Pectin
Pectin
Jansman AJM, Hill GD, Huisman J and van der Poel AFB intake and effects on nutrition and health (review).
(eds) (1998) Recent Advances of Research in Anti- Journal of the Science of Food and Agriculture 80:
nutritional Factors in Legume Seeds and Rape Seeds. 1094–1117.
Wageningen, The Netherlands: Wageningen Pers. Savage GP (1988) The composition and nutritive value of
Martinez San Ireneo M, Ibanez Sandin MD and Fernandez- lentils (Lens culinaris). Nutrition Abstracts and Reviews
Caldas E (2000) Hypersensitivity to members of the (Series A) 58: 319–343.
botanical order Fabales (legumes). Journal of Investiga- Savage GP and Deo S (1989) The nutritional value of
tional Allergology and Clinical Immunology 10: 187– peas (Pisum sativum). A literature review. Nutrition
199. Abstracts and Reviews (Series A) 59: 65–88.
Rowland I (1999) Optimal nutrition: fibre and phytochem- Urbano G, Lopez-Jurado M, Aranda P et al. (2000) The
icals. Proceedings of the Nutrition Society 58: 415–419. role of phytic acid in legumes: antinutrient or beneficial
Sanchez-Monge R, Pascual CY, Diaz-Perales A et al. (2000) function? Journal of Physiology and Biochemistry 56:
Isolation and characterisation of relevant allergens from 283–294.
boiled lentils. Journal of Allergy and Clinical Immun- van der Poel AFB, Huisman J and Saini HS (eds) (1993)
ology 106: 955–961. Recent Advances of Research in Antinutritional Factors
Santos-Buelga C and Scalbert A (2000) Proanthocyanidins in Legume Seeds. Wageningen, The Netherlands:
and tannin-like compounds. Nature, occurrence, dietary Wageningen Pers.
PECTIN
Contents
Properties and Determination
Food Use
Properties and Determination only started at the beginning of the twentieth century.
In this document we highlight the chemistry, origin
L Flutto, Danisco, New Century, KS, USA
and production, and the functional properties of
Copyright 2003, Elsevier Science Ltd. All Rights Reserved. pectin.
Introduction Chemistry
0001 Pectin is a high-molecular-weight carbohydrate poly-
The Homogalacturonic Acid Backbone
mer which is present in virtually all plants where it
contributes to the cell structure. The term pectin Pectin consists of a chain of galacturonic acid units 0003
covers a number of polymers which vary according which are linked by a-1,4 glycosidic bonds. The
to their molecular weight, chemical configuration, galacturonic acid chain is partly esterified as methyl
and content of neutral sugars, and different plant esters. Pectin molecules can have a molecular weight
types produce pectin with different functional prop- of more than 200 000, corresponding to a degree of
erties. The word ‘pectin’ comes from the Greek word polymerization up to 1000 units (Figure 1).
pektos which means firm and hard, reflecting pectin’s Though the esters are the most significant compon- 0004
ability to form gels. ents on the galacturonic acid backbone, other chem-
0002 The gelling properties of pectin have been known icals, such as acetyl, can be important in specific
for centuries, but the isolation of commercial pectin pectin types. Commercial pectin can also be partly
PECTIN/Properties and Determination 4441
OH COOCH3 OH COOCH3 OH
O O O
O
OH OH OH OH OH
O O
O O O
fig0001 Figure 1 Pectin consists of long sequences of anhydro galacturonic acid completely or partly esterified with methanol.
backbone, their position is of significant importance they are only slightly affected by the presence of
to the functional properties of pectin. The distribu- calcium. However, solutions with more than 1%
tion of esters is of special importance as it affects the pectin exhibit pseudoplastic behavior and are strongly
local electrostatic charge density of the polymer and affected by calcium. There is a continuum in texture
so its interaction with other charged molecules, starting with water through thixotropic solutions
whether ions such as calcium, proteins, or other with yield value to stiff gels depending on the pectin
pectin molecules. type and concentration, level of calcium, and pH.
0009 In apple pectin subjected to a mild extraction pro-
Stability High-ester pectins are stable at pH levels of 0015
cess, the ester distribution is reported to be almost
2.5–4.5. Above a pH level of 4.5, b-elimination will
random, while citrus pectin tends to have a somewhat
occur, depolymerizing the galacturonic acid chain.
blockwise distribution.
