Chemical

Properties of Monosaccharides
§ Five important reactions of monosaccharides:
§ Oxidation to acidic sugars
§ Reduction to sugar alcohols
§ Glycoside formation
§ Phosphate ester formation
§ Amino sugar formation
§ These reactions will be considered with respect to glucose.
§ Other aldoses, as well as ketoses, undergo similar reactions.
Reducing sugars
§ Are monosaccharides with a carbonyl group that oxidizes to give a carboxylic acid.
§ Undergo reaction with Benedict’s reagent (Cu2+) to give the corresponding carboxylic acid.
§ Include the monosaccharides glucose, galactose, and fructose.

O O

C H C OH
H C OH H C OH
HO C H HO C H
+ Cu2+ + Cu2O(s)
H C OH H C OH
H C OH H C OH
CH2OH CH2OH
D-gluconic acid
D-glucose
Glucose is a reducing sugar

Reduction to Sugar Alcohols
§ The carbonyl group in a monosaccharide (either an aldose or a ketose) is reduced to a hydroxyl
group using hydrogen as the reducing agent.
§ The product is the corresponding polyhydroxy alcohol - sugar alcohol.
§ Sorbitol - used as moisturizing agents in foods and cosmetics and as a sweetening agent in
chewing gum

§ Oxidation to acidic sugars: The redox chemistry of monosaccharides is closely linked to the alcohol
and aldehyde functional groups present in them.
§ Oxidation can yield three different types of acidic sugars depending on the type of oxidizing agent
used:
§ Weak oxidizing agents such as Tollens and Benedict’s solutions oxidize the aldehyde end
to give an aldonic acid.
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§ A reducing sugar is a carbohydrate that gives a positive test with Tollens and Benedict’s
solutions.

§ Strong oxidizing agents can oxidize both ends of a monosaccharide at the same time (the carbonyl
group and the terminal primary alcohol group) to produce a dicarboxylic acid:
§ Such polyhydroxy dicarboxylic acids are known as aldaric acids.

§ In biochemical systems enzymes can oxidize the primary alcohol end of an aldose such as glucose,
without oxidation of the aldehyde group, to produce an alduronic acid.

§ Glycoside formation: Cyclic forms of monosaccharides are hemiacetals, they react with alcohols to
form acetals:
§ Monosaccharide acetals are called glycosides
§ A glycoside is an acetal formed from a cyclic monosaccharide by replacement of the hemiacetal
carbon —OH group with an —OR group:
§ A glycoside produced from glucose - glucoside
§ A glycoside produced from galactose – galactoside
§ Glycosides exist in both Alpha and Beta forms

§ Phosphate ester formation: The hydroxyl groups of a monosaccharide can react with inorganic
oxyacids to form inorganic esters.
§ Phosphate esters of various monosaccharides are stable in aqueous solution and play important
roles in the metabolism of carbohydrates.

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§ Amino sugar formation: An amino sugar - one of the hydroxyl groups of a monosaccharide is
replaced with an amino group
§ In naturally occurring amino sugars the carbon 2 hydroxyl group is replaced by an amino group
§ Amino sugars and their N-acetyl derivatives are important building blocks of polysaccharides such
as chitin

DISACCHARIDES
§ Consists of two monosaccharides.
Monosaccharides Disaccharide
Glucose + glucose maltose + H2O
Glucose + galactose lactose + H2O
Glucose + fructose sucrose + H2O
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Maltose is
§ A disaccharide also known as malt sugar.
§ Composed of two D-glucose molecules.
§ Obtained from the hydrolysis of starch.
§ Linked by an α-1,4-glycosidic bond formed from the
α −OH on C1 of the first glucose and −OH on C4 of the second glucose.
§ Used in cereals, candies, and brewing.
§ Found in both the α- and β - forms.

Lactose
§ Is a disaccharide of β-D-galactose and α- or β-D-glucose.
§ Contains a β -1,4-glycosidic bond.
§ Is found in milk and milk products.

Sucrose or table sugar
§ Is obtained from sugar cane and sugar beets.
§ Consists of α-D-glucose and β-D-fructose..
§ Has an α,β-1,2-glycosidic bond.

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Sugars and artificial
sweeteners
§ Differ in sweetness.
§ Are compared to sucrose (table sugar), which is assigned a value of 100.

Oligosaccharide
• Carbohydrates that contain 3-10 monosaccharide units boded to each other via glycosidic linkages.
• Not as common as disaccharides in nature. Generally present in association with other complex
molecules.
• Examples:
• Raffinose: made of one each of galactose, glucose and fructose.
• Stachyose: made of 2 galactose, 1 glucose and 1 fructose units.
• Commonly found in onions, cabbage, broccoli and wheat.

