Food Hydrocolloids xxx (2017) 1e13

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Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Hydrocolloids acting as emulsifying agents e How do they do it?

Eric Dickinson
School of Food Science and Nutrition, University of Leeds, Leeds, LS2 9JT, UK

a r t i c l e i n f o a b s t r a c t

Article history: We consider the essential compositional and molecular structural features controlling the formation and
Received 11 December 2016 stabilization of oil-in-water emulsions by hydrocolloid ingredients. The theoretical principles underlying
Received in revised form adsorption of polymers and steric stabilization by polymer layers are outlined with particular reference
12 January 2017
to copolymer morphology and chain branching. These basic concepts are used to interpret at the mo-
Accepted 19 January 2017
lecular level the experimental interfacial functionality of three classes of biopolymer emulsifying agents:
Available online xxx
gum arabic, pectin, and hydrophobically modified starch (OSA starch). Some inferences are made con-
cerning the mechanistic significance of certain generic features in relation to the surface activity and
Keywords:
Polysaccharide
emulsification characteristics of hydrocolloids d the presence of covalently bound protein, the diversity
Emulsifying agent of carbohydrate polymer structure, and the heterogeneity of natural ingredients.
Steric stabilization © 2017 Elsevier Ltd. All rights reserved.
OSA starch
Acacia gum
Sugar beet pectin

Foreword
This author's personal journey to try to understand hydrocolloid
functionality in food emulsions was to a great extent inspired by
the influential research on gum arabic (Acacia senegal) carried out
by Professor Glyn Phillips and his collaborators. The intellectual
challenges offered to me by this subject area were further sustained
through the stimulating discussions that took place every couple of
years at the Gums and Stabilisers Conferences in Wrexham. Surely
one of Glyn's great strengths is his ability to bring together active
scientists and industrialists in a congenial atmosphere of collabo-
ration and discovery. Especially memorable for me in the context of
the present article are two noteworthy scientific events: a work-
shop session on Emulsion Stabilization during the 4th Gums and
Stabilisers Conference (Phillips, Wedlock & Williams, 1988), and,
some 20 years later, an International Forum on Natural Hydrocol-
loid Emulsifiers, also in Wales, organized by Phillips Hydrocolloids
Research in conjunction with the Japanese ingredient company
San-Ei Gen F.F.I. Inc. (Phillips, 2008b). For observers of his bound-
less enthusiasm and commitment to this field over the past 40
years, both before and after his formal retirement from NEWI, it is
difficult to overstate Glyn's contribution to the promotion and
development of our global hydrocolloid research community. Un-
der his compelling spell of Welsh charm and a warm generosity of
E-mail address: E.Dickinson@leeds.ac.uk.
spirit, this researcher d like many others d has been enticed and
welcomed into the extended hydrocolloid research family. So it is a
personal privilege and pleasure for me to dedicate this article to
Professor Phillips on the occasion of his 90th birthday.
1. Introduction
Hydrocolloids are widely employed in the food industry as
functional ingredients for preparing and stabilizing oil-in-water
emulsions. In fact, as judged by the technical literature that
commonly accompanies the supply of commercial food ingredients,
it would appear that almost any available hydrocolloid can provide
protection against emulsion breakdown; but clearly some are more
effective than others. Over the 30-year lifetime of the journal Food
Hydrocolloids there have been numerous published reports on the
functionality of natural gums and individual biopolymers in
emulsified systems. And various authors of these studies have
typically offered some kind of intuitive interpretation of this
functionality in mechanistic terms. Over this same timescale, there
have been regular reports of studies aiming to compare the per-
formance of different hydrocolloid ingredients, and the ongoing
value of these comparative studies has been steadily enhanced by
the development of reliable experimental methodologies for the
quantitative characterization of emulsion stability (McClements,
2005, 2007). On the assumption that useful progress has been
made over this period, one may reasonably ask a couple of related
questions. Firstly, what is the current scientific consensus regarding

