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Pectin

Pectin
Occurs in plant middle lamella
Gel former, e.g., fruit jelly
From
F
the
th G
Greek
k word
d meaning
i to
t congeall
Pectin was discovered in 1790 by
Vauquelin and later (1825) crudely
characterized by Braconnot

Pectic Substance Nomenclature

Protopectin-high methyl ester content

Pectinic acid-intermediate methyl ester
content soluble
content,

Salts are pectinates

Pectin-intermediate methyl ester content,

colloidal
Pectic Acid-little methyl ester content

Salts are pectates

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Pectin--Chemical structure

Some other sugars, mainly L-rhamnose, are also present

Pectin structure

Other monosaccharides (L-rhamnose, Larabinose, D-xylose) in the structure may

limit the size of junctions zones that can
b fformed
be
d and,
d th
thus, att lleastt partially
ti ll
determine ultimate gel strength

Carboxyl Substitution in Pectin

Degree of Methoxylation (DM)

Protopectin
16%
Normal pectin
8%
Low Methoxyl Pectin 2-4%

Degree of Esterification

Protopectin
Normal Pectin
Low Methoxyl Pectin

100%
50%
12.5-25%

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High and low methoxyl pectins

If DE is greater than 50%, it is a high
methoxyl pectin (HM pectin)
If the DE is less than 50%, it is a low
methoxyl pectin (LM pectin)

Degree of amidation (DA)

The DA value indicates the percentage of
carboxyl groups that nave been
converted to the amide form by ammonia
processing
i
Amidated LM pectins may have a DA of
15-25%
Amidated pectins are especially sensitive
to Ca+2 (see W&B, Figure 13.5)

Types of pectins
HM
-COOCH3
(> 50%)
-COOH
+
-COO Na

LM
-COOCH3
(< 50%)
-COOH
+
-COO Na

Amidated
LM
-COOCH3
(< 50%)
-COOH
+
-COO Na
-CONH2
(15-25%)

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Pectic Substances and Gelation

Normal Pectin

Low Methoxyl
y Pectin

Pectic Acid

Gels in the presence of acid and sugar

Doesnt need sugar, but does need calcium ion
Forms insoluble calcium pectate. This reaction is
responsible for the firming effect seen in certain
plant tissues, e.g., canned tomatoes

Pectin gels

Atomic force microscopy image courtesy of Peter Cooke, ERRC, ARS, USDA

Chemistry of pectic substances

Me
O
H
O

H
O
O

O
O
H H

dilute acid
O

or base

O
H O

dilute acid
high temperature

O
O H

depolymerization

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Commercial (Normal) Pectin

Liquid or powdered
Source -- mostly lemon and lime peel (20-30%
pectin).
p
) This is the highest
g
q
quality.
y
Some from apple pomace (10-15% pectin)
Pectin grade = number of pounds of sugar that
one pound of pectin can carry in a jelly

Pectin production
Citrus peel is extracted at pH 1.5-3.0 and
60-100oC
Extract is filtered
Pectin is precipitated by addition of
isopropanol

Commercial (Normal) Pectin

Grade is influenced by DE and molecular

weight
Gel strength -- measured by ridgelimeter
(measures % sag)
sag), penetrometer,
penetrometer Instron,
Instron or
texture analyzer.

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Low methoxyl pectin

Available commercially
Requires no sugar to gel
Requires
q
calcium ion to ggel
Preparation

Enzyme, acid, alkali

Pectin
LM Pectin
Acid preparation is best, produces firmer
gels
Enzyme preparation is inferior as
demethylation is not random

Low methoxyl pectin

Range of pH for gel formation = 2.5-6.5

Pectin uses

Principally used in jellies and jam

However, some is used in

Confections
Beverages
Acidified drinks

See W&B, Table 13.2 for other uses of

pectins

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Jelly making
Need -- pectin + acid + sugar
Pectin

0.5-1.0%
If juice is low in pectin, may concentrate by
boiling or add more as commercial pectin
Peach -- poor gel, pectin contains acetyl
groups
Citrus -- forms a good gel

Jelly making

Acid

Contributes flavor
pH optimum is 3.2
If juice is low in acid, add lemon juice

Jelly making

Sugar

Preservative
Micororganisms cannot grow due to the
j ll high
jellys
hi h osmotic
i pressure
Optimum sugar concentration is about 65%
soluble solids

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Jelly making

Sugar

This is reflected in the final cooking

temperature (colligative properties) of 104.5o
C
During this cooking some of the sucrose is
hydrolyzed to invert sugar which will
discourage sugar crystallization in the jelly

Gel strength in normal

pectin jellies
Jelly strength
Continuity of
structure
[Pectin]
Optimum is
about 1%

Rigidity of
structure

Acidity

[Sugar]

Optimum is 3.2
Low-hard gel
High-no gel

Optimum 65%
Low-weak gel
High-crystals
form

Setting times HM pectins

Rapid set

DE
72-75%

Setting time
20-70 sec

Medium set

68-71%

--

Slow set

62-68%

180-250 sec

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Setting times
Rapid set pectins are used in jams where
quick gelling is desired to prevent
flotation of the fruit
Slow set pectins are used in jellies to
provide time for bubbles to escape
High methoxyl pectin gels can not usually
be melted and reformed

Theory of normal
pectin gel formation

A pectin junction zone

Hydrogen bonds

Pectin junction zones

O
HO

H
OH

OH
OH
O

H
OH
O

CH3

OH
CH3

OH

OH

H
OH

OH

OH

OH
H

H
O

OH

CH3
OH

H
OH

CH3

O
O

OH
H

H
HO

OH
H
O

H
H

OH

HO

OH

OH
OH

O
OH
H
O

OH
CH3

OH

H
OH

OH

OH

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Theory of low
methoxyl pectin gel formation

C l i
Calcium
ion
i

Ionic
bonds

LMP junction zones

H
H

O
O

OH
H

HO

H
OH

H
O H

Ca

OH
H

Ca

O
H

H
OH

O H
CH3

OH

OH

OH
H

O H

O
H

O H

2+

O
OH
H

H
OH

OH

OH

H
O

OH

OH

H
H
OH

O H

O
O

O
H

OH

H
O H

2+

O
HO

CH3

OH

OH

OH
O

O H
O

CH3

Theory of low
methoxyl pectin gel formation

pH needs to be higher (3.2-4.0) because only

carboxylate (COO-) groups can participate
in these types of ionic bonds

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Ability to gel w
with Ca+2

Methyl ester content

and gelling ability

20

40
60
DE

80

100

Characteristics and uses

of low methoxyl pectin gels

These gels can be melted and reformed

repeatedly
No sugar is needed to form the gel, hence
these types of pectins are used in dietetic
products. In practice, a small amount of
sugar is left in the dietetic products as a
tenderizer/texturizer. When included in
these preparations, the resulting jellies are
not as brittle as they would be in the absence
of the sugar.

Uses of low
methoxyl pectin gels

Fat mimetic

From Hercules, this is a LM pectin gelled

with Ca+2 and microparticulated (particle
size < 1 m)
Trade name is Slendid

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Labeling

Both HM and LM pectin may be labeled

pectin

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