Sugars

FTE2012
MOLECULES TO
MATERIALS
Massey University | massey.ac.nz | 0800 MASSEY Copyright Massey University 2023 ©

Course outline
Topic 1: Sugars, Carbohydrates, and Polymers Week 1 & 2 (Tyson Dais)
Topic 2: Organic Materials Week 3 (Tyson Dais)
Topic 3: Proteins Week 4 & 5 (Mark Waterland)
Topic 4: Bioinorganic Chemistry Week 6 & 8 (Mark Waterland)
Topic 5: Solutions Week 9 & 10 (John Harrison)
Topic 6: Gels and Colloids Week 11 & 12 (John Harrison)
Laboratory:
4 lab-based experiments (Weeks 4, 5, 10, & 11). Each experiment will require a medium length report
aimed at a specialist audience. There is also a lab test in Week 12

Course requirements
• Students must attend all laboratory sessions and submit lab reports on time (reports are
submitted as a group)
• Students must achieve a minimum C grade for this Module
• See Module outline on xSiTe
Instructors:
(Weeks 1 – 3) Dr Tyson Dais t.dais@massey.ac.nz
(Weeks 4 – 9) Professor Mark Waterland* m.waterland@massey.ac.nz
(Weeks 10 – 14) Associate Professor John Harrison j.a.harrison@massey.ac.nz
*Mark is the Module Lead for both FTE2011 and FTE2012

Lecture 1 – Structure and terminology for simple carbohydrates
Part 1:
• Background to carbohydrate chemistry
• Labelling structural features of sugars
• Open-chain Fischer projections
• Cyclized Haworth projections
• Chair conformations

Background:
Carb – o – hydrate:
Cx(H2O)x
Commonly C5 = C5H10O5 5 carbons = pentose sugar 3 = tri-

4 = tetra-
5 = penta-
Or 6 = hexa-
7 = hepta-
8 = octa-
Commonly C6 = C6H12O6 6 carbons = hexose sugar 9 = nona-

Fischer projections:
Fischer proposed a way to draw 3D chiral centres in 2D:
The most oxidised carbon points up in the Fischer projection, and the longest carbon
chain points down. In the right hand image these would go into the plane of the page.
The groups on the left (laevus, L) and right (dexter, D) come out of the page. This is
another way of representing a tetrahedral configuration

Fischer projections:
Sugars have many chiral centres, this makes Fischer projections very useful for
representing the open-chain form of a sugar
CHO CHO CHO
H OH HO H H OH
H OH H OH H OH
H OH H OH HO H
H OH H OH HO H
CH2OH CH2OH CH2OH
allose altrose mannose

Anomeric carbon:
The most oxidized carbon is shown at the top of the chain in a Fischer
projection, this carbon can be labelled C1 and is called the anomeric carbon
CHO CHO CHO
H OH HO H H OH
H OH H OH H OH
H OH H OH HO H
H OH H OH HO H
CH2OH CH2OH CH2OH

Anomeric carbon:
The rest of the carbon centres are then given numbers moving down the chain
1 CHO 1 CHO 1 CHO

2 2 2
H OH HO H H OH
3 3 3
H OH H OH H OH
H
4 OH 4 4
H OH HO H
H
5 OH 5 5
H OH HO H
6 CH2OH 6 CH2OH 6 CH2OH

Aldoses and ketoses:
The anomeric carbon (C1) can either be an aldehyde (CHO) corresponding to
an aldose sugar, or a ketone (CO-R) which means a ketose sugar
CHO CHO CHO
H OH HO H H OH
H OH H OH H OH
H OH H OH HO H
H OH H OH HO H
CH2OH CH2OH CH2OH

These three sugars have aldehyde groups and six carbons, so they can be
called aldo-hexose sugars
CHO CHO CHO
H OH HO H H OH
H OH H OH H OH
H OH H OH HO H
H OH H OH HO H
CH2OH CH2OH CH2OH

