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3/24/2011

A. REFRESHING
LECTURE 7
D & L Designation
CARBODYDRATE REACTION  The arrangement of the OH's and H's on these atoms is
very important.
 Structural formulas for sugar molecules are often written in
the vertical arrangement with the aldehyde or the ketone
group at or near the top.
 The sugar is of D (dextro
(dextro)) form when the O H
1C
position of the OH (hydroxyl group) on the
last asymmetric carbon atom (No. 5) is on H 2C OH
the right, the reverse is of L (levo
(levo)) form HO 3C H
 D-glucose is an aldohexose with aldehyde H 4C OH
group (red), and the the asymmetric center H 5C OH
(blue) furthest from the aldehyde 6CH OH 2
D-glucose

ASYMMETRIC CARBON Pyranose and Furanose


Glucose can exist in both a straight-chain and ring form.

2
Monosaccharides contain asymmetric carbon
atoms (e.g. 4 in glucose & 2 in ribulose
ribulose))
1 3
H O
1CH2OH
1C
2C O
H 2C OH
4
HO 3C H H 3C OH

H 4C OH H 4C OH

H 5C OH 5CH2OH 5
6CH2OH D-ribulose
D-glucose

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Pyranose and Furanose

 If the carbon chain is long enough, the alcohol at one end


of a monosaccharide can attack the carbonyl group at the
other end to form a cyclic compound.
 When a six-
six-membered ring is formed, the product of this
reaction is called a pyranose
pyranose,, shown in the figure below.

• When a five-
membered ring is
formed, it is called a
furanose

D-glucose can cyclize in two


ways forming either furanose or
pyranose structures

 The reactions that lead to the formation of a pyranose or a The a and b anomers
furanose are reversible  There are two possible structures for the pyranose and
 For example a-D-glucopyranose or b-D-glucopyranose, furanose forms of a monosaccharide, which are called the
these anomers are interconverted to give an equilibrium a- and b-anomers
mixture that is 63.6% of the b-anomer and 36.4% of the a-
anomer.
 The 2:1 preference for the b-anomer can be understood by
comparing the structures of these molecules.
 In the b-anomer, all of the bulky -OH or -CH2OH substituents lie
+
more or less within the plane of the six-
six-membered ring.
D-ribose -D-ribofuransoe -D-ribofuranose
 In the a-anomer, one of the -OH groups is perpendicular to the
plane of the six-
six-membered ring, in a region where it feels strong
repulsive forces from the hydrogen atoms that lie in similar
positions around the ring.
 As a result, the b-anomer is slightly more stable than the a-anomer +

D-fructose -D-fructofuranose -D-fructofuranose

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The a and b anomers

Glycosidic Linkages
 The a and b anomers of glucose.
 The position of the anomeric
carbon (green
(green or red
red)) relative to
the CH2OH group bound to
carbon 5: they are either on the
(α), or the same
opposite sides (α
(β).
side (β

Alternative Glycosidic Linkages: B. Carbohydrate synthesis


Maltose and Lactose  CHO’s are made in the chloroplast and cytosol
• Maltose contains two molecules of D-glucose, and Lactose is comprised of one  Starch=chloroplast
molecule of D-glucose and one of D-galactose.
• In both cases the monosaccharide units are connected by 1,4-glycosidic  Sucrose=cytosol
Sucrose= cytosol
linkages, i.e. they both contain a C1-O-C4' link.  Synthesis balanced by phosphate levels & triose
• In maltose the C1-O bond is in the a position, while in lactose it is oriented b
to the D-galactose ring. phosphate levels in the compartments
 Balances sugar storage & sugar transport
 Trioses are generated in the plastid
 If cytosol Pi is high,
high, Pi exchanges for trioses
trioses;;
sucrose is made
 If cytosolic Pi is low,
low, trioses stay in plastid;
starch is made

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C. REACTIONS OF
MONOSACCHARIDES
 Carbonyl reactions:  Alcohol reactions
 Osazone formation  Glycoside formation
 Cyanohydrin reaction  Ether formation
 Reduction  Ester formation
 Oxidation
 Action of base
 Action of acid
 Ring chain tautomerism

