Week 3 & Week 4: Carbohydrates

Introduction & Monosaccharides: simple sugars, building blocks of carbohydrates ✅

Oligosaccharides & Polysaccharides ✅

Starches ✅

Starch Applications ✅

Other Polysaccharides Application

3 Chemical functional groups

(R-OH) Hydroxyl group

Ketone group image

Aldehyde group image

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in Ketose

in Aldose

are Reducing sugars

contains chiral carbon atoms: One that can exist in two different spatial arrangement that can not be superimposable on each other.

D-sugars vs L-sugars: L-sugars are less numerous and less abundant in nature ✅

D-glucose is the most abundant carbohydrate

When it is written in an open or vertical straight-chain fashion, the aldehyde group (position 1) at the top and the primary hydroxyl group (position 6) at the bottom

The mirror image is known as a L-glucose

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It contains a polyalcohol and an aldehyde

D-fructose is a prime example of this type of sugar

Isomerisation catalysed by either a base or an enzyme can converted the ketose into aldoses

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Ring formation

Carbonyl groups of aldehydes are reactive and easily undergo nucleophilic attach by the oxygen atom of a hydroxyl group to produce a hemiacetal
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D-Glucose ring formation

It is the hemiactel that is involved in most reactions of glucose
Hemiacetal can react with alcohol to produce a condensation effect to form glycosidic links

Carbon 1 and carbon 5 react to form the ring structure

fructose, the ring structure is formed by ketone group on C2 and hydroxyl at carbon 5

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Sugar with free aldehyde in open chain configuration can reduce cupric ions (Cu2+ )to cuprous ions (Cu+)

Only open chains are able to produce a reducing effect

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cause non-enzymic browning in food

Open chain has the active aldehyde and monosaccharides can only act as reducing sugar in this form

Formation of red precipitate in Fehling solution is dependent on open chain because equilibrium exist

produce brown colour that are desirable and important in some foods

Common browning of foods on heating or on storage is usually due to a chemical reaction between reducing sugars, mainly D-glucose and a free amino acid or a free amino group – Maillard reaction

Maillard reaction may be produced by frying, roasting, baking or storage

Oligosaccharides: contains 2 to 20 sugar units joined by glycosidic bonds ✅

Glycosidic bonds: Joins 2 monosaccharides.

formed by condensation reactions: one molecule of water is released during the joining of two monosaccharides

Hydrolysis

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3 examples

Maltose: Obtained by hydrolysis of starch using enzyme β-amylase

Lactose: Primary carbohydrate source for developing mammals, Occurs mainly in milk

Sucrose: not crystallised, has got great hydrophilicity and solubility, can form highly concentrated solutions of high osmolality

during malting of grains especially barley

Can be used as a mild sweetener for foods

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to utilise lactose for energy, hydrolysis must occur first.

Ingested lactose that is only partially hydrolysed, it results in lactose intolerance


Lactose that passes into the large intestine can undergo anaerobic bacterial fermentation to lactic acid and gases. This can result in diarrhea, bloating and cramping

Lactose that is left present in the lumen results in fluid retention within the gut producing abdominal distention and cramps

Fermentation process to produce yogurt, buttermilk etc. reduces/ removes lactose in milk, decreasing the effect of lactase deficiency

Can be used as sweeteners, preservatives and humectants

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Polysaccharides: polymers of monosaccharides
High molecular weight
Either linear or branched units

Two classification

Homoglycans – made up of same sugar units e.g. starch or cellulose

Heteroglycans – made up of two or more different monosaccharide units e.g. guar gum, locust bean gum

Functionality in Food

Modify and control mobility of water in food systems

Used as thickener

Acts as a gelling agent

Modify and control rheological properties

Produce high viscosity at low concentration

Acts as cryostabilisers – produces freeze-concentrated matrix that limits molecular mobility or restricts ice crystal growth

Properties

Occurs naturally as discrete particles (granules)

Relatively dense

Insoluble

Hydrate only slightly in cold water

Can be dispersed in water to produce low viscosity slurries

Viscosity building (thickening) only occurs when a slurry of granules is cooked

Consists of a mixture of two polymers ✅

Amylose: linear
with 1 4 linked -D-glucopyranosyl units
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Amylopectin: highly branched
Consist of linear - 1,4 linked D-glucose units with  (16) branch points every 15 to 20 glucose units
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Double helix structure