The first sugar is still an aldohexose that we’re familiar with, but the next two
sugars have ketone functional groups, therefore they are ketose sugars
COCH3
1 3 2 1
1 CHO 2C
OCH
3 4 C O C H 2C H 2C H 3
2 3 5
H OH H O
H H O H
3 3 6
H OH H O
H HO H
4 5 7
HO H H O
H H O H
5 6 8
HO H H O
H H O H
CH2OH
6 CH2OH 7C
HO
2 H 9 C H 2O H

Stereochemistry:
When sugars cyclize they typically use the oxygen of the highest numbered
stereocentre to form the ring. Once cyclized we can’t know if the –OH was on
the left (L) or right (D) in the Fischer projection:
CHO CHO CHO
H OH HO H H OH
H OH H OH H OH
H OH H OH HO H
H OH H OH HO H
CH2OH Right = D CH2OH Right = D Left = L CH2OH

Labelling Fischer projections:
We can now use the terms we’ve just learned to label these sugars
3 2 1
1 CHO 1 CHO 4 C O C H 2 C H 2C H 3 1C H O
2 2 5 2
HO H HO H HO H H O H
H
3 OH HO
3 H HO
6 H H O
3 H
H 4 OH H 4 OH H
7 OH H O
4 H
H 5 OH H 5 OH 8C H 2O H 5C H 2 O H
6 CH2OH Hexose 6 CH2OH Hexose Octose Pentose

Aldose Aldose Ketose Aldose
D isomer D isomer D isomer L isomer
Fischer Projection of D-aldohexoses
Can have 2 different conformations (D or L) at 3 positions (C2, C3, C4)

therefore 23 = 8 different isomers

Cyclizing sugars
In solutions, the linear or open-chain (Fischer projection) form only makes up a
small percentage of the species present, a majority of the sugar will convert to
the cyclic form. We will first use Haworth projections to draw cyclic sugars
Start by rotating your Fischer

projection 90° clockwise
and keep track of your labels

Cyclizing sugars
Although the Fischer projection is drawn linearly, we know that carbon (alkyl)
chains are not perfectly flat or straight. If we change how it’s drawn to bring the
highest numbered chiral carbon close to the anomeric carbon, then we can see
how they might react

Cyclizing sugars
The anomeric carbon has a partial positive charge (because of the
electronegative oxygen it’s bonded to), which allows the lone pair of electrons
on the oxygen of the C5-OH group to react with C1

Nomenclature for cyclic sugars
When the open-chain sugar form undergoes cyclization it could form a 5 or 6
membered ring.
We call the 6-memebered rings pyranose sugars and the 5-membered rings
are called furanose sugars
CH2OH
HO H
O O C
HO
2H
OH
HO H
O O
H
O
H
OH
pyranose furanose

Haworth projections
This representation of the cyclic form doesn’t tell us about the relative
stereochemistry of each chiral carbon in the ring. The Haworth projection
addresses this issue. Conventionally, the CH2OH group of a D sugar points up
Pyranose Furanose
Haworth diagram Haworth diagram

Haworth projections
We can then use the Fischer projection to give us the stereochemical
information required to complete the Haworth diagram
Fischer projection Haworth diagram Fischer projection Haworth diagram

of D-allose of D-allopyranose of D-lyxose of D-lyxofuranose

Haworth projections
If the OH groups of chiral carbons point to the right (D) in the Fischer projection
then they will point down in the Haworth projection (which you see when you
rotate the Fischer projection 90º clockwise)


Haworth projections
If the OH groups of chiral carbons point to the left (L) in the Fischer projection
then they will point up in the Haworth projection (which you see when you
rotate the Fischer projection 90º clockwise)


Haworth projections
Note that we can’t know which direction the anomeric OH group (C1-OH,
formed from the carbonyl oxygen when the sugar cyclized). Experimentally, it
will form a statistical mixture of so called α and β anomers (C1 OH)


