Title: Anita Kruger
1Anita Kruger
- time_at_mfm.sun.ac.za
- 072 5454 959
2FOOD CHEMISTRY 3FCHE30
FACULTY OF SCIENCE Department of Horticulture
Food Technology
- SEMESTER 2
- MODULE 4
- Other Carbohydrate Gels
3CARBOHYDRATES
- Monosaccharides
- Polysaccardies Oligosaccharides
- Storage Carbohydrate Animals
- Glycogen (from Glucose)
- Storage Carbohydrate Plants
- Starch
- Structural Polysaccharide Plants
- Cellulose
- Gums
4Pectin Substances-Plant Gums
- Heteropolysaccharides
- Hydrocolloid water-binder
- Hydrophillic colloid imbinding large quatities
of water - Fill intercellular spaces, middel lamella of
plant tissue - Wide channels in young fruit tissue
5Pectin Substances-Plant Gums
- Plant cell wall showing Pectin
6Pectin Substances-Plant Gums
7Pectin Substances-Plant Gums
- Role of Pectin in Plant Tissue (fruits)
- In outer cell walls, closely associated with
cellulose precursor of pectin Protopectin - Absorb water and transfer it among cells
- Responsible for firmness, texture (fruits
veggies) - Softening during ripening
- Breakdown of colloidal stability in fruit juices
8Pectin Substances-Plant Gums
- Change in pectin substances during ripening
- Protopectin in middle lamella between cell walls
soluble pectin - Reduce cell wall thickness
- Softening Ripening
- Decrease the degree of esterification of carboxyl
groups with methyl alcohol
9Pectin Substances-Plant Gums
- Pectin is a polymer of a-Galacturonic acid with
a variable number of methyl ester groups.
- Methylated ester of Polygalacturonic acid
- Chains of 300 to 1000 glalacturonic acid units
- Joined with 1a?4 linkages
- This structure shown here is three methyl ester
forms (-COOCH3) for every two carboxyl groups
(-COOH) - hence it is has a 60 degree of esterification,
normally called a DE-60 pectin
10Pectin Substances-Plant Gums
- Transformation of Protopectin to Pectin
- Pectin-rich Plant Materials (Pomace, Citrus)
- Heated with acidified water - Hydrolyzed
- Protopectin (cellulose) form water soluble pectin
(Same transformation during ripe fruit) - Precipitated form aqueos solutions by
alcohol/acetone as jelly-like coagulum, which
dissolve in water (water soluble) - Pectin Negatively charged colloid/electrolite
- Commercial pectin contains a number of
impurities hemicelluloses, pentosans, galactoses - Can be purified by repeated precipitation and
redissolution (more later)
11Pectin Substances-Plant Gums
- General Structure
- Long, unbranced chains of polygalacturonic
acid, with carboxyl groups partially esterfied
with methyl alcohol - Heteropolysaccharides - High molecular masses (20 000 over 400 000)
- Joined by a-1,4 glycosidic bonds
- Gums have acid groups as well as hydroxyl groups
and long-chain structures Good emulsifier - Acidic goups act as strongly hydrophilic portion
of molecule - Rest of molecule in the chain act as less
hydrophilic portion (almost hydrophobic)
12Pectin Substances-Plant Gums
- Guar Gum / Locust Bean Gum
- Polysaccharide Galactomannans
- Structure Galactose-phosphate and galacomannan
groups - Guar gum (legume)
- is the ground endosperm of seed from the guar
plant (similar to soybean) - Molecular mass 220 000
- Not able to bond easily with proteins/other
polysaccharides - Form gels at 2 3 concentration
- Five to eight times the thickening of starch
- Many uses in pharmaceutical industry
- food stabilizer/source of dietary fiber
13Pectin Substances-Plant Gums
- Approximately 85 of guar gum is guaran
- water soluble polysaccharide consisting of linear
chains of mannose with 1ß?4 linkages to which
galactose units are attached with 1a?6 linkages - The ratio of galactose to mannose is 12
Guaran is the principal polysaccharide in guar
gum.
