O

Oligosaccharides

Oligosaccharide-Introduction
Oligo--Greek, few Definition: 2-20 monosaccharide units More than 20 monosaccharide units is a polysaccharide Poly--Greek, many

Oligosaccharides
In the disaccharides, the aglycon is a monosaccharide unit Higher order oligosaccharides are named tri-, tetra-, penta-, etc. Structures may be predominately linear or branched

Overall structures
Linear

Branched

Structural features

Linear

Features a head-to-tail linkage 1 reducing end 1 non-reducing end 1 reducing end Several to many non-reducing ends

Branched

Acid catalyzed reversion

Maltose 2 Glucose -1,4-linkage

-1,4-linkage

Reversion
If this reaction continues, the oligomers produced will tend to be highly branched and contain a variety of anomers and linkages Readily occurs under water-limiting conditions (nearly dry) A good commercial example of this is the bulking agent Polydextrose

Polydextrose
Polydextrose is produced by the reversion reaction between D-glucose, sorbitol, and citric acid This mixture is heated to produce the oligomer Polydextrose The degree of polymerization (DP) is fairly low Sold commercially as Litesse (and under other names as well)

Polydextrose
CH2OR O OH HO OH CH2OH HOCH HO O OH HO HOCH2 OH HO O OH O HOCH2 O OH OH O HO CH2OR O OH O HO OCH2 O OH HO OCH2 OH O OH O OH CH2 OH O OH CH2 OH O O HO O HO

HOCH2 O OH CH2 O OH OH OR O

R = H, D-glucose, sorbitol, citric acid, or polydextrose moieties

Maltose

Maltose
Obtained from starch by the action of amylase (from Bacillus bacteria) Yield = 80%

Non-reducing end

-amylase

Maltose

Maltose

Maltose

Maltose
Maltose may also be prepared by the action of debranching enzyme and then -amylase on amylopectin Maltose crystallizes from aqueous solution as -maltose.H2O

Maltose uses
A mild sweetener in foods and pharmaceuticals A parenteral injectable for slow release of D-glucose

Maltose
Proper name: 4-O-(-Dglucopyranosyl)-D-glucopyranose Exists as and -anomers Reducing sugar Its glycosidic linkage is acid labile

Lactose

Lactose

Milk sugar

[lactose] in nature: 2.0-8.5% Cow/goat: 4.5-4.8% Human: 7.0%

Provides 40% of the energy obtained during nursing To utilize, lactose must be broken down to D-glucose and D-galactose

Lactose production
Cows milk Adjust to IEP; heat or rennin Whey ultrafiltration

Ion exchange Coagulated casein Concentration Curd Crystalline lactose

Lactose production
Crystallizes as -lactose monohydrate Potential lactose from whey is 23 billion pounds per year So far its potential production has far outstripped its commercial use

Lactose characteristics
Name: 4-O-(-D-galactopyranosyl)-Dglucopyranose Reducing sugar Hydrolyzable Multiple anomeric forms

Lactose uses

Food

Toppings Icings Pie fillings Confections Ice creams

In food, lactose contributes body but little (20% of sucrose) sweetness

Pharmaceutical uses

Provides bulk and rapid dissolution

Present in 20% of prescription drugs Present in 6% of over the counter (OTC) drugs

Natural occurrence
Lactose is relatively high in milk and milk products but lower in fermented dairy products such as yogurt and some cheeses During fermentation some lactose is converted to L-lactate

Lactate production in food

Lactose -galactosidase of bacteria D-Glucose + D-Galactose

Fermentation by bacteria
O O-

HO CH3

L-lactate

Lactose digestion
Digestion in gut mediated by lactase, a galactosidase that occurs in brush border epithelial cells The monosaccharides so produced are rapidly absorbed and enter the blood stream

Lactose intolerance
If lactose is not completely hydrolyzed and absorbed in the small intestine, it will proceed into the large intestine Here anerobic bacteria ferment the lactose to lactic acid and other short chain acids, in addition to CO2, H2, and methane This causes the symptoms of lactose intolerance

Lactose intolerance
Abdominal distention Flatulence Cramping Diarrhea

Lactose intolerance
Usually not seen in children until 6 years of age After 6 years of age, the percent of lactose intolerant people increases with increasing age, with the greatest incidence among the elderly

Genetic control
Lactose intolerance tends to be high among African Americans, Native Americans, Asian Americans, and Mexican Americans Relatively lower in Western European Americans Suggests that production of lactase is under genetic control

Dealing with lactose intolerance

Reduce/remove lactose by fermentation

Yogurt, buttermilk

Add lactase to food (or consume lactase) just before consuming lactose containing food

This may increase the sweetness of the food slightly when the extent of hydrolysis reaches 80%

Other incompletely digested oligosaccharides

Mostly from legumes, especially beans

Raffinose, a trisaccharide Stachyose, tetrasaccharide

Lactose chemistry
Lactose can be reduced to lactitol with hydrogen gas and Raney nickel Lactitol is not absorbed from the small intestine It is fermented in the large intestine to lactic and acetic acid Due to the water attracting properties of these acids, they soften stools and facilitate bowel function

Lactose chemistry
Lactose can be isomerized in alkali to the keto sugar lactulose Lactulose is similar in its physiological effect to lactitol, that is it facilitates bowel function

