Chapter 9. Carbohydrates and Glycoconjugates
importance of carbohydrates?

role of carbohydrates
energy storage
structural polymers (e.g., cell wall, chitin)
lipid and protein conjugates (e.g., cell recognition)
components of other biomolecules (e.g., DNA, RNA, coenzymes)
A. Monosaccharides
characteristics:
3-6 carbons (larger do exist; typically displayed using Fisher projections)
multiple hydroxyl groups
carbonyl group in the form of an aldehyde or ketone
example:

1. nomenclature:
aldose (if aldehyde)
ketose (if ketone)
triose 3 carbons
tetrose 4 carbons
pentose 5 carbons
hexose 6 carbons
2. chirality: for a molecule with n chiral centers, there are 2n stereoisomers. The following examples show both possibilities for a carbohydrate with one chiral center (n=1) and one of the 16 possibilities when n=4.

enantiomers: mirror image related stereoisomers
diastereomers: non-mirror imagerelated stereoisomers
epimers: a special type of diastereomer that differs only at one chiral
center
3. chemistry of carbohydrates: acetal formation
intermolecular example

intramolecular example: aldenhyde and alcohol are in same molecule?
Do all hydroxyls in carbohydrates participate in hemiacetal formation?
no, typically only those leading to 5-membered rings (called furanoses) and 6-membered rings (called pyranoses)

consider case of glucose in detail

comments
cyclic forms (alpha- and beta-D-glucose shown above) have a new chiral center called the anomeric center
flat Haworth projections inaccurate – "chair" conformations would be more accurate

4. biologically important derivatives
a. sugar phosphates (key role in metabolism)
b. deoxy sugars (DNA building block)
c. amino sugars (structural building block)
d. sugar alcohols (lipids, coenzyme)
e. sugar acids
B. Disaccharides
Disaccharides arise from the combination of two monosaccharide units in which a new acetal bond is formed between the hemiacetal of one carbohydrate and a hydroxyl group of a second.

1. maltose: produced in hydrolysis of starch
2. cellobiose: repeating structure of cellulose
3. lactose
4. sucrose
C. Polysaccharides
terminology
homoglycans: same repeating unit
heteroglycans
reducing: has hemiacetal
non-reducing: has no hemiacetal
hemiacetal + Ag+
® Ago + sugar acid1. starch (plants, fungi; amylose + amylopectin)
2. glycogen (animals)
3. cellulose