Carbohydrate Chemistry 30 July 2009

Lourdes L. Balcueva, MD
• diseases associated with carbohydrate metabolism: diabetes
Rate of toxicity: mellitus (DM), galactosemia, glycogen storage disease,
Font 8: notes from lecture and Harper's lactose intolerance
General Objective: • Structure of glucose can be represented in 3 ways:
• To know the structures and properties of ◦ straight chain formula: Fischer
carbohydrates ◦ cyclic: Haworth projection
Specific Objectives: ▪ molecule viewed from the side and above the
• To be able classify carbohydrates according to the plane of the ring
▪ bonds nearer to the viewer are bold and thickened
number of sugar units present and the number of
◦ chair form
carbon atoms
• To enumerate and describe the different
stereoisomers of carbohydrates
• To describe the linkages present in disaccharides and
polysaccharides

CARBOHYDRATES
General formula: Cn(H2O)n
Ex. Glucose: C6H12O6Glu Figure 1. Fischer (left) and Haworth(right)
• Most abundant biomolecule in nature
• Widely distributed in plants and animals
• Main source of energy in humans (oxidation of
carbohydrates is the central energy-yielding pathway in most
non-photosynthetic cells)
• are aldehyde or ketone derivative of polyhydric
alcohol
• all have C=O and –OH functional groups Figure 2. Haworth(left) and chair/boat form(right)
• insoluble carbohydrate polymers serve as protective
and structural elements in bacterial cell walls, plants Classification based on the size of base carbon atom:
(fibers- flushing out of toxins, slow down absorption of • condensation: simple to complex
glucose hence prevent abrupt rise in blood glucose), and • hydrolysis: complex to simple
connective tissues of animals • chaining relies on “bridging” of oxygen atoms through
glycoside bonds
• lubricate skeletal joints
• attached to proteins, act as signals that determine
1. Monosaccharides
intracellular location of glucoprotein
Classified based on: • carbohydrate molecules with only one actual or
 size of base carbon atom potential sugar group
 number of sugar units • cannot by hydrolyzed into simpler carbohydrates
 location of C=O • colorless, crystalline solids
 stereochemistry • soluble in water but not in non-polar
Other functions of CHO: solvents(lipids, benzene)
• have a sweet taste
Glucose:
• backbone is unbranched C chain; all carbon
• most important carbohydrate
atoms are linked by single bonds
• most dietary CHOs are absorbed in the circulation as
glucose • One C atom is double-bonded to an oxygen
• is the major metabolic fuel of mammals and fetuses atom to form carbonyl group.
• sedoheptulose – 7-carbon sugar
• precursor for synthesis of other carbohydrates in the body

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 Figure 3.
Figure 4.
2. Disaccharides
Classification based on stereochemistry:
• when 2 monosaccharides are combined together
 study of the spatial arrangement of molecules
with release of water molecule
• produces 2 monosaccharide/ sugar unit
STEREOISOMERS
• glucose + glucose = maltose; glucose + fructose =
• compounds having the same structural formula but
sucrose; glucose + galactose = lactose
differ in spatial configuration
• hydrolysis of sucrose = mixture of glucose and
• depends on the number of ASYMMETRIC(meaning:
fructose: “invert sugar” (levorotatory fructose inverts
the previous dectrorotatory action of sucrose) with 4 different substituents) C atom
• have the same order and types of bonds
• have different properties
3. Oligosaccharides
• FORMULA: 2n where n is the number of asymmetric
• condensation products of 3-10
carbon atom
monosaccharide units
ex. Glucose: 2n is equal to 16 (glucose has 4
• example: maltotriose (3 a-glucose residues)
asymmetric C carbons, 24=16)
4. Polysaccharides
DIASTEREO-ISOMERS
• condensation products of more than 10
• Monosaccharides with the same molecular
monosaccharides/ sugar units
formula but differ in the configuration about 2 carbon
• can be hexosans or pentosans depending on the
atoms
identity of constituent monosaccharides
Ex. Mannose and galactose
Classification based on the location of C=O:
EPIMERS
1. Aldose
• when sugars differ from one another only in
• if the carbonyl grp. is at the end of the carbon
configuration about one carbon atom (variations in
chain; monosaccharide is an aldehyde
configuration of the -OH and -H on carbon atoms 2, 3 and 4
2. Ketose of glucose)
• if the carbonyl group is at any other position; Ex. Glucose and mannose(C2); glucose and
monossacharide is a ketone galactose(C4)

• Monosaccharides with 5 or more carbon atoms in the

backbone occur as cyclic structures in solution
• Carbonyl group forms covalent bond with oxygen of a
hydroxyl group(usually the 2nd to the last either an
aldose or a ketose) along the chain (refer to Figure 1
and 2)
• α- and β– D glucose interconvert by mutarotation

Figure 5.