Formation of osazones
 Osazones are a class of carbohydrate derivatives found in organic
Cyanohydrin formation
chemistry, and formed when sugars are reacted with phenylhydrazine
phenylhydrazine..
 The famous German chemist Emil Fischer developed and used the  reaction of an aldose with HCN
reaction to identify sugars whose stereochemistry differed by only one  used to increase the chain length of monosaccharides
chiral (tangan) carbon
 results in a cyanohydrin which is then hydrolyzed to an
 A crystalline compound with a sharp melting point will be obtained
acid and reduced to the aldehyde
 D-fructose and D-
D-mannose give the same osazone as D- D-glucose
 Seldom used for identification; we now use HPLC or mass  known as the Fischer-
Fischer-Kiliani synthesis
spectrometry  can prepare all monosaccharides from D- D-glyceraldehyde

Reaction of acetone with sodium cyanide to hydroxyacetonitrile


A general reaction showing the formation of an osazone. D-glucose reacts
with phenylhydrazine to give glucose osazone. The same product is obtained

from mannose

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A hemiacetal is the combination of two functional groups, i.e. an alcohol and


ether attached to the same carbon

Aldehyde + Alcohol <===> Hemiacetal

Keton + Alcohol <===> Hemiketal

A hemiketal is an alcohol and ether attached to the same carbon, along with Monosaccharide has just one ring, a disaccharide has two, and a
two other carbons. A hemiketal is derived from a ketone polysaccharide has many

Monosaccharide has a single ring with a hemiacetal in it, a disaccharide has two
rings linked by an acetal functional group, and a polysaccharide has many rings The reaction
between aldehyde
linked by many acetal functional groups.
and alcohol produces
an acetal and a
hemiacetal (about
halfway to the acetal)

How about the "sugars"


with just 4 carbons.
The OH group on the bottom carbon
could form a hemiacetal with the
The atom C of disaccharide, above the oxygen which links the two aldehyde function to form a ring that
rings together, is connected to two oxygens. The carbon and fits the structure of a monosaccharide
these oxygens are in an acetal linkage (the bonds are heavier)

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The Structure of Glucose


D-glucose can cyclize in two
ways forming either furanose or
pyranose structures

Chair and boat conformations of a pyranose sugar

2 possible chair conformations


D-ribose and other five-carbon of b-D-glucose
saccharides can form either
furanose or pyranose structures

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Oxidation reactions Glucose oxidase


 Aldoses may be oxidized to 3 types of acids
 glucose oxidase converts glucose to gluconic acid
 Aldonic acids:
acids: aldehyde group is converted to a
carboxyl group ( glucose – gluconic acid) and hydrogen peroxide
 Uronic acids:
acids: aldehyde is left intact and primary alcohol  when the reaction is performed in the presence
at the other end is oxidized to COOH of peroxidase and o-
o-dianisidine a yellow color is
 Glucose --- glucuronic acid
 Galactose --- galacturonic acid
formed
 Saccharic acids (glycaric acids) – oxidation at both ends  this forms the basis for the measurement of
of monosaccharide) urinary and blood glucose
 Glucose ---- saccharic acid  Testape, Clinistix, Diastix (urinary glucose)
 Galactose --- mucic acid
 Dextrostix (venous glucose)
 Mannose --- mannaric acid

Reduction
 either done catalytically (hydrogen and a catalyst)
or enzymatically
 the resultant product is a polyol or sugar alcohol
(alditol)
 glucose form sorbitol (glucitol)
 mannose forms mannitol
 fructose forms a mixture of mannitol and
sorbitol
 glyceraldehyde gives glycerol

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Sugar alcohols are very useful


Sructures of some intermediates
sugar alcohols  Mannitol is used as an osmotic diuretic
 Glycerol is used as a humectant and can be nitrated to
nitroglycerin
 Sorbitol can be dehydrated to tetrahydropyrans and
tetrahydrofuran compounds (sorbitans)
 Sorbitans are converted to detergents known as spans and
tweens (used in emulsification procedures)
 Sorbitol can also be dehydrated to 1,4,3,6-
1,4,3,6-dianhydro
dianhydro--D-
sorbitol (isosorbide) which is nitrated to ISDN and ISMN
(both used in treatment of angina)

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