Summary of Carbohydrate Structures

See original handout pages for the following:

1. Open chain and cyclic forms of monosaccharides

2. Disaccharide structures: maltose, sucrose, lactose
3. Shorthand structures of amylose, amylopectin (glycogen),
and cellulose
4. Cyclization of aldoses and ketoses and rules for writing
Hayworth projection formulas (“LURD”, “BUAD”)

This version of the presentation does not have some graphics in the interest of making the file smaller

Chair Conformation of Pyranoses

Fig 9-8

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 Reducing Sugars: Aldoses
6
HO
Fig 9-10
5
O
4
OH 1
2

HO 3 OH
OH
α-D-glucopyranose
2 Cu+2

OH-

Cu2O(s)
OH- 6
HO
5
O
4
OH 1
O
2

Alkaline reagent with copper(II) chelator: HO 3

OH
Tartarate: Fehlings’s solution α-D-glucuronic acid lactone
Citrate: Benedict’s solution

Reducing Sugars: Open Chain Ketoses!

O O
CH2OH
1
CH1 CH1

C O
2 H C OH HO C H
HO C H
2 2
2 Cu+2 Cu2O(s)
3
OH- HO C H
3 + HO C H
3

H C OH
4 H C OH H C OH
4 4
H C OH
5 H C OH H C OH
5 5

CH2OH
6 CH2OH CH2OH
6 6

OPEN CHAIN FORM

Ketose rearrances to mixture of aldoses
which can be oxidized by Cu2+ reagents
either as the open chain form or as the
cyclic form

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 Functions of Monosaccharides
Glyceraldehyde and dihydroxyacetone (C3):
-Intermediates in glycolysis
-Precursors for glycerol used for triglyceride and
phosphoglyceride biosynthesis

Ribose (C5): (CH2O)n partly oxidized, readily available energy source

-Source of energy for plants and animals
-Monomer unit for vitamin-derived coenzymes (NAD , FAD, etc) +

-Monomer unit for RNA

Ribofuranose in RNA and coenzymes

NICOTINAMIDE ADENINE DINUCLEOTIDE

( B3 niacin(amide))

H O

C
NH2
O
-
N
O P O O

OH OH
O NH2
N
N

N N
-
O P O O
O

OH OH

**NAD
(oxidized form)

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 Functions of Monosaccharides
(CH2O)n partly oxidized, readily available energy source

Glucose (C6):
-Source of energy for plants and animals in glycolysis
-Monomer unit for cellulose in plants
Fructose (C6):
-Source of energy for plants and animals in glycolysis

DISACCHARIDES: Maltose
Provides energy for
maltose
HO
O
HO
O
germinating seeds
HO HO (breakdown product of
HO O OH amylopectin and amylose
OH OH
in germinating seeds)
O-α-D-glucopyranosyl-(1 -> 4)-α (or β)-D-glucopyranose
(ending = "ose" since anomeric OH is free)

Hydrolyzed into glucose

by an enzyme called
α-glucosidase

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 DISACCHARIDES: Sucrose
sucrose Storage saccharide in…
HO
O
HO
glucose = α
HO …sugar beets
OH O
O
HO
fructose = β
HO OH
…sugar cane
OH
O-α-D-glucopyranosyl-(1 -> 2)-β-D-fructofuranoside
(ending = "oside" since anomeric O is derivatized)
Hydrolyzed into glucose and
fructose by an enzyme called
invertase

DISACCHARIDES: Lactose

lactose
HO
O OH
HO
HO
O O
HO OH
HO

OH

O-β-D-galactopyranosyl-(1 -> 4)-β -D-glucopyranose

Found in milk, lactose provides

energy to nursing infant
Hydrolyzed by
laccase = β-galactosidase

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 WRITING AMYLOSE POLYMER
HO HO
O O
HO HO
O
HO O OH
O
OH OH

Linear α-(1 ->4) linked polymer of glucose

The reducing end

of the polymer
The nonreducing end (hemiacetal)
of the polymer
Fig 09-16.GIF

THREE-DIMENSIONAL AMYLOSE

~ 20 D

~ 20 D

Fig 09-16.GIF

http://www.wellesley.edu/Chemistry/chem227/sugars/amylose-end.gif

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 BIOLOGICAL FUNCTION OF AMYLOSE
Amylose is a storage polymer for glucose in plants

Q: How is the structure

of amylose related to its
biological function?