Hydroxyl groups are positioned on the exterior of the coil

Interior of helix contains only hydrogen atoms and is lipophilic

Most starch contain about 25% amylose

High amylose corn can contain about 52% or 70-75% amylose

2 Properties

Able to form light polymer network after gelatinisation

Able to form complexes with lipids and proteins

Presence of these complexes also inhibit starch swelling, prevents excessive water absorption of amylopectin to better maintain starch integrity

helps strengthen the formation of protein network

Constitute about 75% of most common starches


Waxy starch – consist entirely of amylopectin

2 properties

Chain branching also retards gel formation

Better solubility

Amylose and amylopectin molecules are arranged radially: Forms crystalline and non-crystalline regions

Crystalline areas (dense area) are formed by clustered branches of amylopectin

Dense layers of starch granules alternate with less denser amorphous layers

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In Starch Granule ✅

2 types

B granules – small (1-10μm), spherical in shape

A granules – large (10-35μm), lenticular in shape

account for 3-5% of total granules present but constitute more than 70% of total starch weight

account for 90% of total starch, less than 30% of total starch weight

Starch Gelatinisation: disruption of molecular order within granules
and Pasting image

Undamaged starch granules are insoluble in cold water but can absorb water reversibly

Heated in water, starch granules undergo gelatinisation

Further granule swelling with continuous heating in excess water

The application of shear leads to total disruption of granules

Evidence of the loss of order includes irreversible granule swelling and loss of regular structure
Leaching of amylose also occurs during gelatinisation

Additional leaching of soluble components (primarily amylose)

Granule swelling and disruption produce a viscous mass

Retrogradation: On cooling, some starch molecules partially reassociate to form a particule or gel

The firmness of the gel depends on the extent of junction zone formation

Junction zone formation is influenced by:

Amount of water present

Presence of other ingredients such as fats, proteins, sugars and acids


consists of a continuous phase of solubilised amylose and/ or amylopectin and a discontinuous phase of granule remnants

8 Types of Starches – Unmodified Starches ✅

Common Starches: 25% amylose and 75% amylopectin

Waxy Starch: Contains only amylopectin no amylose

Forms thickened viscous pastes that do not gel on cooling

High Amylose Starch: Amylose content of about 52% or 70-75%

High gelling properties

Main sources: corn (maize), rice etc.

Waxy maize starch: Clear cohesive pastes used in extended cereal and snack food products, in dry mixes for soups and cakes

Rice Starch: Produces opaque gels useful for baby food

Waxy Rice Starch: Clear and cohesive

Wheat Starch Gels: Weak, slight flavour due to residual flour components

Tuber (potato) and root (tapioca) starches: Weak intermolecular bonding and swell greatly to give high viscosity pastes

Viscosity decreases with moderate shear because the highly swollen granules break easily

Modification of Starch: so that resultant pastes can endure the conditions of heat, shear and acid associated with particular processing conditions and to introduce specific functionalities : ✅

Types

Cold Water Soluble (Pregelatinised) Starch: Uses 20-40% starch slurry & atomized with steam (70C). Directly into spray dryer Suspended granules gelatinised (60% moisture content)

Can be applied to both chemically modified and unmodified starches
Typically used in dry mixes such as instant pudding mixes, instant soups

Cold water Swelling Starch
: 20% starch slurry in 75% ethanol solution
Pressure (4MPa), High temperature (75C)

Can be used in sugar solutions in the production of gum candies - produce rigid gels that can be easily sliced

Useful in making desserts and also to keep particles such as blueberry in muffin batters “suspended

Hydrolysis

Enzyme treatment of starch
: Results in the production of maltodextrins

Acid treatment of starch: Acid is sprayed onto starch,, neutralised, product is recovered washed and dried

Crosslinking: Hydroxyl functional group (-OH groups) present in starch are used for cross linking with di- or poly reagents
E.g. of reagents used are phophoryl chloride or sodium tripmetaphosphate

Maltodextrins properties are linked with the degree of polymerisation (DE)
Those with low DE are non-hygroscopic while those of highest DE tend to absorb moisture

Acid modified starches form gels with improved clarity and increased strength even though they provide less solution viscosity

