Bio 98 - Lecture 11

Carbohydrates

a.k.a. Sugars

I. Definition of a carbohydrate
General formula: (CH2O)n , hydrated carbon Example: C6H12O6 is glucose Many carbohydrates have more complex formulas & contain amino, phosphate, sulfate & other groups

II. Functions

1. Fundamental source of metabolic energy for most life forms.

2. Components of many important biomolecules.

1. Carbohydrates as an energy source

sunlight

plants photosynthesis
CO2 + H2O animals, plants respiration

carbohydrate + O2

ATP

ADP

2. Biological molecules
Penicillin

Cellulose - wood, plant fiber, etc. Chitin - exoskeleton of arthropods Cell walls of bacteria & yeast Glycoproteins, glycolipids - cell membranes DNA, RNA - deoxyribose and ribose

Carbohydrates are often polymers Monosaccharides: glucose, ribose, fructose, etc. Oligosaccharides: di-, tri-, tetra- etc. Sucrose is a disaccharide: glucose + fructose Polysaccharides: can be linear or branched (i.e. starch)

Monosaccharide nomenclature 1. Carbon number: triose, .., pentose, hexose, .., octose 2. Aldoses and ketoses C# 1 2 3 4 5 6 D-glucose D-fructose

HC=O
HC-OH HO-CH HC-OH

H2C-OH
C=O HO-CH HC-OH

HC-OH
H2C-OH

HC-OH
H2C-OH

an aldohexose

a ketohexose

Asymmetric (chiral) carbons allow many distinct monosaccharides; compare mannose, glucose, and galactose, which are all aldohexoses.

How many chiral carbons are in glucose?

O-chem terms relevant to monosaccharide structure

1. diastereomers - identical structures except for configuration (chirality) at one or more carbons; e.g., all aldohexoses are diastereomers of each other. 2. epimers - differ in chirality at only one carbon. Glucose and galactose are epimers at carbon 4. 3. enantiomers - mirror images; designated as D- & L-; does not constitute a name change.

How many aldohexose names are possible? 2 configuration choices at each of 4 asymmetric carbons; however (1.), half of these represent enantiomers (3.). Number of unique names = 24 / 2 = 8.

Ring structures
Most pentoses and hexoses spontaneously form ring (cyclized) structures in solution.
+

HC=O HC-OH

5-member ring: furanose

6-member ring: pyranose

When forming a ring, a new asymmetric center is created, giving rise to 2 possible anomers.

HO-CH HC-OH .. HC-OH H2C-OH

Dglucose(linear form)

Linear form

Haworth projection

hemiacetal

a and b anomers
a-D-glucopyranose

In solution rapid mutarotation occurs

b-D-glucopyranose (~66%)

Linear D-glucose (1%) a-D-glucopyranose (~33%)

Disaccharides
1. Mainly found in plants 2. Three common disaccharides sucrose - sugar cane, sugar beets lactose - milk sugar maltose - malted (germinating) barley, wheat 3. 2 monosaccharides joined covalently by an O-glycosidic bond

Formation of hemiacetal and acetals

Glycosidic bond

Common disaccharides are produced by enzymecatalyzed condensation/dehydration reactions

Can be either a or b due to mutarotation

Notice: there is no hemiacetal

Polysaccharides - aka Glycans

1. homopolysaccharides vs heteropolysaccharides 2. can be branched or unbranched 3. used by animals and plants as a compact storage form of CHOs 4. common examples starch - plants, roots and seeds glycogen - liver of mammals cellulose - plant fiber, wood

Starch = amylose + amylopectin

found in corn, rice, potato, wheat and barley

a linear polysaccharide of glucose units

Amylopectin - a branched form of amylose

Structure of starch

glycogen (animal starch) is like starch, but more highly branched

High-fructose corn syrup

High-fructose corn syrup is produced by milling corn to produce corn starch, then processing that starch to yield corn syrup, which is almost entirely glucose, and then adding enzymes that change most of the glucose into fructose. 1.Corn starch is treated with alpha-amylase to produce shorter chains of sugars called oligosaccharides. 2.Glucoamylase - which is produced by Aspergillus, a fungus, in a fermentation vat breaks the sugar chains down even further to yield the simple sugar glucose. 3.The enzyme xylose isomerase (aka glucose isomerase) then converts some of the glucose to a mixture of about 42% fructose and 5052% glucose with some other sugars mixed in.
http://en.wikipedia.org/wiki/High-fructose_corn_syrup

Protein glycosylation: A post-translational modification

Sugars covalently attached to the polypeptide as oligosaccharide chains containing 4 to 15 sugars Sugars frequently comprise 50% or more of the total molecular weight of a glycoprotein Most glycosylated proteins are either secreted or remain membranebound Glycosylation is the most abundant form of post-translational modification Glycosylation confers resistance to protease digestion by steric protection Important in cell-cell recognition

Blood group antigens on erythrocyte surface

The O substance is a tetrasaccharide which is missing the 5th residue and does not elicit an antibody response (non-antigenic). The A antigen and B antigen are pentasaccharides which differ in composition of the 5th sugar residue