14Pectin Substances-Plant Gums
- Locust Bean
- Derived from the seed endosperm of carob trees
- Form pliable gums
- Both consist mostly of galactomannans
- Cold water soluble
- USES
- Salad dressings
- Ice-cream
- Baked goods (stabilizing and water retention)
15Pectin Substances-Plant Gums
- Agar / Carrageenans
- Agar
- extracted form seaweed
- polymer of agarobiose, a disaccharide composed of
D-galactose and 3,6-anhydro-L-galactose. - Consists mainly of galactose
- Uses Solid medium in microbiological
applications, culturing bacteria, cellular tissue
and DNA fingerprinting - Potent gel former
- Forms gel at about 0.04
16Agarobiose is the repeating disaccharide unit in
agar
Pectin Substances-Plant Gums
17Pectin Substances-Plant Gums
- Carrageenan
- Extracted from seaweed
- Differs from agar in that they have sulfate
groups - (-OSO3-) in place of some hydroxyl groups
- Complex sulphated galactan
- Negatively charged on sulphate group
- Form gels of varying viscosity based on Ca or
K - Can interact with protein due to ionic bonding
- Uses Stabilizers, thickener in instant puddings
and desserts
18Pectin Substances-Plant Gums
- Changes in structure during hydolysis
- Undergo hydrolysis by acid or alkali or suitable
enzymes (alkaline hydrolysis) - First step Removal of number of methoxyl groups
- Leaving ultimately polygalacturonic acid
- Called pectic acid completely free of methoxyl
groups
19Pectin Substances-Plant Gums
- Extraction of Pectin
- Mainly form apple and citrus peels
- Soak in warm water
- Remove colloidel material, carbohydrates, acid
and other water soluble inpurities - Rest of material are dried
- Until moisture content of ca 10
20Pectin Substances-Plant Gums
- Extraction
- Watermoist peel 31
- Waterdry peel 301
- Waterpeel acidified until pH 1,3 and pH1,4
- 1 hour at 90C - 100C (longer at 60C)
- Increase pH to pH 4,5 using Na2CO3
- Press the mixture
- Extraxt is filtered with EtOH/acetone/AlCl3
- Pectin is floccultaed out of mixture
- Neutralize mixture with Na2CO3 or NH4OH
21Pectin Substances-Plant Gums
- Extraction
- Metal salts are removed from the presipitate
later through acidified EtOH - Pectin is further purified by dissolving it in
water and presipitating with EtOH until the
product is pure
22Pectin Substances-Plant Gums
- Marketing of Commercial Pectin
- Available in the pure state
- Characterized according to
- 1. Jellying power (grade)
- Increases with increasing molecular weight
- 2. Degree of methoxylation
- High methoxyl or low methoxyl pectins
- Determines the mechanism of gel formation
- 3. Rate of solidification of the jellies
- Rapid/medium/slow set pectins
- Rate and temperature of setting is also governed
by the extend of esterification
23Pectin Substances-Plant Gums
- Rapid pectins higher degree of methoxylation
- At equal degrees of esterification, pectins with
a higher degree of polymerization require shorter
setting times.
24Pectin Substances-Plant Gums
- 1. Jellying Power Pectin GRADES
- Number of parts of sugar required to gel one part
of pectin to acceptable firmness - OR
- Number of parts of sugar that can be gelled by 1
part of pectin under standard conditions - Usual conditions (Standard conditions)
- pH 3.2 3.5
- Sugar 65 70
- Pectin 0.2 1.5
- Commercial grades vary from 100 500
- Gels of different firmnesses can be formed by
playing around with the pectinsugaracid ratio
25- 1. Jellying Power Pectin GRADES
- Example If you require a minimum of 0.1 g of
pectin to 65 sugar and at a pH of 3.2 the pectin
grade for that would be 650 - 0.1 x 10 1 1 part of pectin
- 65 x 10 650 pectin grade
- Factors contributing to the gelling properties of
pectin - Chain length
- Degree of methoxylation
- pH
- Sugar content
26Pectin Substances-Plant Gums
- 2. Degree of Methoxylation
27Pectin Substances-Plant Gums
- Pectin as extracted normally has more than 50 of
the acid units esterified, and is classified as
"high methyl ester (HM) pectin". - HM pectin
formula
28Pectin Substances-Plant Gums
- Modification of the extraction process, or
continued acid treatment, will yield a "low
methyl ester LM) pectin" with less than 50
methyl ester groups. - LM pectin formula
29Pectin Substances-Plant Gums
- 3. Rate of solidification of the jellies
- Rapid-set pectin
- Degree of methoxylation over 70
- Forms gels with sugar and acid at optimum pH 3.0
3.4 - Begins at 85ºC
