Carbohydrates

• “hydrate of carbon” = (C.H2O)

• Polyhydroxy aldehydes or ketones (C=O)
• Building blocks: Monosaccharides (simple sugars) linked via glycosidic bonds
 
I. Classification of Carbohydrates
1. By functional groups
 

 
I. By number of carbons
# of Aldose- RCHO Ketose- RCOR
Carbon
3 Triose (glyceraldehyde Triulose (dihydroxyacetone)
4 Tetrose (erythrose Tetrulose (erythrulose)
5 Pentose (ribose Pentulose (ribulose)
6 Hexose (glucose Hexulose (fructose)
1. By number of Sugar units
# Units Sugar Examples
1 Monosaccharides Glucose, Fructose, Galactose
2 Disaccharides Trehalose= glu+glu
Sucrose= glu+fru
Maltose= glu+glu
Lactose=gal+glu
3-10 Oligosaccharides Maltotriose,Dextrin
>10 Polysaccharides Starch, Glycogen, Cellulose
 
Polysaccharides
o Aka: GLYCANS
o 2types:
1. Homopolysaccharides — one type of monosaccharide only
2. Heteropolysaccharides — 2 or more than one type of monosaccharide
 
Homopolysaccharides
o Starch (in plants)
 Amylose — unbranched, helical portion (alpha1-->4)
 Amylopectin — branched (alpha1-->4 and alpha1-->6) and water soluble
portion, branching every 25-30 units

 
 
o Glycogen (in animals)
 Present in liver and skeletal muscle
 Similar to amylopectin but more extensively branched
 Branching frequency: every 8-12 glucose units
 
Heteropolysaccharides
a. Glycosaminoglycans [GAG]
 (Mucopolysaccharides)
a. Components of the extracellular matrix (ECM) connective tissues
b. Composition: Amino sugars + Uronic acids

 
Examples of Glycosaminoglycans
GAG Location
Hyaluronic Acid Vitreous humor, synovial fluids
Chondrotoin SO4 Cartilage, Tendons and ligaments
Dermatan SO4 skin
Keratan SO4 Cornea, nails
Heparan SO4 Basement membrane of cells
Heparin Mast cells, liver, lung, skin
 
 

 
 
  
 
a. Functions of Carbohydrates
Uses:
 the primary functions of polysaccharides are to:
1. Provide structure (e.g. cellulose, chitin, pectin, peptidoglycan, agarose)
2. Store energy (e.g starch and glycogen)
 
Structural Polysaccharides
 Cellulose
 Found in plant cell walls
 Linear, linked by ß1—4 bonds
 

 Chitin
 Found in exoskeleton of insects and crustaceans
 Polymer of N-acetylglucosamine (ß1->4)
 

 
 Pectin
 Found in the middle lamella of plant cells
 Partially methoxylated polygalacturonic acid
 
  
 Peptidoglycan
 Found in bacterial cell wall
 N-acetylglucosamine (NAG) and N-acetylmuramic acid (NAM)
 

 Structure of Carbohydrates
a. Fischer Projection Formula
a. Linear or straight-chain formula D and L configuration of sugars
o Reference carbon: penultimate (2nd to the last) carbon or most
distant chiraI center
o D — right or L — left

 Haworth Projection Formula

 Cyclic structures of sugars
 Cyclization occurs in aqueous solutions
 (Hemiacetal/Hemiketal Formation)
 

 
 Anomers = differ only in the configuration at the hemiacetal carbon
 

 
  

 Stereoisomerism
 Carbohydrates are chiral molecules (with four different groups)
 # stereoisomers = 2n (where n = #chiral carbons)
 

 
 Types:
 Functional Isomers
 Anomers
 Epimers
 Enantiomers
 Diastereomers
 
o Functional Isomerism: differ in functional groups
 
  
o Anomers: Differ in configuration at the anomeric carbon
 

 
a. Epimers: Differ in configuration at only one chiral carbon
 

 
a. Enantiomers: Mirror images, nonsuperimposable
Note: all Chiral carbons are inverted
 
 a. Diasteromer: Non-mirror images, nonsuperimposable
 

I. Reaction
 
1. Oxidation of Monosaccharides
a. Oxidation at C-1

 
 
  
 
1. Oxidation at C-6
 

 
a. Oxidation at C-1 and C-6
 

 
 

 
1. Reduction of Monosaccharides
o The carbonyl group of sugars is reduced to produce sugar alcohol
 
  
 

1. Formation of Glycosidic Bonds

 

 
Other examples:
 Maltose: Glu + qlu (a1--> 4) = reducing sugar
 Cellobiose: Glu + Glu (ß1-->4) = reducing sugar
 Trehalose: Glu + Glu (a1-->1) = non-reducing sugar
 Sucrose: Glu + Fru (a1-->2) = non-reducing sugar
NOTE:
 All monosaccharides are redicing sugars
 All polysaccharides and some disaccharides (e.g. trehalose, sucrose) are non-
reducing
 Qualitative Tests
Test Use Reagent Visible Results
Molisch test General test for CHO Alpha- naphthol Violet ring at the
+h2so4 junction
Anthrone test General test for CHO Anthrone Green color
Fehling's Test for reducing sugars CuSO4+Na-K Brick red ppt
tartrate
Benedict's Test for reducing sugars CuSO4+Na2CO3+Na Brick red ppt
(differentiates mono vs. di) citrate
Tollen's Test for reducing sugars Ammoniacal AgNO3 Silver mirror
Maillard's Test for reducing sugars Amino acids Brown coloration
Seliwanoff's For ketoses Resorcinol, HCl Pink/ Cherry red
Bial's For pentoses Orcinol, HCl Blue-green color
Tollen's For pentoses Phloroglucinol Red color
Phloroglucinol
Iodine For starch, glycogen Iodine Starch (blue);
glycogen (red)
Mucic acid test For galactose HNO3 White insoluble
crystals
(galactaric/mucic)
Ozasone test For ID of sugars Phenylhydrazine Yellow-orange
(Kowarsky test) crystals of
different shapes

Broom-like/ fan:
glu, fru, man
Sunflower-like:
sucrose, maltose
Cotton-ball/puff:
lactose