Principles of Biochemistry 1/e - Garrett & Grisham

Chapter 7
(Part 1 of 2)
Carbohydrates and Cell Surfaces
to accompany Principles of Biochemistry With a Human Focus, 1/e by Reginald Garrett and Charles Grisham
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Principles of Biochemistry 1/e - Garrett & Grisham

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

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

7.2 Monsaccharides
An 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

Stereochemistry Review

Read 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

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 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

Cyclic monsaccharide structures 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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Principles of Biochemistry 1/e - Garrett & Grisham 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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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.6 The linear form of fructose cyclizes to the alpha (C2-OH anti to C6) or beta (C2OH syn to C6) hemiketal furanose form. Fructose is an ketohexose. Carbon 2 is the anomeric carbon.

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Principles of Biochemistry 1/e - Garrett & Grisham

Cyclic monsaccharide structures 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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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.7 Glucose, an aldohexose, prefers the pyranose form

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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.8 Ribose, an aldopentose, prefers the furanose form

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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.9. All of glucoses 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

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 Fig. 7.10 Oxidation of monosaccharides C-1 = -ONIC C-6 = -ORONIC Both = -ARIC

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Principles of Biochemistry 1/e - Garrett & Grisham

GLUCOSE

GLUCOSE

GLUCOSE

GALACTOSE

ALLOSE GALLOMAN

MANNOSE

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Principles of Biochemistry 1/e - Garrett & Grisham

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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Principles of Biochemistry 1/e - Garrett & Grisham

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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.12 some deoxy-monosaccharides and Ouabain, a poisonous glyco-steroid, or Cardiac glycoside that affects the heart rhythm.
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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.13 sugar phosphate esters metabolically important. The first two are Glycolysis intermediates; the third is ATP
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Principles of Biochemistry 1/e - Garrett & Grisham

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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Principles of Biochemistry 1/e - Garrett & Grisham

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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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.16 Further reaction of hemiacetals or hemiketals with another alcohol gives acetals and ketals, respectively.
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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.17 For example, reacting glucose with a mole of methanol gives the ? and ? methyl-glucosides. The anomeric carbon does not mutarotate, and the new bond (CH3-O) is Called a GLYCOSIDIC BOND

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Principles of Biochemistry 1/e - Garrett & Grisham

7.3 Oligosaccharides
Don'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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Principles of Biochemistry 1/e - Garrett & Grisham

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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Principles of Biochemistry 1/e - Garrett & Grisham

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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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.18 examples of glycosidic bonds. The sugar using the anomeric carbon is named first. (Acrobat)
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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. page 217. TREHALOSE , glucose-?-1,1-glucose, is a temperature protectant for insects (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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Principles of Biochemistry 1/e - Garrett & Grisham

Fig. 7.19 Other oligosaccharides. The cycloamylose is useful for size exclusion chromatography. Leatrile killed Steve Mcqueen.
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