A: The amylose polymer is a

storage polymer for glucose. It
has a helical structure which
allows for more glucose to be
packed into a given volume.

HYDROLYSIS OF AMYLOSE: α-Amylase

(in saliva and pancreatic juices of animals)
(in plants and all other living organisms)
α-Amylase is an endoglycosylase:
It randomly hydrolyzes within the linear polymer (> 3)
giving a mixture of maltose and glucose

HO HO
O O
HO HO
O O O
OH OH

Linear α-(1 ->4) linked polymer of glucose

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 HYDROLYSIS OF AMYLOSE: β-Amylase
(in germinating seeds, sweet potatoes)

β-Amylase is an exoglycosylase:
It removes maltose units from the nonreducing
ends of the amylose (> 4)

HO HO
O O
HO HO
HO
O O O
OH OH

Linear α-(1 ->4) linked polymer of glucose

The nonreducing end of the polymer

How are Glycogen and Amylopectin Different?

Polymer Occurance Function
Glycogen Liver, muscle Storage polymer
4-10 glucose/linear segments for glucose

Amylopectin Plants ""

> 12 glucose/linear segments

How are the structures of glycogen and amylopectin

related to their biological function?

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 Periodate oxidation (lab) and methylation
can determine degree of brancing
METHYLATION OF GLYCOGEN VERSUS AMYLOPECTIN
HO
O
OH branch point
O
O α (1 - 6)
OH
HO HO HO
O O O O
OH OH OH OH
HO O O O O O OH
OH OH α (1 - 4) OH OH
nonreducing end linkages reducing end
O
CH3I OR CH3OSOCH3
O
H+

Polymer I: 8.5 % 2,3 dimethyl glucose

Polymer II: 2.1 % 2, 3 dimethyl glucose
+ what other products?
(draw structural formulas for all products)
Which polymer is glycogen and which is amylopectin and why?

Enzyme that hydrolyze glycogen

Polymer Hydrolytic Enzymes
Glycogen Glycogen Phosphorylase
gluc-(gluc)n + Pi
(gluc)n + gluc-1-Pi

HO
O
OH branch point
O
O α (1 - 6)
OH
HO HO HO
O O O O
OH OH OH OH
HO O O O O O OH
OH OH α (1 - 4) OH OH
nonreducing end O linkages reducing end
O
-
O P OH
-
O

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 Enzyme that hydrolyze amylopectin
Polymer Hydrolytic Enzymes
Amylopectin Starch Phosphorylase
gluc-(gluc)n + Pi
(gluc)n + gluc-1-Pi

HO
O
OH branch point
O
O α (1 - 6)
OH
HO HO HO
O O O O
OH OH OH OH
HO O O O O O OH
OH OH α (1 - 4) OH OH
nonreducing end O linkages reducing end
O
-
O P OH
-
O

What happens next with these branched polymer?

Fig 15-13.GIF

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 WRITING CELLULOSE STRUCTURE
HO
O O
HO
HO
O O
OH
HO
Actual O
orientation OH
Linear β-(1 ->4) linked polymer of glucose
of adjacent
glucose
residues:

Fig 9-17.GIF

Linear fibers aggregate

into sheets…

Sheets aggregate into

microfibrils…

Microfibrils aggregate
into stiff, rigid structures

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 What is the biological function of cellulose?

Cellulose provides…
1. Structural ridigity to plants
2. Another polymer for glucose
storage

How is the structures of cellulose related to its biological function?

What enzyme can hydrolyze cellulose?

HO
O O
HO
HO
O O
OH
HO
HO
O O
HO OH
HO
O O
OH
HO
O
OH

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