Chapter 11 Carbohydrate

Monosaccharides are the Simplest Carbohydrates

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Carbohydrates = carbon-based molecules rich in hydroxyl groups

o Empirical formula (CH2O)n
Simple carbohydrates = monosaccharides = aldehydes or ketones that have 2 or more hydroxyl groups

Dihydroxyacetone and glyceraldehyde are constitutional isomers same molecular formula, atoms ordered
differently
Stereoisomers are isomers that differ in spatial arrangement (D or L)
o Most vertebrate monosaccharides have the D configuration
o D and L isomers are determined by the configuration of the asymmetric carbon atom farther from the
aldehyde or keto group
o Dihydroxyacetone is the only monosaccharide without at least one asymmetric carbon

Monosaccharides made up of more than 3 carbon atoms have multiple asymmetric carbons, so they can exist
as enantiomers (mirror images) and diastereomers
o The number of possible stereoisomers is 2n, where n the number of asymmetric carbons
o A 6-carbon aldose with 4 asymmetric carbons can exist in 16 possible diastereomers

Know aldehyde sugars Glyceraldehyde, Erythrose, Threose, Ribose, Xylose, Allose, Glucose, Mannose,
and Galactose.

Know keto sugars Dihydroxyacetone, Erythrulose, Ribulose, Xylulose, and Fructose. Be able to draw
Sedoheptulose

These are the structures of most of the

most important sugars.
Notice that all biological sugars are D,
meaning the last hydroxyl before the
CH2OH at the bottom goes to the right
Notice D-glucose and D-mannose differ
only at C-2. Sugars that are
diastereomers differing in configuration
at only a single asymmetric center are
called epimers.

Many common sugars exist in cyclic forms

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The predominant forms of ribose, glucose, fructose, and many other sugars in solution (inside the cell) are not
open chainsthe open chain forms of these sugars cyclize into rings

When an aldehyde sugar

cyclizes you get a hemiacetal
with OH and OR.

Similarly, a ketone can react with an alcohol to form a hemiketal

When a keto sugar cyclizes you

get a hemiketal with OH and OR
where the keto carboxyl used to
be.
Hemiketals and Hemiacetals are
reducing sugars because they
can be easily oxidized.When the
anomeric OH is derivatized giving
OR an OR instead of OH and OR
You have an Acetal or a Ketal (the
hemi goes away) and you also
have a non-reducing sugar.

Be able to draw all assigned sugar structures either in Fischer or Haworth projections.

-D-sedoheptulofuranose & -D-xylopyranose

Boats and Chairs

The chair form, shown here, is the typical conformation of the

pyranose ring.
Notice that having bulky groups mounted axially (straight up or
down, perpendicular to the plane of the ring) leads to strong
steric hindrance, so the OH and CH2OH groups should all be
equatorial (sharing the plane of the ring).
The only aldohexose that can do that, have all bulky groups
equatorial, is beta-D-glucose. And many people think that is
why glucose is the default sugar in biology. It was just very
slightly stabler than all of the other sugars

For the CHAIR form you need to understand that the bond
angles are more realistic in the chair representation than
in the Haworth representation.
Haworth shows axial substituents as STRAIGHT UP and
STRAIGHT DOWN. Here the axial groups are 109 degrees
apart (realistic) rather than 180 degrees apart.

Reducing Sugars
Reducing Sugars reduce an
oxidizing reagent. The sugar
becomes oxidized, the reagent
becomes reduced, and the
reduction of the reagent gives a
visible change.
This is how beta-D-glucopyranose
(or beta-D-glucose) reacts with
Fehlings solution. It is oxidized
to become Gluconic Acid.

A Glycoside has
something attached
to the Anomeric
Hydroxyl (C-1 for
aldehydes, C-2 for
ketones). This
stabilizes the sugar
ring structure.

In biochemical pathways,
sugars are very often
phosphorylated. Three
common phospho-sugars
are shown.

A glycosidic linkage is a substitution on

the ANOMERIC carbon. So adding
anything to carbon 1 of glucose produces
a glycoside.
A substituent at 2, 3, 4, or 6 is just an
ether.
This disaccharide is maltose and a chain
of many maltoses would be amylose, or
starch. Edible starches are based on
this structure.
The linkage here is called an alpha 1, 4
linkage.

Sucrose, lactose, and maltose are the common disaccharides

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Disaccharide = 2 sugars joined by an O-glycosidic bond

Lactose, the disaccharide of milk, consists of galactose joined to glucose by a beta-1,4-glycosidic linkage
Lactose is hydrolyzed to these monosaccharides by lactase in human beings

Lactose (and Cellobiose) have a beta- 1,4 linkage. Lactose or milk sugar is a disaccharide of Galactose beta 1,4
Glucose.
Cellobiose (not shown) is Glucose beta 1,4 Glucose. It is important because the beta 1,4 polymer of glucose is
Cellulose, which of course is not digestible by higher animals.
Lactose is digestible by mammals when they are nursing. Then most mammals undergo a developmental change to
become lactose intolerant.
It is important to understand that the Fructose ring of Sucrose is drawn upside down and backwards. The anomeric
carbon is shown on the left.
It is better to draw this disaccharide in a top and bottom representation, so that both sugars can be in a proper
Haworth form.

Know how to draw, and name systematically, disaccharides such as sucrose, lactose,
and maltose

Sucrose is stable because it is not a reducing sugar. Lactose, or milk sugar, is

indigestible for adult mammals who/which generally don't have enough lactase.
Understand "lactose intolerance"
Many adults are intolerant of milk because they are deficient in lacase.
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Many adults unable to metabolize the milk sugar lactose, experience gastrointestinal disturbances when
drinking milk

Lactose intolerance = hypolactasia caused by deficiency of the enzyme lactase, which cleaves lactose into
glucose and galactose
Lactose is a good energy source for microorganisms in the colon, and they ferment it to lactic acid while
generating methane (CH4) and hydrogen gas (H2); the gas creates the uncomfortable feeling of gut distension
and farting
The lactate produced by the microorganisms is osmotically active and draws water into the intestine and
undigested lactose diarrhea

Here is the basic structure of

Glycogen.
Long starch like chains of alpha1,4 linked glucose, but about
every 10th glucose there is an
alpha 1,6 branch point.
So the whole molecule is
branchy and that makes it easier
to metabolize quickly than the
linear starch molecules

Cellulose on the left

forms straight chains
and flat sandwich
structures. This is part
of why it is hard to
metabolize (although
microorganisms can
make Cellulase).
Starch and glycogen
have alpha 1, 4 links
which make arc shapes
that are easier for
enzymes to interact
with.

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The ABO blood group

antigens are simply small
oligosaccharides.
The differences are minimal,
but if you have Type A blood
and you get a transfusion of
Type B blood, the response
from your immune system
could kill you.
Type O is the universal donor.
[Potential test material this is
important!!!] If youre going
to build A, youve gotta go
circle-box-circle-triangle box.
Build B, circle-box-circletriangle-circle. O is the
stripped down version of A
and B, its the minimal
oligosaccharide. The
structure of O is on the
pathway both to A and to B.

Raffinose is a trisaccharide
found in beans, onions, beets
and other vegetables. Is it a
reducing sugar? What are
the monosaccharides?
Raffinose is responsible for
the gas (flatulence) most
people get after eating beans
and other vegetables. We
cant break down alpha
galactosides.
So the problem is a little like
Lactose Intolerance Beano and other products contain
the enzyme (just as Lactaid
contains Lactase for the betagalactoside in milk sugar).

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