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Hydrocolloids: Structure-Function Relationships

Article  in  Food Science and Technology · September 2009

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Saphwan Al-Assaf Glyn O. Phillips

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Hydrocolloids:
Structure-Function
Relationships
Saphwan Al-Assaf and Glyn O. Phillips review the factors
influencing the functionality of acacia gum and other
hydrocolloids of interest to the food industry
Sources and properties of
hydrocolloids
The hydrocolloids associated with
polysaccharides originate from plant
(e.g. plant cell walls, tree exudates,
seeds, tuber/roots, seaweeds) or
animal sources (hyaluronan, chitin,
chondroitin sulphate). Additionally,
certain types of bacteria (or fungi) can
also produce hydrocolloids (xanthan,
gellan, wellan). They are made up
of monosaccharides (sugar units)
glycosidically linked, through water
elimination, to yield mixtures of
similar but not identical molecules of
differing molecular dimensions, with
the distribution often dependent on
the source, method of extraction and
subsequently processing conditions.
Their composition can be derived
either from the same sugar unit
(cellulose and starch), two different
monomers (alginate, hyaluronan)
or often a number of different
monosaccharides, as in gum arabic
(galactose, arabinose, rhamnose and
uronic acid).
Their good solubility in water
is due to the presence of many
hydroxyl groups, but is influenced by
the nature of the monosaccharides
present. Neutral hydrocolloids are
less soluble than those which contain
uronic acids, which are often in the
polyelectrolyte form (charged or ionic).
When dissolved in water, hydrocolloids
can adopt various conformations
(spherical, random coil or rod-like)
depending on the nature of the
monosaccharides, the inter-sugar
linkage (α or β) and their ability to
associate by intra and intermolecular
interactions. These in turn will
determine the characteristics of the
solution flow behaviour.
Functionality in a given commercial
application is controlled by a number
of factors, the most important of which
are the structure and conformation
in aqueous solutions and the way
these are influenced by specific
or non-specific interactions with
other ingredients. The degree of
polymerisation and size (molecular
weight and dimensions) are other
factors that determine their physical
properties. Hence, considerable efforts
to achieve accurate characterisation are
necessary to determine the structure-
function relationships.
In the food industry, their ability
to emulsify oil droplets, modify flow
properties, gelling ability, stabilisation,
prevent sugar crystallisation, impart
texture and mouth feel of aqueous
foodstuff are often utilised. Figure 1
shows an example of how various
Figure 1. Shear flow viscosity of various hydrocolloid
gums plotted as a function of shear rate. Measurements
were carried out in distilled water at 25oC.
HYDROCOLLOIDS
hydrocolloids gums, from various
sources, can modify the flow properties
as measured by a controlled stress
rheometer.
The viscosity of a given hydrocolloid
is influenced by the concentration,
molecular weight and structure (linear,
branched or slightly branched). At
a given molecular weight, linear
structures are capable of producing
entanglements between polymeric
chains at much lower concentration
compared to branched structures.
This is clearly illustrated in the highly
branched structure of gum arabic
which shows the lowest viscosity
compared to all other hydrocolloids
shown in Fig. 1.
Here, we will initially describe,
in more detail compared to other
hydrocolloids (Fig.1), the structure-
function relationship of acacia gums.
Our objectives are to summarise work
carried out in our laboratory and
to outline recent opportunities and
research in this field (Table 1).
Acacia gum
Acacia gum is the exudate from
the Acacia tree, which is one of the
most ubiquitous genera in the plant
kingdom (1). Gum nodule formation
occurs in the cambial region of the
stems or branches. Gummosis is
promoted when the tree is subjected to
stress conditions such as heat, drought,
and insect attack. The tapping process
is the systematic wounding of the tree
by farmers during the dry season
in November/December in order to
regulate the production. The timing
and intensity of tapping have been
reported to influence the gum yield.