- Gel strenghts depend on molecular weight
- The higher the molecular weight, the firmer the
gel - Gel strength is not influenced by degree of
methoxylation - Used in manufacturing of preserves in order to
prevent whole fruit or chunks settling to the
bottom or rising to the top of the jar, instead
of being evenly distributed throughout the jam
30Pectin Substances-Plant Gums
- Slow-set pectin
- Degree of methoxylation 50 70
- Forms gels with sugar and acid at an optimum pH
2.8 3.2 and at lower temperatures than
rapid-set pectin - Forms jelly below 55ºC
31Pectin Substances-Plant Gums
- Uses of Pectin in Food Manufacturing
- Jams, jellies, marmalades and preserves
- Dehydrating agent must be present for pectin to
form a gel - Typical dehydrating agents used for precipitation
of pectin are alcohol or acetone - In jams and jellies it is the sugar that plays
the dehydrating role - In forming a good jelly, suitable
pectin-acid-sugar ratio should be maintained
32Pectin Substances-Plant Gums
- Syneresis weeping
- If the pH drop lower than 3, you will find that
the gel becomes firmer and may even exhibit
syneresis. - Water is expelled from the gel
- Common in Fruit Jellies
- See syrup forms on the jelly after a couple of
months in storage - Factors contributing to Syneresis
- Low pH (too much citric acid added) leads to
degrading of the pectin netwok water cannot
hold gel structure efficiently anymore - Excess water (low TSS)
- Not enough pectin
33Pectin Substances-Plant Gums
- Pectolytic Enzymes
- Pectin enzymes are capable of degrading pectic
substances - Commercially important for the treatment of fruit
juices/beverages - To aid in filtration/clarification/increasing
yields - Pectolytic Enzymes have to be added during
production of most fruit juices and veggie soups - Also used for the production of galacturonic
acids - Presence of pectic enzymes in fruit/veggies can
result in excessive softening - Pectins may also cause cloud separation in
tomato and fruit juices
34Pectin Substances-Plant Gums
- Commercial Uses
- Clarification of fruit juices/wines
- Aiding the disintegration of fruit pulps
- By reducing the large pectin molecules into
smaller units, and eventually into galacturonic
acid compound become water soluble loses
their suspending power - Viscosity is reduced
- Insoluble pulp particles rapidly settle out
35Pectin Substances-Plant Gums
- Pectic enzymes
- Most microorganisms produce at least one pectic
enzyme - Almost all fungi and many bacteria produce these
enzymes - Which readily degrade the pectin layers holding
plant cells together - Leads to separation and degradation of the cells
plant tissue becomes soft - Bacterial degradation of pectin in plant tissues
is responsible for the spoilage known as soft
rot in fruits/veggies
36Pectin Substances-Plant Gums
- Pectinesterase (PE)
- (or Pectin Pectyl-Hydrolase)
- Found in bacteria, fungi, higher plants
- Large amounts in citrus fruits tomatoes
- PE catalyzes the hydrolytic removal of the
methoxyl groups (saponification) from the pectin
molecule (methylgalacturonic acid) - Requires the presence of a free carboxyl group
next to the methoxyl group to be saponified - Optimum activity at pH 7.5
- Methoxyl group may be released as methanol
- Could be considered a toxic by-product
- Reaction is catalyzed by pectin esterase
- PE is specific for galacturonide esters, will not
attack nongalacturonide methyl esters to any
large extent
37Pectin Substances-Plant Gums
- HTST (high temperature short time) pasteurization
is used to deactivate pectolytic enzymes and
maintain cloud stability in fruit juices - Pectin is a protective colloid that helps keep
insoluble particles in suspension - Cloudiness is required in commercial products
provide desirable appearance - Destruction of high levels of pectinesterase
during production of tomato juice/puree is of
vital importance. - Pectinesterase will act quite rapidly once the
tomato is broken - HOT-BREAK method the tomatoes are broken up at
high temperature so that the pectic enzymes are
destroyed instantaneously
38Pectin Substances-Plant Gums
- Polygalacturonase (PG)
- Also known as pectinase
- Catalyses the Hydrolysis the glycosidic linkages
(a-1,4 bonds) in individual units in pectin
chains - Catalyses the glycosidic hydrolysis of the bond
between galacturonic acid units
