Chapter 8 (part 1)

Carbohydrates

Carbohydrates
Most abundant class of biological molecules on Earth Originally produced through CO2 fixation during photosynthesis

Roles of Carbohydrates
Energy storage (glycogen,starch) Structural components (cellulose,chitin) Cellular recognition Carbohydrate derivatives include DNA, RNA, co-factors, glycoproteins, glycolipids

Carbohydrates
Monosaccharides (simple sugars) cannot be broken down into simpler sugars under mild conditions Oligosaccharides = "a few" - usually 2 to 10 Polysaccharides are polymers of the simple sugars

Monosaccharides
Polyhydroxy ketones (ketoses) and aldehydes (aldoses) Aldoses and ketoses contain aldehyde and ketone functions, respectively Ketose named for equivalent aldose + ul inserted Triose, tetrose, etc. denotes number of carbons Empirical formula = (CH2O)n
O C H HO H C* C* C* OH H OH HO H H CH2OH C C* C* O H OH

CH2OH D-ribose

CH2OH D-ribulose

Monosaccharides are chiral

Aldoses with 3C or more and ketoses with 4C or more are chiral The number of chiral carbons present in a ketose is always one less than the number found in the same length aldose Number of possible steroisomers = 2n (n = the number of chiral carbons)

O C H HO H H C* C* C* C*

H CH2OH OH H OH OH HO H H C C* C* C* O H OH OH

CH2OH D-glucose

CH2OH D-fructose

Stereochemistry
Enantiomers
H C HO H HO HO C* C* C* C* H OH H H H HO H H O O C C* C* C* C* OH H OH OH HO HO H H H

Diastereomers
O C C* C* C* C* H H OH OH H HO HO H H O C C* C* C* C* OH H H OH H HO H H H O C C* C* C* C*

Epimers
H O C OH H OH OH HO HO H H C* C* C* C* H H OH OH H

CH2OH L-glucose

CH2OH D-glucose

CH2OH D-mannose

CH2OH D-galactose

CH2OH D-glucose

CH2OH D-mannose

Enantiomers = mirror images Pairs of isomers that have opposite configurations at one or more chiral centers but are NOT mirror images are diastereomers Epimers = Two sugars that differ in configuration at only one chiral center

Cyclization of aldose and ketoses introduces additional chiral center

Aldose sugars (glucose) can cyclize to form a H cyclic hemiacetal H NEW CHIRAL ALDEHYDE
O C H ALCOHOL H O R2 R1 O CARBON H C* O R2 HEMIACETAL R1

Ketose sugars (fructose) can cyclize to form a H H cyclic hemiketal NEW CHIRAL KETONE O O
CARBON C R ALCOHOL H O R2 R1 R C* O R2 HEMIKETAL R1

Glucopyranose formation

Fructofuranose formation

Monosaccharides can cyclize to form Pyranose / Furanose forms

= 64% = 36% = 21.5% = 58.5%

= 13.5% = 6.5%

Haworth Projections
O C1 H HO H H C2 C3 C4 C5 OH H OH OH H

6 5 4 3 2

-OH up = beta -OH down = alpha

1 Anomeric carbon (most oxidized)

CH2OH

For all non-anomeric carbons, -OH groups point down in Haworth projections if pointing right in Fischer projections

Conformation of Monosaccharides

Pyranose sugars not planar molecules, prefer to be in either of the two chair conformations.

Reducing Sugars
When in the uncyclized form, monosaccharides act as reducing agents. Free carbonyl group from aldoses or ketoses can reduce Cu2+ and Ag+ ions to insoluble products

Derivatives of Monosaccharides

Sugar Phosphates

Deoxy Acids

Amino Sugars

Sugar alcohols

Monosaccharide structures you need to know

1) 2) 3) 4) 5) 6) Glucose Fructose Ribose Ribulose Galactose Glyceraldehyde