Blood Types
• Human blood is classified into four types: A, B, AB, and O blood groups:
– The basis for the difference is the type of sugars (oligosaccharides) present.
– Blood of one type cannot be given to a recipient with blood of another type.
– A transfusion of wrong blood type can cause the blood cells to form clumps - a potentially
fatal reaction.
– People with type O blood are universal donors, and those with type AB blood are universal
recipients.
• In the United States type O blood is the most common and type A the second most common.
• The biochemical basis for the various blood types involves oligosaccharides present on plasma
membranes of red blood cells.
The oligosaccharides responsible for blood groups are D-galactose and its derivatives

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Other oligosaccharides

• Solanin - a potato toxin, is a oligosaccharide found in association with an alkaloid.
– Bitter taste of potatoes is due to relatively higher levels of solanin.
• The oligosaccharides responsible for blood groups are D-galactose and its derivatives.


Polysaccharides

The Polymer Chain
• Polymers of many monosaccharide units bonded with glycosidic linkages
• Two types:
– Linear and branched, homo- and hetero-polysaccharides

• Polysaccharides are not sweet and don’t show positive tests with Tollen’s and Benedict’s solutions
whereas monosaccharides are sweet and show positive tests
• Limited water solubility
• Examples:
– Cellulose, starch in plants
– Glycogen in animals
– Chitin in arthropods
Starch

• A storage polysaccharide is a polysaccharide that is a storage form for monosaccharides and is used
as an energy source in cells.
• Starch:
– Glucose is the monomeric unit
– Storage polysaccharide in plants
– Two types of polysaccharides isolated from starch:
– Amylose: Straight chain polymer - 15 - 20% of the starch and has alpha (1 à 4) glycosidic
bonds
– Molecular Mass: 50,000 (up to 1000 glucose units)
• Amylopectin:
– Branched chain polymer - 80 - 85 % of the starch alpha (1à4) glycosidic bond for straight
chain and alpha (1à6) for branch
– Molecular Mass: 300,000 (up to 100,000 glucose units) - higher than amylose
– Amylopectin is digested more readily by humans (can hydrolyze alpha linkages but not beta
linkages)

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Glycogen
– Human and animal storage polysaccharide
– Contains only glucose units
– Branched chain polymer – alpha (1à4) glycosidic bonds in straight chains and alpha (1à6)
in branches
– Molecular Mass: 3,000,000 (up to 1,000,000 glucose units)
– Three times more highly branched than amylopectin in starch
– Excess glucose in blood stored in the form of glycogen

Glycogenesis
Glucose Glycogen
Glycogenolysis

Cellulose
• Linear homopolysaccharide with beta (1à4) glycosidic bond
• Up to 5000 glucose units with molecular mass of ~900,000 amu
– Cotton ~95% cellulose and wood ~50% cellulose
– Humans don’t have enzymes that hydrolyze beta (1à4) linkages - so they can not digest
cellulose -- animals also lack these enzymes but they can digest cellulose because they have
bacteria in their guts to hydrolyze cellulose
– It serves as dietary fiber in food-- readily absorbs water and results in softer stools
– 20 - 35 g of dietary fiber is desired everyday
HO

HO O O
OH
HO O O
OH β(1-4) OH
O O
HO
OH β(1-4)
OH
O O
O OH β(1-4)
OH

OH

Chitin
– Similar to cellulose in both function and structure
– Linear polymer with all beta (1à4) glycosidic linkages - it has a N-acetyl amino derivative
of glucose
– Function is to give rigidity to the exoskeletons of crabs, lobsters, shrimp, insects, and other
arthropods

HO

HO O O
OH
HO O
O
OH HN
O O
HO
OH HN O
O O
O OH HN O

HN O

O






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• Acidic polysaccharides - polysaccharides with a repeating disaccharide unit containing an amino
sugar and a sugar with a negative charge due to a sulfate or a carboxyl group.
• Structural polysaccharide present in connective tissue associated with joints, cartilage, synovial
fluids in animals and humans
– Primary function is lubrication necessary for joint movement
– These are heteropolysaccharides - have more than one type of monosaccharide monomers
is present.
• Examples:
– Hyaluronic acid
– Heparin

• Hyaluronic acid:
– Alternating residues of N-acetyl-beta-D-glucosamine and D-glucuronic acid.
– Highly viscous - serve as lubricants in the fluid of joints and part of vitreous humor of the
eye.
• Heparin:
– An anticoagulant-prevents blood clots.
– Polysaccharide with 15–90 disaccharide residues per chain.

Nutrition
• Foods high in carbohydrate content constitute over 50% of the diet of most people of the world -- a
balanced dietary food should contain about 60% of carbohydrate:
– Corn in South America
– Rice in Asia
– Starchy root vegetables in parts of Africa
– Potato and wheat in North America
• Nutritionists divide dietary carbohydrates into two classes:
– Simple carbohydrates: dietary monosaccharides or disaccharides - sweet to taste commonly
referred to as sugars - 20 % of the energy in the US diet
– Complex carbohydrates: Dietary polysaccharides -- starch and cellulose - normally not
sweet to taste

Glycemic Foods
• A developing concern about intake of carbohydrates involves how fast the given dietary
carbohydrates are broken down to glucose within the human body
• Glycemic effect refers to:
– how quickly carbohydrates are digested
– how high blood glucose rises
– how quickly blood glucose levels return to normal
• Glycemic index (GI) has been developed for rating foods