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Carbohydrates!

What are carbohydrates?


General formula: Cn(H2O)n
Examples: sugar, starch, fibers
Go foods primary source of energy
In biochemistry, they are known as
saccharides
Carbohydrate composition

Monosaccharides
Simplest carbohydrates; single sugar molecule
Number of stereoisomers: 2n
Where n = # of chiral carbons
Carbohydrate composition

Disaccharides
Linked by O-glycosidic bond
Interaction between the anomeric carbon
(electrophile) and the lone pair e- (nucleophile)
from the primary alcohol
Reducing disaccharide is produced if there is one
free anomeric carbon outside of the glycosidic bond
Carbohydrate composition

Oligosaccharides
Carbohydrates that have 2-10 sugar molecules
glycoproteins, glycolipids
Carbohydrate composition

Polysaccharides
Carbohydrates that have more than 10 sugar
molecules
Storage polysaccharides: glycogen, starch
Monosaccharides
Monosaccharide classification:
Aldoses: terminal aldehyde
Ketoses: keto-group (position-dependent)
Both are functional isomers
Both contain a primary alcohol attached to the last
carbon
Monosaccharides
Monosaccharides
Simplest aldose: D-glyceraldehyde
Simplest ketose: dihydroxyacetone
Fischer projection:
Monosaccharides
Epimers:
D-glucose and D-mannose are 2-epimers
D-glucose and D-galactose are 4-epimers
Fischer projection:
Hemiacetals and Hemiketals
Hemi half
Formed by addition of alcohol (nucleophile) to
the carbonyl (electrophile)
Responsible for the formation of the closed
chain configuration of saccharides
Pyranose and furanose
Hemiacetals and Hemiketals
Monosaccharides
Pyranose (6-membered ring) or furanose (5-membered ring)
glucose (dextrose), fructose, galactose
glucopyranose, fructofuranose, galactopyranose
Haworth projection:
Monosaccharides
5 C sugars furanose
Ribose and xylose -> ribofuranose and xylofuranose

Haworth projection:
Anomers
Differentiation between
alpha- and beta- form of
anomeric carbon (based on
the OH group)

In their cyclic form, anomers


differ in the orientation of the
OH group of the primary
carbon
Monosaccharides
Chair and Envelope conformation
Monosaccharides
Are reducing agents:
All aldoses have reducing property
Due to the free anomeric carbon
All ketoses have reducing property
Can be hydrolyzed to aldose
Disaccharides
Maltose ( 1-4 glycosidic bond between 2 glucose molecules)
O-(-D-glucopyranosyl)1,4--D-glucopyranose
Disaccharides
Cellobiose (-1,4 glycosidic bond between 2 glucose molecules)
O-(-D-glucopyranosyl)1,4--D-glucopyranose
Disaccharides
Sucrose (table sugar) (-1 of glucose and -2 of fructose)
non-reducing
O-(-D-glucopyranosyl)1,2--D-fructofuranose
Disaccharides
Lactose (milk sugar) (-1,4 between galactose and glucose)
O-(-D-galactopyranosyl)1,4--D-glucopyranose
Polysaccharides
Glycogen and starch
Homopolysaccharides hydrolysis will yield only one kind of monosaccharide
GLYCOGEN energy storage liver / muscle
STARCH energy storage in plants
CELLULOSE structural
Overall non-reducing (contains a very small concentration of
anomeric carbons in the entire structure)
Polysaccharides
Amylose helical
6 glucose residues per turn
-1,4 glycosidic bonds
Amylopectin
-1,4 glycosidic bonds and -1,6 glycosidic branches every 24-30 residues
Glycogen
-1,4 glycosidic bonds and -1,6 glycosidic branches every 8-12 residues
Isolation of Polysaccharides
starch from cassava
Addition of H2O
glycogen from chicken liver
Addition of HOAc
Addition of EtOH
Hydrolysis of the Isolates
Acid Hydrolysis complete hydrolysis
Monosaccharide product
Enzymatic Hydrolysis incomplete hydrolysis
Breaks specific bonds
Salivary amylase will break down -1,4 glycosidic
bonds
Iodine Test
Molischs Test
Reagents
H2SO4, EtOH and -naphtol
Principle involved
Strong acid to dehydrate monosaccharide to produce furfural or
hydroxymethylfurfural
Intermediate furfural derivatives will condense with -naphtol
Visual positive result
Purple ring at interphase for all carbohydrates
Bials-Orcinol Test
Reagents
HCl, FeCl3 and orcinol
Principle involved
Strong acid to dehydrate monosaccharide to produce furfural or
hydroxymethylfurfural
Will then condense with orcinol
Visual positive result
Blue-green solution for aldopentoses
Seliwanoffs Test
Reagents
HCl, resorcinol
Principle involved
Strong acid to dehydrate monosaccharide to produce furfural or
hydroxymethylfurfural
Will then condense with resorcinol
Visual positive result
Cherry-red solution for ketohexoses
Benedicts Test
Reagents
CuSO4, Na2CO3, Na3C6H5O7
Principle involved
Cu2+ oxidizing agent
Cupric ions reduced to cuprous, form Cu2O precipitate
Sodium citrate used to keep Cu ions in solution
Visual positive result
Brick-red precipitate for all reducing saccharides
All monosaccharides are reducing saccharides
Barfoeds Test
Reagents
Cu(CH3COO)2, acetic acid
Principle involved
Cu2+ oxidizing agent
Cupric ions reduced to cuprous, form Cu2O precipitate
Visual positive result
Brick-red precipitate for all reducing monosaccharides
Monosaccharide (< 3 mins)
Disaccharide (~10 mins) -> considered as a negative result
Mucic Acid Test
Reagents
Concentrated HNO3
Principle involved
HNO3 is a strong oxidizing agent
formyl functional group will get oxidized to carboxylic acid
Primary alcohol group will get oxidized to carboxylic acid
Visual positive result
Test for galactose (galactaric acid / mucic acid -> sugar acid product)
Plane of symmetry not optically active
D-aldoronic acid
Redox reactions of aldoses
Phenylhydrazone Acid Test
Reagents
phenylhydrazine
Principle involved
phenylhydrazine is a strong oxidizing agent
formyl functional group will get oxidized to carboxylic acid
Secondary alcohol will get oxidized to ketone
Product is phenylhydrazone
Phenylhydrazone + phenylhydrazine = osazone
Visual positive result
Yellow orange crystals (osazones)
D-glucosazone (for glucose and fructose and mannose)
No sucrosazone
Mechanism for Phenylhydrazone Test
Nelsons Test
Nelsons A and Nelsons B
Nelsons A: Rochelle salt sodium potassium tartrate, Na2CO3, NaHCO3,
Na2SO4
Will also keep Cu ions in solution
Nelsons B: CuSO45H2O, H2SO4
Nelsons A and Nelsons B -> tartaric acid product
Colorimetry of Absorbance is based on the intensity of the product of
arsenomolybdate and the copper oxide solution
blue / blue-green solution
Thin Layer Chromatography
Mobile phase:
Para-anisaldehyde: visualizing agent
Green colored spots based on complex with the sugar
The more OH groups, the more polar
glucose > maltose > dextrin in Rf value