This mechanism requires an esterified carboxyl
group next to the glycosidic bond to be cleaved
Neutral Sugars
(Figure 3), so low-ester pectins are more stable at
0010 Pectin always contains varying amounts of neutral higher pH values.
sugars such as d-galactose, l-rhamnose, l-arabinose, The pectin molecular structure is quite resistant 0016
and d-xylose. Some of these neutral sugars are con- to heat. At pH around 3.5 pectin is only marginally
stituents of side chains to the galacturonan backbone. depolymerized at high temperatures. The heat-stability
4442 PECTIN/Properties and Determination
Hairy region
Galacturonic acid
Methylated galacturonic acid
Sm om
Rhamnose
h
oo oga
th lac
Arabinose or galactose
re tu
gi ro
on na
Xylose (high content in apple pectin)
, n
Acetyl group (high content in sugar
beet pectin)
COOCH3
OH O
OH
OH
OH
COOH
OH O
OH
OH
OH Rhamnogalacturonan
O O CH3
O CH3
OH C O
OH C
O OH
O O
OH OH
OH OH
O
O O
O
O C OH
O C OH
O CH3
O CH3
of pectin is greatly improved when the water activity neutralized with cations of calcium, potassium, and
of the system is lowered through the addition of magnesium which are present in the plant tissues.
sugar. Pectin is today commercially produced mostly 0018
agent. The exact nature of the pectic substance is not pharmaceutical products. Their principal properties
completely understood. It is, however, generally rec- are gel formation with both high- and low-ester
ognized that it is a complex structure in which pectin pectins, viscosity build-up, and protein stabilization
is attached to other cell wall components such as with high-ester pectins. As methods develop for
cellulose, hemicellulose, and proteins by covalent obtaining a better understanding of the pectin mol-
bonds, hydrogen bonds, and/or ionic interactions. ecular structure, it is likely pectin will be attributed
In the plant the residual carboxyl groups are partly new functional properties in the future.
PECTIN/Properties and Determination 4443
0022 Gelling will occur upon cooling of a media where of the galacturonic acids affects both the charge dens-
favorable conditions are met. Cooling is necessary to ity of the polymer and the number of sites for hydro-
decrease molecular movement and permit the forma- phobic interaction. As pectin molecules with a high
tion of intermolecular interactions. degree of esterification are less charged, they can
0023 As the pectin chains carry negative charges they form gels at a higher pH and will also start gelling
will tend to repel each other. This repulsion will at a higher temperature.
4444 PECTIN/Properties and Determination
Junction zone
H+
H2O
Sucrose
Hydrogen bonding
C C C
O O O O
O
H H H c
o o
H H
CH3
O CH3 Hydrophobic
O O O interaction
C C C H
o o
c
fig0005 Figure 5 High-ester pectin gels through hydrogen bonding and hydrophobic interactions in an acidic water and sugar matrix.
120
DE = 63
% obtainable firmness
100
DE = 73
80 DE = 81
60
40
20
0
3.0 3.2 3.4 3.6 3.8 4.0
Jelly pH
fig0006 Figure 6 High-ester pectin: the degree of esterification (DE) determines the optimal pH for the gelation.
0030 This last effect forms the basis for the classification The effect of neutral sugars on high-ester pectin 0033
of high-ester pectins into rapid-set, medium-rapid- gelling can be twofold and would need to be studied
set, slow-set, and extra-slow-set pectins as the degree more extensively. Neutral sugars present on the pectin
of esterification is decreased from more than 70% to molecule could result in steric hindrance of inter-
50% (Figure 6). molecular interaction and thus decrease the ability
0031 The distribution of the ester groups on the back- of the pectin to form gels. However, they could also
bone will also affect pectin gelation, as a marked participate in gelling through hydrophobic inter-
blockwise distribution of esters will result in a signifi- action and contribute to an increased cohesion of
cant contribution of calcium gelling. This contribu- the gel.
tion of calcium gelling will significantly increase the
gelling temperature of the pectin (Figure 7). pH and ionic strength of the gelling system The 0034
Rhamnose
Galacturonic acid
Methylated
Marked block
galacturonic acid
structure
Neutral sugar
Calcium
network and precipitation can occur. The optimum the cooling rate is increased, the gelation rate is also
pH for gelation is controlled by the degree of ester- increased. However, during rapid cooling and with a
ification of the pectin as well as the soluble solids low storage temperature, gelling can actually become
content of the medium (Figure 6). very slow, reflecting the difficult development of
0035 Through their effect on the neutralization of the hydrophobic interactions in these conditions. With
pectin molecule, cations present in the system will an intermediate cooling rate and temperature range,
affect gelling. High ionic strength shifts the optimum hydrogen bonds and hydrophobic interactions
pH range towards higher values. This is particularly together can contribute to the build-up of a network
visible with sodium ions. However, with ions such as with the highest elasticity.
calcium or potassium that can bridge high-ester
pectin molecules in areas with a low density of ester, Properties of high-ester pectin gels Due to the nature 0039
there is a possible increase in junction zones. This of the molecular interactions involved in high-ester
effect can become significant for high-ester pectin pectin gelation, gels made with these pectins will
with marked blockwise distribution of ester groups typically not be thermo-reversible or shear-reversible.