The gum will start to collect in the
wound within 4-6 weeks depending
on the weather condition. The gums
are secreted as sticky fluid and grow
up to 1.5-7.5 cm in diameter, and
gradually dry and harden on exposure
to the atmosphere. Collectors harvest
the partially dried gum, and multiple
collections up to three times at three-
week intervals from the same tree are
possible. A yield of 0.5-2 kg is obtained
per tree annually. The quality of
product collected from the various
collection intervals is the subject of
current investigation with the view of
establishing a method to reduce the
17
HYDROCOLLOIDS
natural built-in variation which has
been widely acknowledged.
Acacia species are distributed
throughout tropical and warm
temperate areas of the world, with the
largest concentrations occurring in
Australia (955 species), with also high
numbers in the Americas (about 185
species), Africa (144 species) and Asia
(89 species). Across Sub-Saharan Africa
they form the so-called ‘gum belt’.
There are more than 30 Acacia species
in Sudan which is currently the largest
producer in the world. Acacia senegal
and Acacia seyal remain the most
commercially exploited species of the
whole Acacia resource.
The current WHO/JECFA
Specification (1998), which is
internationally accepted, has also been
approved by Codex Alimentarius:-
Synonyms: Gum arabic (Acacia senegal),
gum arabic (Acacia seyal), Acacia gum;
arabic gum; INS No. 414.
Definition: Gum arabic is a dried
exudate obtained from the stems and
branches of Acacia senegal (L.) Willd. or
Acacia seyal (fam. Leguminosae).
The European Specification (E 414)
is slightly broader and defines Acacia
gum as a dried exudation obtained
from the stems and branches of
natural strains of Acacia senegal (L.)
Willd. or closely related species of
Acacia (family Leguminosae).
Recent EC legislation has approved
gum arabic as an ingredient which
can be labelled as a food dietary
fibre. This recent change has created
an opportunity and demand for A.
seyal due to its lower viscosity, which
can be used at higher concentration
compared to A. senegal. The low
viscosity, as mentioned above, is
due to its highly branched structure
and therefore can be dissolved up
to 50% wt% to produce a solution of
moderate viscosity. In ancient Egypt,
gum acacia was used as a binder in
cosmetics and inks, and as an agent
in the mummification process. It was
introduced to Europe through various
Arabian ports and came to be called
‘Gum Arabic’ after its place of origin or
port of export (2).
Gum arabic (Acacia senegal) is
predominately carbohydrate made
up of approximately galactose (44%),
rhamnose (13%), arabinose (27%),
18 FS&T VOL 23. ISSUE 3
glucuronic acid and 4-O-methyl
glucuronic acid (16%) (3). It also
contains 2-3% peptide moieties as
an integral part of the structure.
Various fractionation techniques have
demonstrated the heterogeneous
complex nature of this polysaccharide
by the presence of three main
fractions. These fractions are:
arabinogalactan protein complex
(AGP), arabinogalactan (AG) and
glycoprotein (GP). Each fraction
contains a range of different molecular
weight components with different
protein contents (4). The AGP
fraction is composed of hydrophilic
carbohydrate blocks linked to a protein
chain and has been reported to have
a wattle blossom-type structure due to
being readily degraded by proteolytic
enzyme - see Fig. 2 (5). There are
other alternative models proposed for
the structure of gum arabic such as
the twist hairy rope, extensin, AGP-
GPI lipid anchor, and revised wattle
blossom model which were recently
reported (6). Treatment of gum arabic
with protease results in a complete loss
of its emulsifying properties (7) and
interfacial elasticity (8). It is now widely
accepted that gum arabic’s role as an
emulsifier is achieved as a consequence
of its ampliphilic character due to the
presence of protein and polysaccharide
moieties. It works by reducing the
oil-water interfacial tension, thereby
facilitating the disruption of emulsion
droplets during homogenisation.
The peptides are hydrophobic and
Figure 2. (a) Schematic representation of the ‘wattle blossom’ structure of the arabinogalactan protein fraction
in A. senegal, (b) coating of the oil droplet by the AGP fraction.
strongly adsorb on to the surface of
oil droplets, whilst the polysaccharide
chains are hydrophilic and extend out
into the solution, preventing droplet
flocculation and coalescence through
electrostatic and steric repulsion forces,
which can be summarised by the term
electrosteric (2) (see Fig. 2).