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 Figure 6.
Figure 7.
• The L and D isomerism is determined by its spatial
relationship with the parent compound of carbohydrates, the
3-carbon sugar glycerose (glyceraldehyde).
• D-(right) and L-(left) isomers- structure refers to the position
of the –OH group on the penultimate C atom hence,
MIRROR images!!!
• analogy: left and right hands are mirror images of each
other, however they are not superimposable.
• All biologically important sugars are present in a D-
conformation!!!
Figure 8.
• In solution, glucose is dextrorotatory (dextrose)
• Crystalline sugar: α-D glucopyranose
OPTICAL ACTIVITY • In solution: α-D glucopyranose (38%) and β-D
• the ability of a solution to rotate the plane of plane- glucopyranose(62%)
polarized light towards the right or towards the left
• to the right or dextrorotatory: ( + )
• to the left or levorotatory: ( - )
• gives rise to 2 structures that are mirror images of
each other called Enantiomers
• direction of rotation is independent of the stereochemistry of
sugar
example: fructose is D(-)

Figure 9.
PYRANOSE AND FURANOSE RINGS
• Fischer formula can account for some properties of glucose
• results from general reaction between aldehydes and but the cyclic structure is favored on thermodynamic
alcohols forming hemiacetals or between ketones and grounds and accounts for the remainder of its chemical
alcohols forming hemiketal properties
• pyranose is a 6-membered ring; furanose is a five-
membered ring
• only aldoses with 5 or more carbon atoms can form
pyranose rings
• - OH at C5 reacts with aldehyde grp at C1
• results in asymmetry at C1(anomeric C atom)
resulting in α- and β-stereoisomers of D-glucose
• for glucose in solution, more than 99% is in pyranose form
• Alpha and beta anomers
Figure 10.
α-(OH below ring) and β-(OH above) stereoisomerism in the
anomeric C
GLYCOSIDIC BOND
• Joins together 2 monosaccharides through a
(CONDENSATION) reaction between the anomeric
carbon of one unit and a hydroxyl group of another.
• If the 2nd group is a hydroxyl, the O-glycosidic bond is an
acetal link

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 -If the hemiacetal portion is glucose = glucoside; if Figure 13. β-D-galactopyranose (1→4) β-D-
galactose = galactoside; and so on. glucopyranose
• If the 2nd group is an amine, an N-glycosidic bond is formed. • Note the free –OH group on the anomeric C!!!!!!!!
• In glucose, only the C3 has –OH above the ring
Nomenclature:
• Monosaccharide on the left: unit where the anomeric
carbon is involved
• O precedes the name of the first monosaccharide
• α- or β- configuration of the first unit
• furanosyl or pyranosyl
• (no. of C atom of first unit  no. of C atom of 2nd
unit)
• AGLYCONE is the name of the 2nd compound if it is
not CHO (may be methanol, gycerol, sterol, phenol or base
such as adenine)

Figure 14.

**α-D-glucopyranose (1→2)β-D-fructoside
• --side: because there is no free –OH group on the anomeric
C
• absence of an anomeric carbon with a free potential
aldehyde or ketone group-- no longer exhibits reducing
properties

Figure 11. DISACCHARIDES

Figure 12. β-D-glucopyranose (1→4) β-D-
glucopyranose
• Monosaccharides joined covalently by O-glycosidic bond
• anomeric C and –OH of C4 in glucose
Figure 15.
• Ribose- RNA, Deoxyribose- DNA, duh 
• Deoxy sugars – hydroxyl group has been replaced by
hydrogen
• Examples: deoxy sugar L-fucose in glycoproteins and 2-
deoxyglucose (inhibitor) of glucose metabolism

Figure 16.

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 • glucose=dextrose , aspartame=AA, aspartic acid +
phenylalanine

Figure 21.