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2 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13
the underlying mechanistic basis of this type of hydrocolloid
functionality? And, secondly, how can one explain the evident
differences in emulsification performance between hydrocolloids
of different chemical structure and biological origin?
A clue to the intrinsic functional identity of the hydrocolloid is,
of course, to be found in the name itself d a hydrophilic (poly-
meric) material with colloid-like character. That is, the hydrocolloid
is a highly water-soluble (or water-dispersible) material that
readily dissolves (or disperses) to form highly hydrated entities of
colloidal (nanoscale) dimensions. Each dissolved polymer molecule
of a hydrocolloid ingredient is deemed to interact strongly via
hydrogen bonding with its surrounding water molecules (and also
with any neighbouring hydrocolloid molecules). Due to the ten-
dency of these large hydrophilic macromolecules to overlap and
join together into entangled networks and macroscopic gels, most
food hydrocolloids have the capability to function as viscosity
modifiers and thickeners in aqueous media at relatively low con-
centrations. This universal behaviour allows these hydrocolloid
ingredients to make a significant contribution to the provision of
long-term stability to aqueous suspensions of solid particles or oil-
in-water emulsions. In particular, the generation of a hydrocolloid-
containing medium with a very high viscosity at a limiting low
applied shear stress facilitates effective immobilization of dispersed
oil droplets, thereby inhibiting gravity-induced creaming and any
accompanying serum separation during extended emulsion stor-
age. Xanthan gum, for instance, is especially effective in providing
stabilization by means of such rheological control (Dickinson, 2004,
2009b). Furthermore, this same non-adsorbing hydrocolloid poly-
mer is also a common participant in the closely related phenomena
of phase separation and depletion flocculation, with further
important implications for emulsion serum separation and gravity
induced creaming instability (Dickinson, Ma, & Povey, 1994;
Moschakis, Murray, & Dickinson, 2006).
To be effective as an emulsifying agent, the hydrocolloid ingre-
dient should possess some surface activity. That is, it should have
the capacity to lower the interfacial tension at the oilewater
interface; and this tension lowering should occur over a timescale
that is relevant to the process of emulsion preparation. In other
words, the rate of polymer adsorption at the freshly formed oile-
water interface, and the associated rate of development of the
transient adsorbed layer during emulsification, should exceed the
rate of dropletedroplet collisions caused by the hydrodynamic
forces of laminar and turbulent flow (Walstra & Smulders, 1998;
Walstra, 2003). In molecular terms, this means that the predomi-
nantly hydrophilic macromolecules of the hydrocolloid ingredient
should contain a sufficient proportion of accessible hydrophobic
groups to enable them to stick to and spread out at the interface,
thereby stabilizing the freshly formed emulsion droplets against
immediate recoalescence. A further practical consideration is that
the emulsifying agent should not be prone to strong aggregation or
gelation; otherwise the resulting high viscosity of the aqueous
phase will inhibit the disruption of the dispersed oil phase into
sufficiently small droplets. In practice, these criteria are fully
satisfied by only a small number of hydrocolloid ingredients.
Consequently, even though essentially all polysaccharide thick-
eners and gelling agents can contribute usefully to the long-term
stability of emulsions after preparation, only a limited number of
hydrocolloids are suitable as primary emulsifying agents.
The origin of the surface activity of certain hydrocolloids has
previously been attributed to specific molecular features
(Dickinson, 1988, 2003, 2009a). The only food protein that can
properly be described as a hydrocolloid d namely, gelatin d has
been found to demonstrate significant surface activity and useful
emulsifying properties under favourable conditions (Dickinson &
