Carbohydrates in Food Systems

Randy Wehling Dept. of Food Science & Technology University of Nebraska-Lincoln rwehling1@unl.edu

Importance of Carbohydrates

Carbohydrates make up over ___% of the biological matter in the world

__________ is the most abundant organic chemical on earth _______ (table sugar) is produced commercially in larger quantities that any other pure organic chemical

Importance of Carbohydrates in the Diet

In the US, carbohydrates account for about ________ of the calories consumed by the average person In some parts of the world, carbohydrates may account for as much as ___% of an average individuals caloric intake

Classes of Carbohydrates

Monosaccharides: The smallest molecules that maintain the properties associated with carbohydrates Oligosaccharides: __ ___ monosaccharide units ___________ linked together Polysaccharides: Long chains of monosaccharides __________ linked together. Occur as a means of ______ storage, or as __________ components. Chains can be ______ or ________.

Monosaccharides

Are ____________ aldehydes or ketones. Monosaccharides containing an aldehyde are known as _______; ketone containing monosaccharides are _______. Contain __ __ carbon atoms

Have the general formula (CH2O)n

The suffix -___ is used to signify a sugar (glucose, etc.)

Monosaccharides (cont.)

D & L sugars are _____________, and are ______ images of each other
Three dimensional structures can be represented with a twodimensional image, known as a __________ projection

D or L is determined by the orientation of the _____________ (next-to-last) OH group

Isomers

Isomers Compounds that have the same molecular formula, but differ in their arrangement of atoms in space __________ isomers Compounds with the same molecular formulae, but different structures. They can have different functional groups or be ________ isomers Stereoisomers Atoms of two molecules are attached in the same order, but have a different orientation in space

Effect of Orientation of Hydroxyl Groups on Chemical and Physical Properties

1) 2) 3) 4)

Solubility Melting point Sweetness Enzyme action

glucose 50% 146 C more fast

galactose 32% 170 C less slow

Aldoses

Reactions of Monosaccharides

Monosaccharides do not give positive tests for aldehydes or ketones The carbonyl reacts with an hydroxyl on the molecule to form an internal ______ or ______

Formation of Pyranose Ring Structure

Pyranose Ring (contd)

Glucose and other 6 carbon aldose sugars form six member rings. Some sugars form five member rings. Five and six member rings are stable because the rings angles are close to the bond angles of carbon (109.5). Four and seven member rings are not. Six member rings are called _________; five member rings are called __________. Ring structures can be depicted using a __________ projection

Pyranose Ring (cont.)

When the pyranose ring is formed from 6 carbon Daldoses, the OH on the carbon next to the ring oxygen can be either above or below the plane of the ring resulting in two _________ form: the OH is _____ the plane of the ring form: the OH is ______ the plane of the ring

Pyranose Form of Important Aldoses

Reactions of Sugars

All monosaccharides and many disaccharides can function as ________ agents, if they have a free aldehyde or ketone, or a free _________ hydroxyl. Reducing properties can be used to measure sugars If the aldehyde or ketone is tied up in a chemical bond, the sugar cannot act as a reducing agent The most important reaction of reducing sugars in foods is the ________ reaction, which occurs at high temperatures between reducing sugars and the free amine groups of basic amino acids.

Maillard Reaction

Maillard reaction is responsible for formation of __________ pigments that give a ______ color to certain foods, i.e. bread crust. Volatile flavor and aroma compounds, including a large number of volatile aldehydes, are also formed. _______ is made nutritionally unavailable, and some reaction products may be mutagenic Reaction rate is influenced by __ and _____ _______

Fructose

Fructose is the most important ______ in foods

Fructose can form either a five-member or six-member ring

Chemical Basis of Sweetness

AH,B,X system of sweetness perception proposed by Shallenberger

Involves _______ donor and receptor sites, and a site for ___________ interaction __________ ring has OH groups in the proper dimensions to interact with the receptor cells

Relative Sweetness of Sugars and Alternative Sweeteners:

Sweetener Sucrose Glucose Galactose Fructose Maltose Lactose High conv. corn syrup Index 1.00 0.70 0.80 0.32 1.40 0.30 0.50 0.20 0.65

Relative Sweetness (contd.)