Haworth projections
The α-anomer has the C1-OH pointing down on a Haworth projection and the
β-anomers has the C1-OH pointing up
Haworth diagram Haworth diagram Haworth diagram Haworth diagram

of α-D-allopyranose of β-D-allopyranose of α-D-lyxofuranose of β-D-lyxofuranose

Haworth projections
Chemists typically don’t draw C-H’s in skeletal structures, so we can make our
Haworth diagrams a bit tidier
Haworth diagram Haworth diagram Haworth diagram Haworth diagram
of α-D-allopyranose of β-D-allopyranose of α-D-lyxofuranose of β-D-lyxofuranose
D, aldohexose, D, aldohexose, D, aldopentose, D, aldopentose,

pyranose, pyranose, furanose, furanose,
α-anomer β-anomer α-anomer β-anomer
Haworth projections
Example: convert the below Fischer projection of a ketoheptose sugar into the
corresponding β-pyranose Haworth projection
COCH3
OH
H OH
OH
H OH
Rotate 90º clockwise Convert to the β-anomer
HO H
and number each C of the pyranose form
OH
H OH
CH2OH
1-deoxy-D-gulo-2-heptalose 1-deoxy-β-D-gulo-2-heptapyranose

Haworth projections
Example: convert the below Fischer projection of an aldohexose sugar into the
corresponding α-furanose Haworth projection
Rotate 90º clockwise Convert to the α-anomer
and number each C of the furanose form
The furanose form means C4-OH will

react with C1
D-glucose α-D-glucofuranose

Chair diagrams
We can use chair diagrams (just like cyclohexane) to represent cyclic
pyranose sugars in another, more
chemically accurate way.

Chair diagrams
Recall that there are two different positions
that substituents can take in chair diagrams:
axial (ax) or equatorial (eq)
Bonds that go straight up or down are axial
Bonds that go out and slightly up or down

are equatorial

Chair diagrams
At C1, C3, and C5 (in our diagram here) the
substituents are either axial downwards or
equatorial (slightly) upwards.
For C2 and C4, the substituents are either
axial upwards or equatorial (slightly)
downwards
To draw chair diagrams, we can apply the

same rules for converting a Fischer
projection to a Haworth projection.
Right on Fischer = down on Haworth/chair
Chair diagrams
To draw chair diagrams, we can apply the
same rules for converting a Fischer
projection to a Haworth projection.
Right on Fischer = down on Haworth/chair
This means the α-anomer will be axial at

C1, and the β-anomer will be equatorial

Representing monosaccharides
D-allose β-D-allopyranose β-D-allopyranose

(Fischer) (Haworth) (Chair)

α-D-allopyranose
β-D-allopyranose
D-allose
(Fischer)

It’s important to
remember that, in
the solution phase,
there will be a 63.7% 35.5%
statistical mixture
of all five of these
species present
0.6% 0.2%
Worked examples
For the given Fischer projection, draw the β-anomer as a chair diagram and
label the substituents as either axial or equatorial. Also draw a Haworth
projection for the furanose form as a mixture of anomers
D-glucose
Worked examples
For the given Fischer projection, draw the β-anomer as a chair diagram and
D-glucose
Worked examples
For the given Fischer projection, draw the α-anomer as a chair diagram and
1-deoxy-D-gulo-2-heptalose
Worked examples
For the given Fischer projection, draw the α-anomer as a chair diagram and
1-deoxy-D-gulo-2-heptalose
Lecture 1 – Structure and terminology for simple carbohydrates
Part 2:
• Identifying and naming glycosidic linkages
• Worked examples of naming linkages
• Reducing and non-reducing sugars
• Some famous di-, tri-, oligo-, and polysaccharides

Disaccharides
2 sugars connected – sucrose, lactose and maltose:
Sucrose Lactose Maltose
This 3D structure gives them the unique properties they have – even though
they are very similar in some cases!
Glycosidic linkages
The ester-type bond between monosaccharides are called glycosidic linkages
Glycosidic linkages always involve the anomeric position of one the sugars