39Pectin Substances-Plant Gums
- PG can be divided into
- Endoenzymes act within molecule on a-1,4
linkages Endopolygalacturonases - Cause rapid decrease in viscosity of pectin
solutions without considerable increase in
reducing groups - Attack the molecule at random, breaking it to
shorter chains liquefying enzymes - Fruits/filamentous fungi, NOT in yeasts or
bacteria - Exoenzymes catalyze the stepwise hydrolysis
(split) of galacturonic acid molecules, from
nonreducing end of chain - Exopolygalacturonases - Plants (carrot/peaches)/fungi/bacteria
40Pectin Substances-Plant Gums
41Pectin Substances-Plant Gums
- Pectin Transeliminase (PT)
- Catalyses a dehydration reaction that breaks the
alpha-1,4 glycosidic bond - Splits the glycosidic bonds of a glucuronide
chain by trans elimination of hydrogen from the
4- and 5-position of the glycuronide moiety - Attacks only glycosidic bonds between
methoxylated units - Glycosidic bonds in pectin are highly susceptible
to this reaction - PT are of the endotype and are obtained
exclusively from filamentous fungi, Aspergillus
niger - The purified enzyme has an optimum pH 5.1 5.2
42Pectin Substances-Plant Gums
- Amount of enzyme required for clarification of
juice - Depends on type of enzyme
- Amount of bentonite/glucose powder
- Bentonite is an activated clay used to form a
heavy complex with colloidal material and to
remove the presipitate through filtration. - Type and pH of Juice
- Time and temperature of method used
43Pectin Substances-Plant Gums
- Enzyme treatment is usually followed by a
pasteurisation process - To destroy yeasts
- Inactivate Pectolitic and oxidising enzymes
- Denaturise proteins
44Pectin Substances-Plant Gums
- Role of Pectin in Cloud Formation
- When juices are produced from fruit, the initial
extraction process produces a liquor (or serum)
as well as a particulate component - Cloudy juices consist of a suspension of very
fine particles in a clear medium (serum) - Some particulate will form a sediment settle at
the bottom of the tank - Rest remains as cloud in juice
- Some juices require this cloud to give the juice
its specific consumer appeal and mouthfeel - Tomato juice/guava juice/orange juice/lemon juice
45Pectin Substances-Plant Gums
- Cloud Structure
- Differs from one juice to another, although the
basic structure is the same - In orange juice the cloud consists of micelles
(colloidal particles) that contain a positively
charged protein core coated by a layer of
negatively charged pectin - Neg. charged due to the free carboxyl ( COO-)
groups on pectin - These neg. charges cause electrostatic repulsion
between micelles (electrostatic charge of the
suspended particles) - Prevents them from settling down
- Maintenance of the cloud
- Interference with the cloud structure will very
likely precipitate it
46Pectin Substances-Plant Gums
- Clarification of Cloudy Juices
- Removal of the particulate matter
- Negative charges (surface of particles) will
create insoluble complexes with other soluble
polyelectrolytes of opposite charge - Will then precipitate easily
- WINE polyethylenamine is used for the
clarification of cloudy wines - The precipitate thus formed will settle, carrying
with it all suspended matters as well as tannins - Another method for attaining similar effects
consists of treating cloudy liquids with
commercial preparations of pectolytic enzymes,
Pectinol - Usually obtained from molds and contain PE and
endo-PG
47Pectin Substances-Plant Gums
- Clarification of Cloudy Juices
- Can also be done by filtration of the juice of
wine - Adsorbing the cloud onto a stationary phase
- Requires you to run juice through a column or
over a bed of adsorbent (ex. Polyethyleneamine) - Positive charges on the resin attracts negatively
charged cloud and binds it - Bentonite is used in the wine industry
- Adding a flocculant to the juice
- Adding aluminium sulphate the Al precipitates
the cloud due to electrostatic attraction. - Using pectolytic enzymes
- PE and PG can disrupt pectin and therefore cloud
structure leading to precipitation
48Pectin Substances-Plant Gums
- Industrial Manufacture of Pectins
- Commercial Pectins are manufactured in two main
forms - Liquid pectins concentrated solutions of
pectins extracted from waste plant materials
(pomace/citrus peels) - dry-pectin powders
- Commercial practice the resulting products are