The interfacial membrane formed
around the oil droplets prevents them
from aggregating (flocculating and/
or coalescing). Recent study of the
interfacial rheology of acacia gums
has shown that A. senegal produces
an elastic interfacial film at liquid/
liquid and liquid/air interfaces. The
elasticity and viscosity increase with
increasing the concentration and the
% of the AGP component (8. 9) and
there is a direct relationship between
the proportion of the AGP component
and emulsification stability. We
have proposed that the proportion
of the AGP and molecular weight
parameters can be readily determined
by gel permeation chromatography
coupled on line to multi-angle laser
light scattering, refractive index
and UV detectors (GPC-MALLS).
Consequently, the molecular weight
parameters of good and poor
emulsifiers can be readily identified
(10) and have currently been used by
a number of users and suppliers as a
standard method for quality control
system. The technique has been also
applied to investigate the molecular
weight distribution for a wide range
of commercial samples of A. senegal
provided by a range of suppliers in
the three different forms (kibbled,
spray-dried and instant soluble) and
has provided valuable information
about the state of the materials,
effect of processing, adulteration and
identification of Acacia species other
than Acacia senegal.
Xanthan
Xanthan is the name given to
extracellular polysaccharide secreted
by a wide range of bacteria belonging
to the genus Xanthomonas. It is an
anionic hydrocolloid with a cellulose
backbone β-(1-4)-D glucose substituted
at C3 on alternate glucose residues
with a trisaccharide side chain (11).
The non-carbohydrate substituents
include O-acetate on the inner
mannose residue and pyruvate on the
terminal mannose residue. Different
strains or fermentation conditions give
rise to differing degrees of acetylation
and pyruvylation, which moderate
the functionality. In Fig. 1, xanthan
at 1% shows a very high viscosity at
low shear rate (deformation) and thus
preferred as a thickener or stabiliser
for dispersed solids or emulsion, while
its high shear thinning behaviour gives
low viscosity when subjected to mixing
or pouring. It is relatively unaffected
by ionic strength, pH (1-13), and
therefore found use in products such
as salad dressings. Xanthan in its
natural state has been proposed to be
bimolecular antiparallel double helices.
It may form a very stiff intramolecular
(single molecule hairpin) double
stranded helical conformation by the
annealing of the less stiff ‘natural’
denatured elongated single stranded
chains. The glucan backbone is
protected by the side chains, which
makes it relatively stable to acids,
alkalis and enzymes (particularly
cellulase).
Carboxymethyl cellulose
Carboxymethyl cellulose (CMC)
is chemically modified cellulose.
Its structure is based on the β-(1,
4)-D-glucopyranose polymer of
cellulose. Cellulose is insoluble in
water and when it is modified by
replacing hydroxyl group with
carboxymethyl group. This is how the
insoluble cellulose can be made water
HYDROCOLLOIDS
Application Necessary functionality and features needed for best
performance
Emulsification in beverages Coating of an oil droplet by the high molecular
weight fraction rich in protein (AGP).
Direct correlation between the proportion
and molecular weight of the AGP and the
emulsification performance and stability due the
elasticity of film formed at the interface. Heat
induced hydrophobic associations in the solid
state result in the highest performance due to
increasing the proportion of the AGP. This is the
basis of enhanced gums commercially available
under the trade name Supergum™.
Confectionery Preventing sugar crystallisation and emulsifying
fat to ensure even distribution throughout the
product. Long- term emulsion stability is not
required particularly for products with high
sugar and low moisture contents such as jujubes,
pastilles, caramel and toffees.
Thickening properties (viscosity) and film
forming are required as a glaze in candy products.
Binding agent for the paste base.
Encapsulation of essential Forming a protective film to avoid penetration of
oils; aromatic compositions, oxidising agents, and allowing controlled release.
plant essences. Need for increased wetability and good viscosity
Oleoresin spices, control. Typically, A. seyal is used since it has
fruit juices, vitamins, lower viscosity and can sufficiently provide short-
polyunsaturated fatty term emulsion stability prior to spray drying.
acids, enzymes, acids, trace Higher concentration of gum can also be used to
elements, mineral oils, provide a matrix as well as encapsulation.
pesticides
Bakery for toppings and Free flowing, adhesion properties, control the
glazes water absorption and to impart smoothness.
