glycosidic bond (an acetal)
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Methylation of Glucose
Exhaustive methylation forms one glycocidic bond and the rest are ethers.
CH3I
HO-CH2
OHHO
O
OH
OH
CH3O-CH2
OOCH3
CH3O
OCH3
OCH3
HOH
H+
CH3O-CH2
OOH
CH3O
OCH3
OCH3
excess
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Sugar Derivatives
Also, oxidized or reduced or phosphorylated or amino sugars
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Sugar Oxidation at C-1
Gluconic acid
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Sugar Oxidation at C-6
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Sugar Phosphates
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N-Acetylmuramic acid
N-acetylglucosamine + lactate, A component of bacterial cell wall.
NH-C-CH3
HO-CH2
OOHHO
CH3-CH-COOH
O
O
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N-Acetylneuraminic acidN-acetylmannosamine + PEP
C-CH3
HO-CH2
OH CHO
HO
OH
O
NHC-CH3
HO-CH2
OHHO
O
O
NHOH
COO-HOH
CH2
C-O-PO3=
..
C-CH3
HO-CH2
OH CH
HO
OH
O
NH
COO-
H-O
CH2
C-O-PO3=
..
OH
C-CH3
HO-CH2
OH CH
HO
OH
O
NH
COO-
CH2
C=O
OH
CH3-CCHOH
OH
O
O
NH
OH
COO-
CH2OH
CHOH
Pi
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Common disaccharides
1. Maltose: -D-glucopyranosyl-(14)--D-glucopyranose
2. Cellibiose: -D-glucopyranosyl-(14)--D-glucopyranose
3. Lactose: -D-galactopyranosyl-(14)--D-glucopyranose
4. Sucrose: -D-glucopyranosyl-(12)--D-fructofuranoside
The anomeric OH in 1, 2, & 3 may be or but sucrose may not.
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Maltose, a disaccharide
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Other disaccharides
Cellibiose
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Common Homopolysaccharides
1. Amylose (linear starch)An-(14)-D-glucose polymer
2. Cellulose (linear)A -(14)-D-glucose polymer
3. Amylopectin (branched starch)An -(14)-D-glucose polymer branched -(16)
4. Glycogen (branched)An -(14)-D-glucose polymer branched -(16)
5. Chitin (linear)An -(14)-D-N-acetylglucosamine polymer
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GlucopolysaccharidesHomopolysaccharides
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A 1-6 branch point
This branch occurs in glycogen and amylopectin. However, glycogen is more highly branched.
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A high energy glucose carrier
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Heteropolysaccharides Glycosaminoglycans(disaccharide repeating units)
Chondroitin-6-sulfate:-D-glucuronic acid-( 13)-N-acetyl-D-galactosamine-6-sulfate-( 14)-
Keratan sulfate:-D-galactose-( 14)--acetyl-D-glucosamine-6-sulfate-( 13)-
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Heteropolysaccharides Glycosaminoglycans(disaccharide repeating units)
Dermatan sulfate:-L-iduronic acid-( 13)-N-acetyl-D-galactosamine-4-sulfate-( 14)-
Hyaluronic acid:-D-glucuronic acid-( 13)-N-acetyl-D-glucosamine-( 14)-
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A Proteoglycan
A glycoconjugate:(polysaccharide linked to a protein or peptide)
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ProteogycanElectronmicrograph
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Complex Carbohydrates
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L-Fucose
L-fucose is 6-deoxy-L-galactose
CHO
HO C H
H C OH
HO C H
H C OH
CH3
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Linkages in Glycoproteins
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N-Linked Carbohydrate
High mannose
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N-Linked Carbohydrate
Complex carbohydrate
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Dolichol phosphate (isoprenoid)
This is the endoplasmic reticulum membrane anchor on which the core carbohydrate for a glycoprotein is synthesized. It is then modified in a Golgi body.
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From Golgi to Lysosome
Mannose-6-P is a marker that directs some hydrolytic proteins from a Golgi body to a lysosome where glycolipids and glycosaminoglycans are degraded.
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Hydrolysis of theN-acetylglucosamine to leave a Mannose-6-P residue.
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Review - Glycoconjugates
1. Proteoglycans (glycosaminoglycans + protein).Mostly carbohydrate (~85%), e.g. cartilage
2. Glycoproteins (most 1-10% carbohydrate). N and O linked complex carbohydratese.g. receptors
3. Peptidoglycans (carbohydrate + small peptide). e.g. bacterial cell wall
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Proteoglycan
Sketch
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PeptidoglycanBacterial cell wall (murein): A long linear
polymer of:
-N-acetyl-D-glucosamine-( 14) -N-acetyl-Muramic acid-( 14)-
A tetrapeptide is attached through the carboxyl of the lactate moiety of muramic acid.
Lactate-CO-L-Ala-D-isoGlu-L-Lys-D-Ala-
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Peptidoglycan
Bacterial cell wall:
Lactate-CO-L-Ala-D-isoGlu-L-Lys-D-Ala-
In gram (+) bacteria crosslinks are formed by a pentaglycine bridge from the D-Ala residue above to the L-Lys in another peptide. (Outer surface is carbohydrate)
In gram (-) bacteria crosslinks are formed by a direct link from the D-Ala residue above to the L-Lys in another peptide. (Outer surface is cell membrane)
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Gram Positive (+) Cell Wall
Up to 20 layers of peptideglycan
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Gram Negative (-) Cell Wall
Monolayer of peptideglycan
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End of Chapter 11
Copyright © 2007 by W. H. Freeman and Company
Berg • Tymoczko • Stryer
BiochemistrySixth Edition