not pure substances - Their degree of purity depends largely on
- The methods of manufacture
- Molecular size of pectin substances
- Degree of esterification
- Amount of accompanying ballast material present
49Pectin Substances-Plant Gums
- Manufacturing procedures comprise the following
main steps - (1) Removal of material
- (2) Removal of ballast
- (3) Acid hydrolysis of protopectin and
dissolution of pectin - (4) Precipitation
- By alcohols or acetone
- Or mineral salts such as aluminium hydroxide with
opposite electric charge to negatively charged
pectinic acids - (5) Purification and drying
50Pectin Substances-Plant Gums
- The use of HM-pectin in fruit jellies/jams
- Dissolving dry pectin
- Pectin must be in a complete gel form to be used
to maximum capacity - A standard pectin solution
- Dry pectin with correct amount of water
- Mix quickly with Mechanical mixer
- Until clear viscous solution
- Measured part is added to jam mixture
- Or dry pectin can be mixed with sugar before
adding to jam this will prevent lumps - At high temperature pectin are degraded (Grade of
pectin) - Ideally pectin will be added in the final stage
of the evaporation process when the jam mixture
are boiling
51Pectin Substances-Plant Gums
- Solidification of Pectin Gelling
- Pectin are generally safe but precautions need to
be taken against preset - There are two main gel forming characteristics
that have an important role in the quality of
fruit jellies - (1) Gel point/Gel temperature/solidification
point/solidification temperature - (2) Solidification time
52Pectin Substances-Plant Gums
- (1) Gel point/Gel temperature/solidification
point/solidification temperature - The gel strength at the gel point is very weak.
But increases first rapidly and then more slowly
until maximum gel strength are reached after a
couple of weeks - Factors influencing solidification temperature
are - Rate of cooling down
- The faster the product cools down the lower the
solidification point - Degree of esterification (DE)
- The higher the DE the higher the solidification
temp. - DE can be determined by titration with an alkali
the amount of free carboxyl groups will be
accounted for
53Pectin Substances-Plant Gums
- pH of the Jelly
- Lower pH higher solidification temperature
- (2) Solidification time
- The solidification time is the time elapsed since
the ideal conditions for gel forming where
reached until the time the actual solidification
process starts - Factors influencing solidification time are
- Rate of cooling down
- The faster the product cools down the faster
solidification process starts and the
solidification temperature is reached sooner - Degree of esterification (DE)
- At the same rate of cooling down, rapid set
pectin will solidify at 88C and slow set pectin
will only solidify at 54C this is due to
differences in DE
54Pectin Substances-Plant Gums
- Molecular Mass (Mr) of the Pectin
- The higher the Mr the shorter the
solidification time - Solidification time differs from 1 to 6.5
minutes, depending on all the factors influencing
it. - Setting of pectin can start all ready during the
evaporation process - When this occurs the structure of gel will be
disrupted and made weaker due to turbulence - Gel lumps will form and the product will have a
appearance - Therefore setting of gel may only start after the
fill process especially for pure jellies like
apple/guava
55Pectin Substances-Plant Gums
- Setting of pectin can also take too long
- Especially in whole fruit/jelly combinations such
as marmalade - The suspended fruit material can settle down
- In this case the gel structure must form quickly
for the solid materials to stay in suspension - The solidification time must therefore be
controlled - It is of most important to use a pectin of
correct DE - The rate of cooling can e adapted
- But the filling process must continue smoothly to
prevent preset
56Pectin Substances-Plant Gums
- ERH and Microbiological Stability of Jam
- The preservation of jam depends on the increase
of the osmotic pressure or the decrease of the
ERH (Equilibrium Relative Humidity) - Little microbiological spoilage occurs in jam
with 68 70Brix, but at 65Brix molds can
develop at the surface of jam - Jam with a relative low TSS can be manufactured
to have less of a sweet taste and a more distinct