Uses

Can be used as film formers and adhesives in products such as pan-coated nuts and candies

Can also be used to form strong gels such as in gum candies

Linking starch chains with phosphate diester reinforces the granules and reduces both the rate and degree of swelling and subsequent disintegration

As crosslinking is increases,

the granule becomes more and more tolerant to physical conditions

The starch becomes more acid-stable

The starch becomes less and less dispersible by cooking

Crosslinked starches are used in canned soups, gravies, puddings and in batter mixes

Cellulose: A high- molecular weight, linear, insoluble homopolymer of repeating β-D-glucopyranosyl units joined by (1→4) glycosidic linkages

Occurs as a basic structural polysaccharide in cell walls of higher plants

Insoluble and hence serve as dietary fibre

Derivatives : ✅

Microcrystalline cellulose (MCC): A purified insoluble cellulose.

used primarily as a flavour carrier and as an anticaking agent

Colloidal MCC is water dispensible and has similar properties to those of water-soluble gums

used to stabilize foams and emulsions especially during high-temperature processing

Carboxymethylcellulose (CMC): Consists of long, fairly rigid molecules that bear a negative charge due to numerous ionized carboxyl groups,

stabilises protein dispersions especially near their isoelectric pH value

tend to be both highly viscous and stable

Can be used as

Thickener for cottage cheese and cheese spread

Emulsion stabiliser in sauces, soups and dressings

Protein stabilisers and retarder of crystal formation in ice cream

Methylcelluloses: cellulose treated with methyl ester groups
& Hydroxypropylmethylcellulose: cellulose treated with both propylene oxide and methyl chloride


Both are cold water soluble

Used as fat replacers in food

provide fat-like properties so that fat content of a product can be reduced


They reduce adsorption of fat in products being fried

Guar and Locust Bean Gum: Both gums are the ground endosperm of seeds with main component, Galactomannans
Guar gum – guar bean seeds
Locust Bean Gum – carob tree

Guar – evenly spaced galactosyl units


Locust bean gum – long naked chain sections

Soluble in water giving highly viscous solutions

Stable in pH range 4-10

Typically used as a thickener, viscosity modifier, and stabiliser of dispersion in food and beverages

in cold water only swells and form a viscous dispersion

Does not gel on its own

Increases agar and carrageenan gel elasticity and strength

Typically used as
Emulsion stabiliser
Thickening agent for dairy products and filling for frozen foods and bakery products

Xanthan Gum: Produced by bacterium (xanthomonas campestris)

Interacts with guar gum, gives synergistic increase in solution viscosity
Interacts with LBG produces a heat reversible gel

Unique characteristics:

Used as a thickener for sauces, to prevent ice crystal formation in ice cream and as a low calorie substitute for fat

Soluble in hot or cold water

High solution viscosity at low concentration

Soluble and stable in acidic systems

Excellent compatibility with salt

Good solution stability when exposed to freezing and thawing

Carrageenans: Extracted from seaweed

Stable over a wide range of pH

3 different types: kappa (), iota (), and lamba ()

Dissolved in water to form high viscous solutions

Key uses
Typically used to gel, thicken, or suspend, so they are used in emulsion stabilisation for syneresis control, and for bodying, binding and dispersion

Iota carrageenan – used in dessert gel formulations

Kappa carrageenan – used to ice cream to control meltdown, used in infant formulation to create fat and protein stabilisation

Lambda carrageenan – used in aerosol whipped cream/ shakes to stabilise overrun

Pectin: from citrus peel and apple pomace ✅

Two types depending on degree of esterification (DE)

High-methoxy pectin - over 50% DE, gels in medium with more than 55% soluble solid content

Low-methoxy pectin – DE less than 50%, gelation is controlled by introducing calcium ions and occurs in a medium with 20% soluble solids at pH between 2.5 and 6.5

Uses/ Applications of Pectin

Leading agent used to impart a gelled texture to foods, mainly fruit based foods

Used in jams and jellies as a gelling agent

Used in fruit preparation for yogurt

Used in confectionary products

stabilised by hydrophobic binding of methyl ester groups as well as intermolecular hydrogen bonding

stabilised by inter chain binding by Ca2+

Made by hydrolysis of purified wood pulp, followed by separation of constituent microcrystals of cellulose

electrostatic repulsion causes its molecules in solution to be extended