(Figure 7). When submitted to mechanical stress, the broken gel
will then show a high level of syneresis.
0036 Water activity and sugar types Water activity and
sugar types will both affect the way hydrophobic Gelling of Low-Ester Pectin
interactions can develop between the pectin mol- Low-ester pectin has traditionally been used for gel- 0040
ecules. As water activity is reduced, the hydrophobic ling food products when the conditions required to
interactions are easier to form, causing faster gelling achieve a gel with high ester pectin were not met.
to occur and the final gel strength to be increased. Recently however, low ester pectins have also found
0037 The commonest way of reducing water activity in a applications in high sugar and low pH systems
food system is through the use of sugars. The effect of because of their specific texture characteristics.
sugars on hydrophobic interaction and so on gel Though the same base mechanism applies, low 0041
structure will be specifically linked to their molecular ester conventional and amidated pectin differ in
conformation and their interaction with the neighbor- their gelling properties and offer a broad range of
ing water molecules (Figure 8). functional properties.
0038 Influence of cooling rate and storage temperature Gelling mechanism The gelation of low-ester 0042
Cooling decreases molecular movement and allows pectins is the result of ionic linkage through calcium
polymer molecules to interact at close distances. As bridges between carboxylic groups from two pectin
4446 PECTIN/Properties and Determination
63 DE corn syrup
Gel strength
42 DE corn syrup
fig0008 Figure 8 Effect of various sugars on high-ester pectin gel strength. DE, dextrose equivalent.
OH O OH O OH O
HO COO− HO COO− HO COO−
O O O O O O
COO− HO COO− HO COO− HO
O O O
− C C C C C
O O H N O O O O O O
H H H H
Ca++
H H H
O
O C− O O O O O H
C C C C C
fig0009 Figure 9 Eggbox model. Schematic overview of established low-ester pectin gel mechanism, showing calcium-induced junction
zones. Inset shows detail of the various types of possible hydrogen bonding that participate in the junction zone, together with the
calcium chelation (far left).
chains with the participation of hydrogen bonding. many oxygen atoms and because of flexibility with
The linkage generally takes place upon cooling a regard to the direction of its coordinate bonds.
pectin and calcium system. The most commonly The exact calcium requirements to obtain a gel 0043
accepted model of association is the eggbox model highly depend on the degree of esterification of the
(Figure 9). In this model, pectin chains could be pectin, the recipe, and process parameters such as the
bridged by calcium ions, which incorporate in their rate of cooling. An increase in ionic strength, increase
coordination shells two polyanion oxygen atoms in pH, or decrease in the degree of esterification
from one pectin molecule and three from another lowers the amount of calcium required to achieve
chain. Even though a number of positive ions can sol–gel transition. An optimum calcium level can be
bridge pectin molecules, especially magnesium and defined for a given pectin in specific conditions.
potassium, calcium is particularly effective in com- Above this optimum level, pregelation will occur,
plexing with carbohydrates, largely because its ionic i.e., gelling will occur at too high temperatures to
radius (0.1 nm) is big enough to coordinate with obtain a coherent gel structure (Figure 10).
PECTIN/Properties and Determination 4447
significant influence on gelling and the final structure strength can be observed at a higher ionic strength.
obtained. The main parameters are the number and This is usually explained by the neutralization of the
distribution of ester and amide groups as well as the polymers by the extra ions, which allows the chains to
molecular weight of the pectin molecule and the pH, be closer, leading to a more organized and cohesive gel.
ionic strength, and water activity of the gelling
system. Influence of water activity As the solids level 0054
160
140
120
40
20
0
3.10 3.30 3.50 3.70 3.90 410
pH
fig0011 Figure 11 pH influences on Ca-curves in low-sugar system (31% soluble solids), with high reactive amidated pectin. Triangles,
100 mg Ca; squares, 200 mg Ca.
In practice, this leads to a choice of pectin with a Due to the lower proportion of carboxyl groups, 0058
higher degree of esterification (less calcium-reactive) high-ester pectin has a weaker electrostatic inter-
at a higher solids level. action with protein than low-ester pectin but proves
to be more effective. Indeed, it seems to be important
Properties of Low-Ester Pectin Gels that significant parts of the pectin molecule do
not interact with the protein surface in order to
0055 The properties of low-ester pectin gels are very de-
achieve the steric repulsion effect. It is also the key
pendent on the type of pectin used (conventional or
to minimizing interactions between pectin and
amidated) along with the procedure and formulation
cations available in the system.
employed to make the gel. Typically, they are thermo-
Both the DE of the pectin and the distribution of 0059
reversible and show a high degree of thixotropy. In
the esters on the polymer affect its stabilization prop-
specific conditions it is however possible to obtain
erties. Excessively large blocks of carboxyl groups
heat-resistant or very brittle gels with no shear revers-
will tend to interact with the ions present in the
ibility.
system, such as calcium, rather than with the protein
– an interaction which will lead to an increase in
Protein Stabilization with High-Ester Pectins
viscosity or even gelation.