fruit taste - In this case a preservative must be added to
prevent molds forming Sorbic acid can be used
57Pectin Substances-Plant Gums
- During cooling condensation of water occurs on
the inside surface of the tin - The top layer of jam becomes diluted
- If the inside of the tin is not sterile, then
microbiological spoilage can occur during and
after storage - The fill temperature of jam therefore needs to by
high enough to sterilize the tin and cover,
because the final product will not undergo
further heat treatments
58Pectin Substances-Plant Gums
- Points to consider during Production
- (1) Yield
- Fruits/sugar/citric acid and pectin needs to be
in the correct ratio during the evaporation
process to reach a TSS-value of 62 73Brix - The final TSS-value are determined by the type of
product - TSS has an influence on
- Taste
- Colour
- Gel strength
- Profit of process
- Each ingredient of the jam mixture contributes to
the cost of the jam manufacturing
59Pectin Substances-Plant Gums
- Example of the composition of jam
- This mixture contains 55.5 g solved solids for
100.5 g and need evaporation to be concentrated
until 68 g/100 g (68Brix)
60Pectin Substances-Plant Gums
- (2) Control of TSS in manufacturing of Jam
- Strict control over TSS-value is important in the
final stage op production - Jam thermometers are used to monitor the
evaporation process - When a predetermined boiling temperature is
reached the process will be stopped - Refractometers are used to control the process
- The boiling point of jam is determined by the
- TSS-value
- Air pressure of mixture
61Pectin Substances-Plant Gums
- (3) Evaporation rate and boiling pot construction
- There are more than one reason for the
evaporation rate to be as fast as possible - Non-enzymatic browning being the most important,
needs to be limited - For the same reason the cooling time needs to be
as quick as possible - Jam pots are made of Red Copper
- Excellent conductivity
- Build in steam coil - Hasten the process
- Red Copper can enhance the colour of green figs
and watermelon jam - Can also leaf off tastes and destroys ascorbic
acid in fruit
62Pectin Substances-Plant Gums
- Evaporation rate depends on
- Amount of water per charge that needs to be
evaporated, in other words, the amount of fruit
per boiling cell - Total availability of heating surface and
conductivity of metal used to manufacture boiling
pot - Steam pressure determines the heat capacity and
amount of steam that is available for evaporation
process - Today more than 80 of the worlds jams are
manufactured in open pots
63Pectin Substances-Plant Gums
- (4) Crystallization of sugar
- The degree of saturation of sucrose-solution is
67.1Brix at 20C. Jam are in most cases
evaporated until 68 69Brix and whole fruit
jam as high as 70Brix - Lots of water are bound by pectin, thus leading
to a very low amount of unbound water in jam - To low to prevent crystallization
- Sucrose inversion takes place during evaporation,
and therefore crystallization occurs seldom
64Pectin Substances-Plant Gums
- (5) Inversion of Sucrose
- Sucrose are inverted to Glucose by fruit acid or
added Citric acid during the boiling process - The inverted product can also be added through
additional invert sugar that has been
pre-produced with citric acid or hydrochloric
acid - Inversion takes place at n high temperature when
enough acid is present - Crystallization usually occurs in jams with no
gel structure because sufficient acid where not
available for the inversion of these products - Inversion are usually taken to 28 32 - At this
level the sugar will not crystallize - Unless the TSS-value are abnormal
- If the pH is too low, due to too much acid
inversion will go too far and the danger occurs
where glucose can be crystallized out
65Diabetic Jams
- Example 1
- They are made with the same great tasting fruits
as our regular jams, but we use Sugar Care
sweetener instead of sugar, and LMO Pectin, made
specifically for Diabetic Jam. - Sugar Care is one of the newest Diabetic
sweeteners on the market and has NO aftertaste.
Sugar Care is made by Hormel Health Labs. - Because of the sweetener and the LMO Pectin some
of the Jams will not be as clear or transparent
as those made with regular Sugar and Pectin. - Example 2
- Diabetic Jam-Using Sorbitol and Pectin
- the commercial pectin, saccharin tablets
andgelatin