17.5 properties of monosaccharides physical properties chemical properties oxidation reduction...
TRANSCRIPT
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17.5 Properties of Monosaccharides Physical properties Chemical properties
Oxidation Reduction Formation of ring (hemiacetal) structures Glycoside (acetal) formation
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Physical Properties Taste = sweet
Solids at room temperature Water soluble (H-bonding)
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Chemical Properties Review: Reactions of aldehydes and ketones
1. Oxidation (aldehydes) to form carboxylic acids
2. Reduction to form alcohols
3. Formation of hemiacetal/hemiketal
4. Hemiacetal/hemiketal + alcohol → acetal/ketal
Now we’ll see all of these with
monosaccharides…
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1. Oxidation of Monosaccharides Monosaccharides are reducing sugars if their carbonyl
groups oxidize to give carboxylic acids Benedict’s reagent can oxidize aldehydes adjacent to -OH
group
In the Benedict’s text, D-glucose is oxidized to D-gluconic acid. Glucose is a reducing sugar.
C
C
C
C
C
CH2OH
HO
OHH
HO H
OHH
OHH
C
C
C
C
C
CH2OH
OHO
OHH
HO H
OHH
OHH
+ Cu2+
D-Glucose D-Gluconic acid
+ Cu2O(s)
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2. Reduction of Monosaccharides The reduction of the
carbonyl group produces sugar alcohols, or alditols
D-Glucose is reduced to D-glucitol (also called sorbitol)
Used in sugar-free products
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Learning Check
Write the products of the oxidation and reduction of D-mannose.
C
HO H
HHO
OHH
OHH
CH2OH
O
H
D-Mannose
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3. Monosaccharides + alcohol Formation of hemiacetal/hemiketal
(cyclic structures)
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Hemiacetal Review What is a hemiacetal? How is a hemiacetal formed?
What if the alcohol and carbonyl are attached?
C
O
HCH3 + CH3OH C
OH
HCH3
OCH3
H+
HO
CH2CH2
CH2CH2
C
H
O
=
CH2 CH2
C
OCH2
CH2
O
H
H
H+
CH2 CH2
C
OCH2
CH2
O
H
H
HO
CH
CH2
CH2CH2
C
H
O
=
CH2 CH2
C
OCH
CH2
O
H
H
H+
CH2 CH2
C
OCH
CH2
O
H
HCH2OH
CH2OH CH2OH
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Hexose hemiacetals Favor formation of 5- or 6-membered rings
Hydroxyl group on C5 reacts with the aldehyde or ketone
The Haworth structure can be written from the Fischer projection The D-isomer has the last CH2OH group located above the ring
The –OH group on the left (C3) is drawn up
The –OH groups on the right (C2, C4) are drawn down
Carbonyl C becomes chiral (anomeric carbon); drawn on the right
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Anomers are isomers which differ in placement of hydroxyl on anomeric C
The –OH is drawn down for the -anomer, and up for the -anomer
-D-Glucose -D-Glucose
Mashed potatoes or mashed paper?
OCH2OH
OHOH
OH
OH
OCH2OH
OHOH
OH
OH
and Anomers for D-Glucose
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and Anomers for D-Glucose
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Mutarotation In solution, -D-glucose is in equilibrium with β-D-glucose Mutarotation involves the conversion of the cyclic anomers
into the open chain At any time, there is only a small amount of open chain
aldehyde
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Cyclic Structure of Fructose
As a ketohexose, fructose forms a cyclic structure when the —OH on C5 reacts with the ketone on C2
Result is 5-atom ring Anomeric carbon is C2
CH2OH
C
C
C
C
CH2OH
O
HO H
OHH
OHH
D-Fructose
CH2OH
OH
OH
OH
CH2OHO
CH2OH
OH
OH
CH2OH
OHO
-D-Fructose -D-Fructose
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and Anomers for D-Fructose
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Write the cyclic form of -D-galactose:
Learning Check
C
C
C
C
C
CH2OH
OH
OHH
HO H
HHO
OHH
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4. Monosaccharide hemiacetals/ hemiketals + alcohol
When a cyclic monosaccharide reacts with an alcohol: A glycoside is produced (acetal/ketal) The bond is a glycosidic bond or glycosidic linkage
Glycosides do not exhibit open chain forms Glycosides are not reducing sugars
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17.7 Disaccharides A disaccharide consists of two monosaccharides
Disaccharide Monosaccharides
Maltose + H2O Glucose + Glucose
Lactose + H2O Glucose + Galactose
Sucrose + H2O Glucose + Fructose
H+
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Maltose Malt sugar Obtained from starch Used in cereals, candies, and brewing A disaccharide in which two D-glucose molecules are
joined by an (1 4)glycosidic bond
A reducing sugar (has a hemiacetal)
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Lactose Milk sugar Composed of galactose and glucose linked by a
(1 4) glycosidic bond Lactose intolerance A reducing sugar
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Sucrose Table sugar Composed of glucose
and fructose joined by 1 2-glycosidic bond
Has no isomers because mutarotation is blocked
Not a reducing sugar (no hemiacetal)
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Benedict’s Test on Disaccharides
From left to right, the four test Tubes contain Benedict’s reagent, 2% maltose solution, 2% sucrose solution, and 2% lactose solution.
Both maltose and lactose arereducing sugars. The sucrose hasremained unreacted.
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Disaccharides Summary
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Learning CheckIdentify the monosaccharides in lactose, maltose, and sucrose as glucose, fructose, and/or galactose:
A. Lactose
B. Maltose
C. Sucrose
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17.8 Polysaccharides
Polysaccharides are
polymers of
monosaccharides
“Complex” carbohydrates
Important polysaccharides
of D-glucose are:
Starch (Amylose and
Amylopectin)
Glycogen
Cellulose
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Starch and Glycogen Storage polysaccharides
Form monosaccharides used for energy
Starch Plants
Amylose is a continuous chain of D-glucose molecules linked by (1 4)-glycosidic bonds.
Amylopectin is a branched chain of D-glucose molecules linked by (1 4)- and (1 6)-glycosidic bonds.
Glycogen Humans, animals Similar to amylopectin,
but more highly branched.
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Structure of Amylose
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Structure of Amylopectin
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Cellulose Structural polysaccharide
Plant cell walls (cellulose) and animal exoskeletons (chitin)
Cellulose is a linear polymer of glucose molecules linked by (1 4)-
glycosidic bonds
Enzymes in saliva can hydrolyze (1 4)-glycosidic bonds in starch,
but not (1 4)-glycosidic bonds in cellulose
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Learning Check
Identify the types of glycosidic bonds in:1) Amylose
2) Glycogen
3) Cellulose
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End of Chapter 17!