Sucrose

Sucrose
One of the principal sugars in fruits and honey Isolated from sugar cane Produced in China during the 1st century B.C. In ancient days it was very expensive and, thus, reserved for the nobility

Sucrose utilization
Per person per day disappearance data: 160 grams Per person per day consumption data: 55 grams

Sucrose structure
Odd as it is a head-to-head type structure (anomeric carbon to anomeric carbon) Non-reducing The glycosidic bond is high energy, thus unstable

Easily hydrolyzed in dilute acid or enzymes (sucrase or invertase)

Invert sugar
H+ Glucose---Fructose [ ] D +66.5o Glucose + Fructose Invert sugar []D -33.3o

Sucrase and invertase

Human sucrase (-glucosidase)

Yeast and bacterial invertase (-fructofuranosidase)

Sucrose synthesis

Synthesized mainly in plants leaves, then transported throughout the plant Stored in root or tuber structures

UDPGlucose + Fructose-6-phosphate

Sucrose phosphate

Sucrose

Sucrose from sugar cane

Isolation involves processing 12-18 month old sugar cane through a series of steps that involve crushing, treating with lime, heating, filtration, and crystallization This produces raw sugar and blackstrap molasses The raw sugar is further cleaned up by treating with lime and phosphate, decolorizing, and crystallizing

Sucrose from sugar beet

Utilizes countercurrent extraction of sugar beet slices (called cosettes) The extracting solution (12% sugar) is then treated with lime, carbon dioxide, filtered, decolorized with SO2, and concentrated to crystallize the sugar Impurities: raffinose and stachyose

Raffinose and stachyose

Galp(16)Galp(16)Glcp(12)Fruf
Sucrose

Raffinose Stachyose

Other sugar products

Brown sugar

Incompletely purified table sugar or (more commonly) made by adding back cane sugar molasses to table sugar to get desired brownness and taste Industry refers to this as soft sugar Pulverized table sugar + 3% corn starch as an anti-caking agent

Powdered sugar

Other sugar products (cont.)

Fondant sugar

Very fine sucrose crystals surrounded with a saturated solution of invert sugar, corn syrup, or maltodextrin Used in icings and confections Agglomerated sucrose crystals Low density, rapid dissolving Refined aqueous solution of sucrose

Transformed sugar

Liquid sugar

Sucrose crystal and solution properties

Sucrose can form highly concentrated solutions

Syrups Honey Sweetener Preservative Humectant

Uses

Cryoprotectant function
In a solution of sucrose, as freezable water freezes, the [sucrose] increases Thus, freezing point decreases As [sucrose] increases, viscosity increases Eventually the liquid phase solidifies as a glass

This explains how some carbohydrates can protect against dehydration (via crystallization) that destroys structure and texture on freezing

Sucrose solution structure

In crystal state only 6

O H HO O O OH

HOH 2C HO HO H
In solution and crystal state

O2 O HO
1

Derivatives of sucrose

Sucrose esters

Low derivatization (1, 2, 3 fatty acids)

Surfactants

(emulsifiers)

Octaacetate
Very Used

bitter to denature ethanol

Longer fatty acids

6-8 Olestra

fatty acids (stearic, palmitic, oleic) (frying oil fat substitute from Proctor and Gamble) Not metabolized or absorbed

Sucralose
OH Cl OH OH O O OH Cl O OH Cl

Sucralose
650x sweeter than sucrose Good taste quality and intensity Adequate water solubility Not hydrolyzed in small intestine 60 times more stable to acid than sucrose Approved for use in the US on 4/1/98

Sucralose uses
Tabletop sweetener Beverages Baked goods Chewing gum Dry mixes Fruits spreads Frozen desserts

Isomaltulose
HOH2C HO HO OH O
50% as sweet as sucrose
Isomaltulose

OH HO

O CH OH 2 OH

-D-Glucopyranosyl-(16)-D-fructofuranose

Isomaltulose preparation
Prepared enzymatically from sucrose Enzyme is from Protaminobacter rubrum Transfers glucose in sucrose from O-2 to O-6

Isomaltulose

Uses (in Europe)

Non-cariogenic candies Speciality chocolate Chewing gum Cookies

Palatinit
Hydrogenation of isomaltulose with hydrogen and a catalyst produces Palatinit About 45% as sweet as sucrose Crystalline

Palatinit (GPM and GPS)

HOH 2C O HO HO OH OH O OH OH OH OH

GPM

HOH2C O HO HO OH
GPS

OH OH O HO HO OH

Palatinit uses
Chocolate Marzipan Chewing gum

Leucrose
OH HOH2C HO HO OH O HO OH O O OH

-D-Glucopyranosyl-(15)-D-fructopyranose

Leucrose
Derived from sucrose by treatment with Leuconostoc mesenteroides 50% of the sweetness of sucrose

Kestose and neosugar

Kestose (GF2)

Nystose (GF3)

Fructofuranosyl nystose (GF4)

Neosugar preparation
A concentrated solution of sucrose is treated with invertase or a fungal transferase This causes the transfer of D-fructosyl units onto sucrose, thus producing kestose and the other neosugars 50% as sweet as sucrose Non-cariogenic Approved for use in Japan