Texture and flavour Interact and bind water, to thicken as a gel. Gel
modification in formation with enhanced water absorption. High
confectionery proportion of AGP.
Foam stabilisation - “Lace curtain” effect on beer. Maximise content
structure forming of high molecular weight component rich in
protein which responsible for producing the
foams. Other products include marsh mallows
and whipping creams.
Wine Emulsifier and stabiliser for colour particularly
in red wine by forming a protective film layer
to prevent precipitation; reduce perception of
acidity and tannin harshness; provide sensory
impacts that include nose, palate and mouth
feel modifications. Best performance achieved
with high proportion of AGP to give long-term
emulsion stability.
Dietary fibre Dairy products, processed fruits, bakery items,
frozen desserts, meat products and food for
diabetics. Need ability to fermentation in colon to
give short-chain fatty acids, with bulking ability.
A. seyal is typically used due to its low viscosity
compared to A. senegal.
Table 1. Summary of gum arabic applications in various food products.
19
HYDROCOLLOIDS
soluble. The solubility depends on
the degree of substitution (DS) and it
could be up to 3 (maximum number
of possible sites), but it is generally
in the range 0.6- 0.95 derivatives
per monomer unit. Not only is the
degree of substitution important but
also the distribution along the chain
(uniformity or otherwise called the
degree of blockiness). More uniform
distribution yields smoother and
less thixotropic solutions (1). The
properties of CMC are also affected
by the degree of polymerisation
(Mw). High Mw preparations have
high viscosity and film forming
properties compared to low Mw.
Therefore, combination of the
above factors yields a wide variety of
products. Additionally, the physical
characteristics such as the particle size
and shape can be varied over a broad
range to produce a vast number of
special types of grades which are
termed cellulose gums. In food, CMC
is used to inhibit syneresis, repress the
formation of sugar crystals, improve
body, contribute gelling properties
and improve surface glaze. In baking,
for example, CMC is effective in
increasing loaf volume and improving
quality.
Hyaluronan
Hyaluronan is an example of animal
source and is type AB polymer. It is
made up of repeating disaccharide
units of β-(1-4)-D-glucuronic acid
and β-(1-3) N-acetyl D-glucosamine.
It is found naturally in vitreous
humour synovial fluid and umbilical
cord and in many animal tissues in
smaller concentrations. Hyaluronan
can also be produced from certain
strains of Streptococcus bacteria
by fermentation, extraction and
subsequent purification from the
broth. This hydrocolloid traditionally
has been used in a wide variety
of areas such as joint diseases
supplement, eye surgery, ear surgery,
tear substitution, wound healing,
skin care, as a component of artificial
matrices and in bioengineering for
tissue scaffolding. Recent advances
have resulted in reducing the cost of
production significantly, which made
it possible to produce food grade
preparations. In solution, it adopts
20 FS&T VOL 23. ISSUE 3
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a random coil conformation and has
unique rheological properties resulting
from its large molecular volume
and from extensive interaction and
entanglement of the molecular coils.
Pectin
Pectin is widely used in the food
industry as an emulsifier, stabiliser
and a gelling agent. It is extracted
from plant cell walls such as those of
citrus, tomato, sugar beet and apple.
Pectin is composed of (1-4) linked
α-D-galacturonic acid residues in
either the free acid (salt) or methyl
ester form. This homogalacturonan
region is referred to as the ‘smooth
region’. The homogalacturonan
backbone is occasionally interrupted
by α-(1–2)-linked α-L-rhamnopyranose
residues, referred to as the ‘hairy
region’. Neutral sugar side chains are
connected through O-4 or O-3 to the
rhamnose units. Pectins are frequently
classified in two categories, namely,
the high methoxyl pectins with a
degree of methylation DM > 50% and
the low methoxyl pectins with DM <
50%. Low methoxyl (LM) pectin gels
form as a result of interactions with
calcium over a wide range of soluble
solids and pH values. On the other
hand, high methoxyl (HM) pectin
forms gels at low pH (pH 3.5) and in
the presence of sugar. The principle
use of pectin to date has been in the
making of jams and jellies. However,
it has more recently been employed as
a stabiliser in juice beverages and acid
dairy drinks.