Please cite this article in press as: Dickinson, E., Hydrocolloids acting as emulsifying agents e How do they do it?, Food Hydrocolloids (2017),
http://dx.doi.org/10.1016/j.foodhyd.2017.01.025
Lopez, 2001). For this uniquely hydrophilic food protein, the sur-
face activity is nevertheless attributable to the intrinsic hydro-
phobicity of a small proportion of its amino-acid residues. Some
food polysaccharides appear inherently surface-active due to the
presence of short hydrophobic side-chains such as methyl and
acetyl groups. Other carbohydrate polymers contain a small
amount of proteinaceous material that is firmly linked to the
polysaccharide by covalent bonding or physical complexation. It is
supposed that these specific molecular structural features enable
natural ingredients such as gum arabic (Acacia senegal) and certain
kinds of pectin to function as highly effective emulsifying agents. In
addition, ingredient suppliers have introduced various kinds of
hydrophobic chemical modifications into starch and cellulose
polymers in order to prepare ‘green’ biopolymer-based surface-
active polymers having favourable emulsification properties. For
the cases of both the natural and the chemically modified bio-
polymers, this article will assess how the work of some researchers
has recently contributed to our improved understanding of their
interfacial hydrocolloid structureefunction relationships.
Once an oil-in-water emulsion has been prepared, the main
function of the hydrocolloid emulsifier is to act as a steric stabi-
lizing agent to protect the dispersed droplets against aggregation
and coalescence during subsequent processing and storage
(Dickinson, 1992; McClements, 2005, 2009). There are three main
requirements for effective steric stabilization by interfacial poly-
mers: complete surface coverage, strong adsorption, and the exis-
tence of a thick adsorbed layer. In the first place, there should be
sufficient hydrocolloid present during emulsification to fully cover
the newly formed oilewater interface. Secondly, the stabilizing
polymer molecules should remain effectively attached to the
interface over the life-time of the emulsion system. And, thirdly, the
adsorbed layer should contain some bulky hydrated polymer
chains that can extend well into the aqueous medium. In combi-
nation with steric stabilization, the coexistence of a fraction of non-
adsorbed polymeric material can make an additional contribution
to colloid stability through the depletion stabilization mechanism
(Semenov & Shvets, 2015). Furthermore, the presence of charged
groups on some hydrocolloid molecules provides the source of a
supplementary electrostatic contribution to the stabilization
mechanism, especially under conditions of low ionic strength
(Dickinson, 1992; McClements, 2005; Semenova & Dickinson,
2010).
To understand why one particular hydrocolloid ingredient
might possess superior emulsifying properties to another we must
first have reliable knowledge of the chemical identity and distri-
bution of the hydrophobic groups along the carbohydrate polymer
chain. In addition, we need to have an appreciation of how the
molecular architecture of the hydrocolloid affects the interfacial
structure of the adsorbed polymer layer. Finally, we need to
establish how the adsorbed layer structure influences the interac-
tion forces between individual hydrocolloid-coated droplets and
hence the overall colloidal stability of the emulsion system. This
article represents an attempt to assess how close we are to reaching
such a state of fundamental understanding for some of the main
classes of hydrocolloid emulsifying agents. Attention is directed
here towards the behaviour of soluble hydrocolloid ingredients that
exist as individual molecular species in aqueous media. The inter-
ested reader is invited to look elsewhere for information on the
emulsion-stabilizing properties of two important varieties of par-
ticulate biopolymer ingredients d polysaccharide-based solid
particles and hydrocolloid microgels (Dickinson, 2013, 2015a,
2016a,b; Berton-Carabin & Schroe €n, 2015; Lam, Velikov, & Velev,
2014; Rayner et al., 2014; Tavernier, Wijaya, van der Meeren,
Dewettinck, & Patel, 2016).
 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13 3

