Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Chapter 7 Carbohydrates to accompany Biochemistry, 2/e by Reginald Garrett and Charles Grisham All rights reserved. Requests for permission to make copies of any part of the work should be mailed to: Permissions Department, Harcourt Brace & Company, 6277 Sea Harbor Drive, Orlando, Florida
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Outline 7.1 Carbohydrate Nomenclature 7.2 Monosaccharides 7.3 Oligosaccharides 7.4 Polysaccharides
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Stereochemistry Review Read text on p 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
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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 10.2 and 10.3 are diastereomers Two sugars that differ in configuration at only one chiral center are epimers
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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 Cyclic form of glucose is a pyranose Cyclic form of fructose is a furanose
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Cyclic monsaccharide structures and anomeric forms Cyclic forms possess anomeric carbons For D-sugars, alpha has OH down, beta up For L-sugars, the reverse is true
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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 and Figure 7.20 Note carefully the nomenclature of links! Be able to recognize alpha(1,4), beta(1,4), etc
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 7.4 Polysaccharides Functions: storage, structure, recognition Nomenclature: homopolysaccharide vs. heteropolysaccharide Starch and glycogen are storage molecules Chitin and cellulose are structural molecules Cell surface polysaccharides are recognition molecules
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Starch A plant storage polysaccharide Two forms: amylose and amylopectin Most starch is 10-30% amylose and % amylopectin Branches in amylopectin every residues Amylose has alpha(1,4) links, one reducing end
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Starch A plant storage polysaccharide Amylose is poorly soluble in water, but forms micellar suspensions In these suspensions, amylose is helical –iodine fits into the helices to produce a blue color
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Why branching in Starch? Consider the phosphorylase reaction... Phosphorylase releases glucose-1-P products from the amylose or amylopectin chains The more branches, the more sites for phosphorylase attack Branches provide a mechanism for quickly releasing (or storing) glucose units for (or from) metabolism
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Glycogen The glucose storage device in animals Glycogen constitutes up to 10% of liver mass and 1-2% of muscle mass Glycogen is stored energy for the organism Only difference from starch: number of branches Alpha(1,6) branches every 8-12 residues Like amylopectin, glycogen gives a red- violet color with iodine
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Dextrans A small but significant difference from starch and glycogen If you change the main linkages between glucose from alpha(1,4) to alpha(1,6), you get a new family of polysaccharides - dextrans Branches can be (1,2), (1,3), or (1,4)
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Dextrans A small but significant difference from starch and glycogen Dextrans formed by bacteria are components of dental plaque Cross-linked dextrans are used as "Sephadex" gels in column chromatography These gels are up to 98% water!
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company 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
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Structural Polysaccharides Composition similar to storage polysaccharides, but small structural differences greatly influence properties Beta(1,4) linkages make all the difference! Strands of cellulose form extended ribbons
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Other Structural Polysaccharides Further reading - pages Chitin - exoskeletons of crustaceans, insects and spiders, and cell walls of fungi –similar to cellulose, but C-2s are N-acetyl –cellulose strands are parallel, chitins can be parallell or antiparallel
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company Other Structural Polysaccharides Alginates - Ca-binding polymers in algae Agarose and agaropectin - galactose polymers Glycosaminoglycans - repeating disaccharides with amino sugars and negative charges
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company
Biochemistry 2/e - Garrett & Grisham Copyright © 1999 by Harcourt Brace & Company