Sweetener High fructose corn sweetener 90% 55% 42% Invert sugar Sorbitol Xylitol Cyclamate Aspartame Acesulfame K Saccharin Index
1.20 1.60 >1.00 1.00 >1.00 0.50 1.00 30 180-200 200 200-700 (350)

Intestinal Transport of Sugars

Some sugars are absorbed only by slow ________ driven by _________ __________ differences, other sugars are actively transported against a concentration gradient. Only _____________ are transported across the intestinal wall. Oligosaccharides must be hydrolyzed by enzymes into the component _______________. Sugars must form a ________ ring in order to be actively transported

Sugar Alcohols (Polyols)

Are produced by hydrogen reduction
Sugars alcohols can be used in ________ ________ foods Cannot form a ____ structure, and therefore are not actively transported Yield ___ ___ kcal/g vs. __ kcal/g for glucose or sucrose

Water Binding

Hydroxyl groups can _______ with water molecules, reducing the availability of water to microorganisms. Sugars are therefore used as _____________, especially in intermediate moisture foods. The dimensions of the pyranose ring correspond well with the dimensions of the water lattice. One glucose molecule can bind ___ water molecules Sugar alcohols do not form a ring, and thus bind less water. May not be as effective as preservatives

Oligosaccharides

_______ (table sugar, cane sugar, beet sugar) D-glucopyranosyl-D-fructofuranoside Does not act as a reducing agent

Easily hydrolyzed by acid or enzyme

Oligosaccharides (cont.)

_______ (milk sugar)
Reducing disaccharide of -_________ and _______ Not very sweet or soluble Loss of -galactosidase (_______) enzyme from digestive system results in _______ ____________

Oligosaccharides (cont.)

________
Reducing disaccharide composed of two _______ units linked 1,4 Found in some ______ and in foods containing _____ syrups

Oligosaccharides (cont.)

Raffinose and Stachyose

Oligosaccharides containing glucose, fructose, and galactose found in beans, peas, and other legumes Humans and other monogastrics lack the enzymes to completely break down these sugars in the small intestine

Prebiotics

Carbohydrates that preferentially stimulate the growth of beneficial microorganisms (probiotics) in the intestinal tract Prebiotics are not broken down in the small intestine Oligosaccharides known to have prebiotic activity include various fructooligosaccharides such as kestose and nystose

Starch

Found in grains, potatoes, tubers and roots

High molecular weight polymer used by plants to store excess energy.

Composed of two fractions: amylose and amylopectin

Amylose

Mostly linear polymer of -glucose linked 1,4. Contains a few -1,6 branch points.
Molecular weight ranges from 250,000 to 1 X 106 Long chain forms a helix with hydrogens oriented to the interior of the helix. Allows formation of clathrates.

Amylopectin

One of the largest polymers in nature (m. w. = 1 X 108)

A highly branched polymer of glucose linked 1, 4 with 4.5% 1,6 links Glucose chains are much shorter than in amylose, averaging 20 25 glucose residues

Starch Granules

Amylose and amylopectin molecules are organized in microscopic granules Granules range from 2 100 m in diameter
Granules are highly organized, with both amorphous and crystalline regions

Starch Granules (cont.)

Because of their high degree of organization, starch granules exhibit birefringence under polarized light

Gelatinization

When starch granules are heated in excess water, they imbibe water, swell and lose their high degree of organization. Crystalinity and birefringence are lost.

Pasting and Gelation

The granules swell and molecules are solubilized as they are heated in water, resulting in an increase in viscosity of a starch slurry. This is why starch is used as a thickener in gravies and sauces.
As a starch paste cools, H-bonding between the molecules increases, water is trapped between the glucose polymer chains, and a gel is formed. Examples are pudding and pie fillings.

