chapter 7a' carbohydrates b and w
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Principles of Biochemistry 1/e - Garrett & Grisham
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Chapter 7(Part 1 of 2)
Carbohydrates and Cell Surfaces
to accompanyPrinciples of Biochemistry With a
Human Focus, 1/eby
Reginald Garrett and Charles Grisham
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Principles of Biochemistry 1/e - Garrett & Grisham
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Outline
• 7.1 Carbohydrate Nomenclature • 7.2 Monosaccharides• 7.3 Oligosaccharides • 7.4 Polysaccharides• 7.5 Glycoproteins• 7.6 Proteoglycans
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Principles of Biochemistry 1/e - Garrett & Grisham
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7.1 Nomenclature
Carbohydrates are hydrates of carbon• Monosaccharides (simple sugars)
cannot be broken down into simpler sugars under mild conditions
• Oligo = "a few" - usually 2 to 10 • Polysaccharides are polymers of the
simple sugars
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Principles of Biochemistry 1/e - Garrett & Grisham
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7.2 MonsaccharidesAn organic chemistry review
• 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
• Review Fischer projections and D,L system
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Principles of Biochemistry 1/e - Garrett & Grisham
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Principles of Biochemistry 1/e - Garrett & Grisham
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Principles of Biochemistry 1/e - Garrett & Grisham
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Principles of Biochemistry 1/e - Garrett & Grisham
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Stereochemistry ReviewRead text on p. 204-210 carefully!
• D,L designation refers to the configuration of the highest-numbered asymmetric center
• D,L only refers the stereocenter of interest back to D- and L-glyceraldehyde!
• D,L do not specify the sign of rotation of plane-polarized light!
• All structures in Figures 7.2 and 7.3 are D
• D-sugars predominate in nature
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Principles of Biochemistry 1/e - Garrett & Grisham
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Principles of Biochemistry 1/e - Garrett & Grisham
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More StereochemistryKnow 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
• Any 2 sugars in a row in 7.2 and 7.3 are diastereomers
• Two sugars that differ in configuration at only one chiral center are epimers
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Principles of Biochemistry 1/e - Garrett & Grisham
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Cyclic monsaccharidestructures and anomeric forms
• Glucose (an aldose) can cyclize to form a cyclic hemiacetal.
• Fructose (a ketose) can cyclize to form a cyclic hemiketal
• Aldohexoses prefer the pyranose form • Ketohexoses prefer the furanose form
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Fig. 7.5 The linear form of glucose cyclizes to the alpha (OH anti to C6) or beta (OH syn to C6) hemiacetal pyranose form. Glucose is an aldohexose. Carbon 1 is the anomeric carbon. The interconversion of the cyclic forms (?or ?anomers) is called mutarotation. The beta/alpha ratio for glucose is 63/37.
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Fig. 7.6 The linear form of fructose cyclizes to the alpha (C2-OH anti to C6) or beta (C2-OH syn to C6) hemiketalfuranose form. Fructose is an ketohexose. Carbon 2 is the anomeric carbon.
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Cyclic monsaccharidestructures and anomeric forms
• Cyclic forms possess anomeric carbons • For D-sugars, alpha (OH anti to 6C) has
OH down, beta (OH syn to 6C) up • For L-sugars, the reverse is true
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Fig. 7.7 Glucose, an aldohexose, prefers the pyranose form
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Fig. 7.8 Ribose, an aldopentose, prefers the furanose form
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Fig. 7.9. All of glucose’s OH s can be placed equatorially, which makes glucose the most stable and most abundant of monosaccharides
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Principles of Biochemistry 1/e - Garrett & Grisham
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Monosaccharide Derivatives• Reducing sugars: sugars with free
anomeric carbons - they will reduce oxidizing agents, such as peroxide, ferricyanide and some metals (Cu and Ag)
• These redox reactions convert the sugar to a sugar acid
• Glucose is a reducing sugar - so these reactions are the basis for diagnostic tests for blood sugar
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Principles of Biochemistry 1/e - Garrett & Grisham
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Fig. 7.10 Oxidation of monosaccharides
C-1 = -ONIC
C-6 = -ORONIC
Both = -ARIC
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GLUCOSE
GLUCOSEGLUCOSE
GALACTOSE ALLOSE MANNOSE
GALLOMAN
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Principles of Biochemistry 1/e - Garrett & Grisham
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More Monosaccharide Derivatives
• Sugar alcohols: mild reduction of sugars • Deoxy sugars: constituents of DNA, etc. • Sugar esters: phosphate esters like ATP
are important • Amino sugars contain an amino group in
place of a hydroxyl group • Acetals, ketals and glycosides: basis for
oligo- and poly-saccharides
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Fig. 7.12 some deoxy-monosaccharides and Ouabain, a poisonous glyco-steroid, or Cardiac glycoside that affects the heart rhythm.
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Fig. 7.13 sugar phosphate esters metabolically important. The first two areGlycolysis intermediates; the third is ATP
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Fig. 7.14 Substitution of an OH for an amine group, NH2, gives sugar amines.These are the basic blocks for glycosaminoglycans (heparin, chondroitin, etc)
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Fig. 7.15 Muranic and neuroaminic acids are components of of the polysaccarides in higher order organisms as well as bacterial cell walls. The collective name of of the N-acetyl and N-glycolyl derivatives are sialic acids
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Fig. 7.16 Further reaction of hemiacetals or hemiketals with another alcohol gives acetals and ketals, respectively.
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Fig. 7.17 For example, reacting glucosewith a mole of methanol gives the ? and?methyl-glucosides. The anomeric carbondoes not mutarotate, and the new bond (CH3-O) is Called a GLYCOSIDIC BOND
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Principles of Biochemistry 1/e - Garrett & Grisham
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7.3 OligosaccharidesDon't memorize structures, but know the
important features• Be able to identify anomeric carbons and
reducing and nonreducing ends • Sucrose is NOT a reducing sugar • Browse the structures in Fig. 7.18, 7.19• Note carefully the nomenclature of links! Be
able to recognize alpha(1,4), beta(1,4), etc
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Oligosaccharides (cont.)
• Glycolipids and glycoproteins• Found in cell membranes or secreted
proteins. Their function might be:• Allow attachment & solubility of proteins• Help proper folding (steric crowding)• Charged sugar repel ea other and extent the
3rd structure.• Protection from degradation• Recognition (cell signalling)
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Oligosaccarides (cont.)
• Glycophorin (GP) of RBC membranes has 16 oligosaccarides(60-70 monosaccarides)
• They are the MN (GP) blood types (other glycoproteins)
• Soluble glycoproteins include immunoglobulins and transport proteins.
• They usually end in sialic acid (SI). If SI lost, they are degraded by liver
• Mann-6-P is signal for lysoenzymes to move to lysosomes.
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Fig. 7.18 examples of glycosidic bonds. The sugar using the anomeric carbon is named first. (Acrobat)
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Fig. page 217. TREHALOSE , glucose-?-1,1-glucose, is a temperature protectant forinsects (they have hemolymph, not blood), fungi, yeast, bacterial spores, etc. Honey bees do not have it. They keep their honeycomb at 18 0C at all times.
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Fig. 7.19 Other oligosaccharides. The cycloamylose is useful for size exclusion chromatography. Leatrile killed Steve Mcqueen.