Figure 17. • Starch

1. homopolymer of glucose forming a-glucosidic chain
called a glucosan or glucan.
2. most abundant dietary carbohydrates in cereals,
potatoes,, legumes, and other vegetables
3. 2 main constituents:
1. amylose (15-20%)– non-branched
helical
structure
2. amylopectin (80-85%) – branched chains
Figure 18. with 24-30 glucose residues united by 1 → 4
linkages in the chains and 1 → 6 linkages at
branched points

Figure 19.
• a positive Benedict’s reaction forms a brick red precipitate
Figure 22.
POLYSACCHARIDES
• Carbohydrate polymers
Storage polysaccharides
• Energy storage- starch and glycogen

Figure 23. Glycogen

• Glycogen
1. storage in animals
2. more highly branched than amylopectin

Figure 20. Structural polysaccharides

• Used to provide protective walls or lubricative coating
to cells—cellulose and mucopolysaccharides
• Cellulose

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 • Insoluble
• Chief constituent of plant cell walls
• β-D glucopyranose units linked by β -1→4 bonds
forming long chain
• Cannot be digested!! - salivary amylase could only act
on α(1 → 4) linkages
• Source of bulk in our diet
• Glycosaminoglycans/Mucopolysaccharides
• with amino sugars and uronic acids
• when attached to protein molecule : proteoglycan
• proteoglycans have large number of -OH groups and
negative charges
• examples: hyaluronic acid, chondroitin sulfate, heparin
Structural Peptidoglycans
• Bacterial cell walls
• Cell membranes and Lipoproteins:
• 5% CHO in glycoproteins and glycolipids
• glycocalyx -has been shown with the use of lectins;
example: concanavalin A binds α-glucosyl and α-
mannosyl residues
• glycophorin – major integral membrane glycoprotein of
human RBC
• carbohydrates are also present in apo B of lipoproteins
AMYLOSE
• Abundant in potatoes, rice, tapioca, wheat and other
grains
• Hydrolysis will yield:
Soluble amylose- glucose units with
a 1 4 glycosidic linkage forming
unbranched long chain
Insoluble amylopectin- forms paste-like
gel; branched by a 16 linkage
Figure 24.
• Difference in linkage makes it unusable
• We lack an enzyme that can hydrolyze cellobiose (recall that
salivary amylase can only act on α(1 → 4) linkage
Others polysaccharides:
• Inulin:
◦ fructosan
◦ soluble in water and used to determine the glomerular
filtration rate
• Dextrins:
◦ intermediates in the hydrolysis of starch
• Chitin:
◦ structural - found in exoskeleton of of crustaceans,
insects and in mushrooms
◦ consists of N-acetyl-D-glucosamine units joined by β (1
→ 4) glycosidic linkages
The following are additional notes from Harper's:
Physiologically Important Monosaccharides
• metabolic intermediates in glycolysis and pentose
phosphate pathway
• pentoses – nucleotides, nucleic acids and several
coenzymes
• most important hexoses are: glucose, galactose,
fructose and mannose
• caroxylic acid derivates such as:
◦ D-glucuronate (glucuronide formation and in
glycosaminoglycans)
◦ L-iduronate (glycosaminoglycans)
◦ L-gulonate (intermediate in uronic acid pathway)
Important Glycosides in Medicine
• cardiac glycosides
◦ contain steroids as aglycones
◦ include derivatives of digitalis and strophanthus
(ouabain, inhibitor of NA K ATPase of cell
membrane)
• antibiotics such as streptomycin
Amino sugars (Hexosamines)
• D-glucosamine – constituent of hyaluronic acid
• D-galactosamine (chondrosamine) – constituent of
chondroitin
• D-mannosamine
• antibiotics such as erthyromycin also contain amino
sugars
Glycoproteins/ mucoproteins
• in fluids, tissues and cell membranes
• contain branched or unbranched oligosaccharide
chains
• Sialic acids: N- or O-acyl derivatives or neuraminic
acid; constituents of glycoproteins and gangliosides
• Neuraminic acid: 9-carbon sugar derived from
mannosamine (epimer of glucosamine) and pyruvate
Toxicity ends here (hopefully). =)
-Arriane and Len
“We mortals have many weaknesses; we feel too much, hurt too
much, or too soon we die, but we do have the chance of love.”
-Sir Walter Raleigh in 'Elizabeth: The Golden Age
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