Glycosidic linkages
The bond is then described by the numbers of the carbons of the rings that are
bonded through the -O- linkage, and whether the anomeric carbon (C1) is in the
α or β – configuration

Glycosidic linkages
This is therefore a 1-4 β linkage

Glycosidic linkages
This is therefore a 1-4 α linkage

Examples of glycosidic linkages
3 2
2
1 β 3 1 β
1
1-3 β linkage
1-3 β linkage

Examples of glycosidic linkages
1-4 β linkage 1
4
3 2
β
2 β
1 3 1
1
2
1-4 α linkage β
1
1 4 1
α
3 2 1-2 β and 1-3 β linkages

Acetals (were aldehydes) or Ketals (were ketones)
Every anomeric carbon of a sugar is
in its acetal or ketal form.
If we label the anomeric carbon C1
Then an acetal will have 2x C1–O
bonds, 1x C1–C bond, and 1x C1–H
bond
If the oxygen outside of the ring has a
C atom attached then we call it an
acetal, but if it has an H atom
attached then we call it a hemi acetal!

If C1 is bonded to an oxygen and a
carbon outside of the ring then it is a
ketal.
If the oxygen atom outside of the ring
has an H atom attached then we call
it a hemi-ketal.

So C with 2 O’s & 1 H = acetal type

and C with 2 O’s & 2 C’s = ketal type
If one of the oxygens has an H then

it’s also a hemi

Identifying acetals, hemi-acetals, ketals, and hemi-ketals
• Start by identifying the anomeric carbons
• Then look at what it’s attached to:
2 O’s and 2 C’s
Ketal

Identifying acetals, hemi-acetals, ketals, and hemi-ketals
• Start by identifying the anomeric carbons
• Then look at what it’s attached to:
Acetal
Ketal Hemiketal Hemiacetal

Forming glycosides (acetals or ketals, from their hemi- forms)

Reducing and non-reducing sugars
If there’s an OH attached to the anomeric position (so either hemi-acetal or
hemi-ketal), then the ring is able to open into the linear aldehyde/ketone form
Acetal

If it is an aldehyde (i.e. a hemi-acetal in the cyclic form) then it is called a
‘reducing sugar’ as the aldehyde can be oxidised to the carboxylic acid (thereby
reducing some other species)
Acetal

Hemi-ketals can convert back to the open-chain sugar form but a ketone
functional group cannot (easily) be oxidized, therefore will be non-reducing.
Acetals and ketals are locked in their cyclic forms (can’t convert to the open-
chain sugar) therefore they are non-reducing
Acetal

Oxidized monosaccharides
Reducing sugars provide one source of oxidized monosaccharides (the –CHO).
But the primary –CH2OH group can also be oxidized to –COOH
Aldaric acid
‘a’ for all
Aldonic acid
‘o’ for one (C1)
Alduronic acid

Reduced monosaccharides
The carbonyl group of monosaccharides can also be reduced to an alcohol,
which prevents ring closure. These are often called sugar alcohols

Trisaccharide & tetrasaccharide (oligo) examples
3 or 4 sugars connected – raffinose and stachyose

Polysaccharide examples
1000’s of sugars connected
Cellulose – glucose held by 1,4-β bonds:

Cellulose strands pack together forming

hydrogen bonds between each strand
Hemicellulose is a naturally occurring branched variant of cellulose, between

500 – 3000 sugars. In addition to glucose, hemicellulose contains large
amounts of xylose, and also some mannose, galactose, rhamnose, and
arabinose sugars.