0056 In acidified conditions, casein and, more generally,
food proteins will tend to agglomerate and sediment Conditions Most food proteins (isoelectric point 0060
if the viscosity of the system is low enough. In these around 5) can form complex coacervates with anionic
conditions the proteins are also very sensitive to polysaccharides such as pectin (isoelectric point
dehydration and can easily become sandy after heat around 3.5) in the intermediate-pH region, where
treatment. With the rapid development of acidified the two macromolecules carry opposite net charges:
dairy beverages worldwide, now expanding with pH above the isoelectric point of the polysaccharide
other protein sources such as soy, the need for effect- but below that of the protein.
ive protein stabilizers in a low-pH environment is In the case of pectin–protein interaction, the 0061
growing strongly. High-ester pectin has proven to be strength of the complex will depend on several
a very useful stabilizer in these conditions. factors, such as the distribution of the carboxyl
groups on the galacturonic acid backbone, but also
0057 Mechanism It is generally accepted that, at suffi- on the three-dimensional protein structure and the
cient pectin concentrations, the adsorption of the distribution of ionizable groups on its surface. The
carboxyl blocks of the pectin molecule to the protein whole interaction will also depend on several system
surface will stabilize the protein system through steric parameters such as pH, ionic strength, presence of
repulsion (Figure 12). So, the presence of blocks of sugars, or fat.
free carboxyl groups on the galacturonic backbone Through its role in the ionization of both the protein 0062
has an important influence on the protein-stabilizing and pectin molecules, pH is the most significant factor
property of pectin. affecting electrostatic pectin–protein interactions. It
PECTIN/Food Use 4449
Rhamnose
Galacturonic acid
Neutral sugar
Part of casein
Marked block
structure
also plays a very significant role in the protein struc- Rheology of Liquids; Stabilizers: Types and Function;
ture and how proteins interact in a complex system Applications
such as milk.
0063 The optimum pH range for interaction between Further Reading
high-ester pectin and casein is 3.6–4.5. At a lower
pH, the block structures of the high-ester pectin Dickinson E (1998) Stability and rheological implications
will not be sufficiently ionized for proper protein of electrostatic milk protein–polysaccaride interactions.
Trends in Food Science and Technology 9: 347–354.
binding as the pH is too far below the pKa of the
Kravtchenko TP, Voragen AGJ and Pilnik W (1994) Char-
pectin. Above the isoelectrical point of the protein,
acterization of industrial high methoxyl pectins. Gums
the protein–polysaccharide complex is very weak or and Stabilizers for the Food Industry 7: 27–35.
nonexistent and the electrostatic protein–protein May CD (1990) Industrial pectins: sources, production and
repulsion is dominant. It is, however, clear that application. Carbohydrate Polymers 12: 19–99.
this repulsion is not sufficient to stabilize the proteins. Rolin C and De Vries J (1990) Pectin. In: Harris P (ed.) Food
Gels, pp. 401–434. London: Elsevier.
Thakur BR, Singh RK and Handa AK (1997) Chemistry
Conclusion and uses of pectin – a review. Critical Reviews in Food
0064 Pectin exhibits a wide range of functional properties Science and Nutrition 37: 47–73.
and enjoys a very good public image as a natural Walter RH (ed.) (1991) The Chemistry and Technology of
Pectin. London: Academic Press.
product derived from fruit. Today it is widely used
as a textural ingredient and stabilizer in a variety of
food applications, and there is little doubt that its
usage will grow as new functionalities are revealed.
Food Use
See also: Cholesterol: Absorption, Function, and
L Flutto, Danisco, New Century, KS, USA
Metabolism; Citrus Fruits: Composition and
Characterization; Dietary Fiber: Physiological Effects; Copyright 2003, Elsevier Science Ltd. All Rights Reserved.
Fermented Milks: Types of Fermented Milks; Gums:
Properties of Individual Gums; Food Uses; Dietary
Importance; Jams and Preserves: Methods of Introduction
Manufacture; Chemistry of Manufacture; Pectin: Food
Use; Protein: Interactions and Reactions Involved in Food Pectin has been used traditionally in food ever since 0001
Processing; Rheological Properties of Food Materials; man started cooking fruits and vegetables. As a