Retrogradation and Syneresis

As a starch gel ages, more H-bonds are formed between glucose polymer chains and crystallinity returns. This is referred to as rectrograde and results in gels becoming opaque.
Amylose recrystallizes faster than amylopectin. Amylopectin retrogradation is thought to be involved in bread staling. Emulsifiers can be added to bread to slow staling. As a gel ages and interactions between starch chains increase, water molecules can be squeezed out of the gel. This is known as syneresis.

Production of High Fructose Corn Sweetener

Starch is isolated from corn by wet-milling process

Starch slurry is cooked, then converted to glucose syrup by treating with -amylase and glucoamylase enzymes Glucose syrup is treated with immobilized glucose isomerase enzyme to create an equilibrium mixture of glucose and fructose (52:48).

Comparison of Sweetener Composition

Hydrolyzed sucrose (invert sugar): 50% glucose/50% fructose
High fructose corn sweetener: 42% fructose, 52% glucose, 6% maltose and other oligosaccharides of glucose

Honey 48% fructose, 39% glucose, 1% sucrose, 12% maltose and other sugars

U.S. Per Capita Consumption of Caloric Sweeteners

Modified Starches

Starches can be chemically modified to change their pasting and gel forming properties
Chemical crosslinking and substitution are the most common modifications Improves stability of starch pastes and slows the retrogradation process

Cellulose

Glucose units linked by ______ bonds
Linear polymer containing 6,000 12,000 glucose units on average The most abundant organic chemical on earth. It is a __________ polysaccharide that is a major constituent of the ____ _____ of higher plants The 1,4 linkage is resistant to acid hydrolysis and attack by amylases

Hemicelluloses

A group of carbohydrate polymers associated with the cell walls of higher plants
Polymers made up of sugars including xylose, arabinose, mannose, galactose and glucose Are sometimes referred to as __________

Pectins

Polymers of ______________ acid, linked 1,4, that are the structural materials of plant soft tissues.
Linear polymers with short side chains of other sugars branching from the linear backbone Pectins can form _____ at low ___ Pectins can be isolated from various sources (most commonly apples) and used in making jellies, jams, and fruit preserves.

Gums

Water soluble polysaccharides used as __________ and ___________ in foods
Gums are derived from sources including: seaweed, seeds, tree exudate, microbial fermentation, apple pomace and citrus peel (pectins), and wood pulp (chemically modified celluloses) Are typically added to foods at levels ___%

Uses of Gums

___________
Stabilization of ___________ Suspension of _________ Control of _______________ ______________

Sources of Gums

Seaweed extracts: Alginates Agar Carageenan

Locust bean gum Guar gum

Seed gums:

Exudate gums:

Gum Arabia (Acacia) Gum Ghatti Gum Karaya Gum Tragacanth

Sources of Gums (cont.)

Microbial gums: Xanthan Dextran Gellan

Methylcellulose Carboxymethylcellulose Hydroxypropylmethylcellulose

Modified cellulose:

Pectins

Dietary Fiber

Composed primarily of __________ polysaccharides from plants found in the ____ _____. Good sources of fiber are whole grains, fruits and vegetables. These components are not digested by humans (or any monogastric). They are resistant to amylase enzymes and acid. Fiber components are classified as _______ or ________, based on their solubility in ______

Insoluble Fiber

Thought to be important to ______ health. Provides bulk that contributes to regularity. May reduce contact time of mutagens and carcinogens by decreasing transit time through the _____. May also act as absorbent. Components include: __________ Hemicelluloses and pentosans ______ (polymer of phenolic compounds closely associated with carbohydrate cell wall components) Resistant ______ (raw or retrograded)

Soluble Fiber

Composed primarily of _______ and _____ polysaccharides that are water soluble but not hydrolyzed in the digestive system. Has been shown to reduce serum ___________ levels, and in some cases serum _______ levels. ________ from oat and barley fiber have been shown to be particularly effective. These are polymers of glucose containing both -1,4 and -1,3 links.
May also exhibit a prebiotic effect