Starch – purely 1,4-α glucose bonded units is called amylose (~25%)

Starch – 1,4-α glucose with 1,6-α branching is called amylopectin (~75%)

Branching takes place every 24 to 30 glucose units
Can contain up to 2 million glucose units

Native starches have limited use in the food industry as they often produce
weak rubbery pastes when heated and undesirable gels when cooled.
Starches are often modified chemically, physically, or enzymatically to give
them more favourable heat, pH, shear, temperature, or processing resistance.
Modified starches are common food additives, for thickening, stabilizing, and
emulsifying applications.
We can look at two examples of modified starches that are used as food
additives: acetylated distarch adipate (E1422) and hydroxypropyl distarch
phosphate (E1442)
Acetylated distarch adipate (E1422)
This starch has been treated with acetic anhydride (up to 8% w/w) and adipic
anhydride (up to 0.12%) to give high temperature resistance. E1422 is often
used as a stabilizer and thickener
Adipic anhydride forms cross-links

(next lecture) between the C2 or
C3 OH groups of each glucose unit
Acetic anhydride reacts with hydroxyl
groups, especially at the anomeric
position to modify the structure

Hydroxypropyl distarch phosphate (HDP, E1442)
HDP is a modified resistant starch derivative, meaning that it is resistant to
digestion, and therefore has good bulking and sweetening properties with no
associated calorific value. Starch is esterified with sodium trimetaphosphate or
phosphorus oxychloride, then etherified by propylene oxide

Glycogen – glucose held by 1,4-α bonds with 1,6-branching, but much much
more branching than starch (6 vs 20 units)
Starch is energy storage in plants

Glycogen is energy storage in animals

Summary
• Monosaccharides
• Functional groups: Aldoses and Ketoses
• Number of carbons: Triose, Tetrose, Pentose, Hexose, etc
• Oligosaccharides
• Disaccharides: Maltose, Lactose, Sucrose
• Tri/Tetra-saccharides: Raffinose and Stachyose
• Polysaccharides
• Cellulose
• Starches
• Glycogen

Sugars

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FTE2012

Massey University | massey.ac.nz | 0800 MASSEY Copyright Massey University 2023 ©

Massey University | massey.ac.nz | 0800 MASSEY Copyright Massey University 2023 ©

*Mark is the Module Lead for both FTE2011 and FTE2012

Massey University | massey.ac.nz | 0800 MASSEY Copyright Massey University 2023 ©

Massey University | massey.ac.nz | 0800 MASSEY Copyright Massey University 2023 ©

Commonly C5 = C5H10O5 5 carbons = pentose sugar 3 = tri-

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CH2OH CH2OH CH2OH

allose altrose mannose

CH2OH CH2OH CH2OH

allose altrose mannose

1 CHO 1 CHO 1 CHO

6 CH2OH 6 CH2OH 6 CH2OH

CH2OH CH2OH CH2OH

allose altrose mannose

CH2OH CH2OH CH2OH

allose altrose mannose

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CH2OH Right = D CH2OH Right = D Left = L CH2OH

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6 CH2OH Hexose 6 CH2OH Hexose Octose Pentose

Can have 2 different conformations (D or L) at 3 positions (C2, C3, C4)

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Start by rotating your Fischer

and keep track of your labels

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Massey University | massey.ac.nz | 0800 MASSEY Copyright Massey University 2023 ©

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Fischer projection Haworth diagram Fischer projection Haworth diagram

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Fischer projection Haworth diagram Fischer projection Haworth diagram

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Fischer projection Haworth diagram Fischer projection Haworth diagram

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Fischer projection Haworth diagram Fischer projection Haworth diagram

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Haworth diagram Haworth diagram Haworth diagram Haworth diagram

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D, aldohexose, D, aldohexose, D, aldopentose, D, aldopentose,

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Rotate 90º clockwise Convert to the α-anomer

and number each C of the furanose form

The furanose form means C4-OH will

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Bonds that go straight up or down are axial

Bonds that go out and slightly up or down

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To draw chair diagrams, we can apply the

This means the α-anomer will be axial at

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D-allose β-D-allopyranose β-D-allopyranose

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Sucrose Lactose Maltose

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This is therefore a 1-4 β linkage