References
1. Clicksman, M. (1969). Gum
Technology in the Food Industry,
Academic Press, Inc.
2. Islam, A, M. et al., (1997). A review
of recent developments on the
regulatory, structural and functional
aspects of gum arabic. Food
Hydrocolloids, 11, 493-505.
3. Williams, P. A. and Phillips,
G. O. (2006). Physicochemical
characterisation of gum arabic
arabinogalactan protein complex.
Food and Food Ingredients Journal of
Japan. 211,181-188.
4. Randall, R. C. et al., (1989).
Fractionation and characterisation
of gum from Acacia senegal. Food
Stay ahead with the latest
Hydrocolloids, 3, 65-75.
innovative meat research from Custom Alerts
5. Fincher, G. B. et al., (1983). cover:
Arabinogalactan-Proteins - structure,
biosynthesis, and function. Ann. Rev. JOURNAL
Plant Phys., 34, 47-70. ARTICLES,
6. Al-Assaf S. et al., (2009). Molecular
associations in acacia gums. Struct.
FSTA Custom Alerts are uniquely tailored, electronic For your FREE TRIAL PATENTS,
Chem., 20 (7), 325-336. alerts from the FSTA – Food Science and Technology of MEAT * Custom Alerts™
7. Randall, R. C. et al., (1988). The role Abstracts ® database sent directly to your and more information on STANDARDS,
of the proteinaceous component on desktop, saving you the time-consuming the service, go to: BOOKS,
the emulsifying properties of gum
arabic. Food Hydrocolloids, 2, 131-140. task of searching multiple websites and www.fstadirect.com/meat
REVIEWS,
8. Elmanan, M, et al., (2008). Studies journals to find information.
on Acacia exudate gums: Part VI. CONFERENCE
Interfacial rheology of Acacia senegal PROCEEDINGS,
and Acacia seyal. Food Hydrocolloids,
22, 682-689. REPORTS
9. Al-Assaf S. et al., (2007).
Characterisation and properties of and much
Acacia senegal (L.) Willd. var. senegal more …
with enhanced properties (Acacia
(sen) SUPER GUM (TM)): Part 1.
Food Hydrocolloids, 21, 319-328.
10. Al-Assaf S. et al., (2003). Quality File: 164569-9-9FST ILS
Ad size: A4 1/2L (185mm wide x 130mm high)
control of gum arabic. Food and Food * We have records available in all areas of food science, food technology and nutrition, so please contact us for more information on your area of interest at ifis@ifis.org
Ingredients Journal of Japan, 208, 771-
780.
11. Morris, V. J. (2006). Bacterial
polysaccharides. In: Food
Polysaccharides and their Applications
(Vol. A). (eds M. Stephen, G. O.
Phillips and P. A.Williams). 2nd
Edition, Taylor & Francis, London.
413-454.
12. Al-Assaf S. et al., (2006).
Controlling the molecular structure
of food hydrocolloids. Food
Hydrocolloids, 20, 369-377.
A full list of the references used in
compiling this paper is available
from the author*.
Dr Saphwan Al-Assaf* is a Reader in
Hydrocolloids Chemistry and Director of
the Phillips Hydrocolloids Research Centre,
Glyndwr University (formerly NEWI),
Mold Road, Plas Coch Campus, Wrexham
LL11 2AW, UK.
Professor Glyn O. Phillips is the Chairman
of Phillips Hydrocolloid Research Ltd, 45
Old Bond Street, London W1S 4AQ.
*Corresponding author.
Tel: +44 (0)1978 293321
Email: s.alassaf@glyndwr.ac.uk
Web: www.newi.ac.uk.
164569-9-9FST ILS.indd 1 10/8/09 10:51:52