The rest of the article is organized as follows. We consider basic

generic principles describing the theory of interfacial stabilization
by model polymers with different sorts of molecular architecture.
Following on from this theoretical overview comes an analysis of
the relevance and applicability of these basic physico-chemical
principles to the known molecular structures and colloid stabiliz-
ing properties of three different hydrocolloid ingredients. The au-
thor's overall objective is to try to illuminate an underlying essence
of physical understanding whilst cautiously recognizing the di-
versity and molecular complexity of the individual systems
involved.

2. Adsorbed polymer layers and colloid stability

Our general understanding of polymer adsorption in relation to

colloid stability has been mainly derived from statistical thermo-
dynamic models of lattice chains adsorbing at solid impenetrable
surfaces. In particular, useful results for specific polymer models
have been generated numerically from the ScheutjenseFleer self-
consistent-field theory (Fleer, 2010; Fleer, Cohen Stuart,
Scheutjens, Cosgrove, & Vincent, 1993; Scheutjens & Fleer, 1985)
and by Monte Carlo simulation (Dickinson & Euston, 1992;
Dickinson & Lal, 1980). Where direct comparisons have been
made between these two alternative approaches, the reported level
of agreement is generally very satisfactory (Chen, Liu, & Hu, 2001;
Sun, Peng, Liu, Hu, & Jiang, 2007). In this article we shall assume the
validity of the commonly accepted view that “the ScheutjenseFleer
theory provides a useful framework for discussing the relative
interaction effects of food biopolymers” (Lips, Campbell, & Pelan,
1991). We also recognize, however, that such a simple statistical
approach is somewhat idealized in relation to the complexity of
food hydrocolloids. For instance, the theory typically assumes that
polymers are composed of flexible linear polymer chains, whereas
the polysaccharide backbone of a hydrocolloid is fairly stiff and is
commonly decorated with side-chains of variable length and
chemical complexity. In addition, polymer adsorption at an oile-
water interface is obviously not the same as polymer adsorption at
an impenetrable solid surface. Despite such differences, however,
there is a reasonably widespread consensus of opinion, supported
by extensive experimental evidence on well-defined synthetic
polymer systems, that the simplified statistical models do provide a
sound mechanistic basis for describing the essential features of
adsorption and colloidal stabilization by all sorts of macromole-
cules, including food biopolymers.
A key message from the statistical models is that steric stabili-
zation is most effectively achieved through the adsorption of co-
polymers. As illustrated schematically in Fig. 1(a), an adsorbing
copolymer molecule combines two key features: anchoring groups Fig. 1. Schematic representations of different kinds of polymer chains in the vicinity of
that stick directly to the surface, and chain regions that extend a planar solid surface: (a) random copolymer; (b) homopolymer (strong adsorption);
away from the surface. The hydrophobic anchoring groups have a (c) homopolymer (weak adsorption); (d) diblock copolymer; (e) triblock copolymer; (f)
branched copolymer. Non-adsorbing (hydrophilic) chain regions are denoted by thin
strong affinity for the ‘oil-like’ surface and a low affinity for the bulk
grey lines; adsorbing (hydrophobic) regions are denoted by thick black lines.
aqueous phase; and vice versa for the extended hydrophilic chains.
Repulsion between two closely approaching surfaces arises from
the entropically unfavourable overlap and compression of their hydrocolloid polymers due to their typically large molecular vol-
copolymer-coated adsorbed layers. Overlap of layers on different umes. Another important thermodynamic condition for effective
surfaces is unfavourable thermodynamically because it produces a stability is that the bulk aqueous phase should be a ‘good’ solvent
local osmotic pressure gradient from the mixing of chains in the for the hydrophilic dangling chains. Any shift in the value of an
overlap zone. Polymer layer compression is also entropically intensive variable like pH and temperature, which results in a
unfavourable because it restricts the volume available to each lowering of the effective solvent quality, is likely to be detrimental
chain, thereby causing a statistical bias away from the (most- to the ability of the adsorbed copolymer to inhibit flocculation.
probable) equilibrium configurations. Experience in the laboratory Homopolymers d that is, polymers which contain segments
has shown that, for an adsorbed layer to provide effective steric that are identical (or chemically very similar) d are not so effective
stabilization and thus prevent flocculation of copolymer-coated as steric stabilizers. This is because they cannot form adsorbed
droplets, it should be at least several nanometres thick. This sort layers of the requisite thickness and structural coherence. Suppose
of adsorbed monolayer thickness is readily achieved with most that all segments of a homopolymer have a strong tendency to stick

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4 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13

to the surface: this would mean that the configuration produced on bridging interaction between the approaching surfaces is essen-
adsorption at low polymer concentration would be essentially flat, tially negligible.
as shown in Fig. 1(b). In a system with a high concentration of such Let us now consider in more detail how polymer chain archi-
adsorbing homopolymers, there would be a strong tendency to- tecture influences the steric stabilizing ability of a predominantly
wards bulk-phase aggregation and precipitation; and many of the hydrophilic copolymer. For this purpose we refer to numerical re-
polymers would inevitably become stuck to two (or more) droplet sults produced using the ScheutjenseFleer self-consistent-field
surfaces, causing bridging flocculation. Conversely, let us suppose theory for multi-block copolymers with and without side-chains
that the homopolymer consists of segments that are rather hy- (Ettelaie, Murray, & James, 2003). The authors’ basic model as-
drophilic: there would then be good solubility in the aqueous sumes a multi-block linear chain of 512 segments with the generic
medium, but the molecules would only have a weak tendency to chemical formula (AnBn)x (x ¼ 256/n). The type-A segments are
stick to the surface, producing an ill-defined polymer-decorated assumed to be weakly adsorbing, and their attractive interaction
interface with no more than partial surface coverage (see Fig. 1(c)). with the surface is characterized by an arbitrary low value of the
Such a transient and structurally incoherent adsorbed layer lacks FloryeHuggins adsorption energy, i.e. cAs ¼ e1 kT, where kT is the
the capability to confer effective stability to closely approaching thermal energy. This value of cAs is considered to be approximately
droplet surfaces. representative of the attractive energy associated with a single
There are many kinds of copolymers. A random copolymer like small hydrophobic residue. The hydrophilic type-B segments are
that illustrated schematically in Fig. 1(a) has several separate re- taken to be completely non-adsorbing (cBs ¼ 0). The calculated
gions available for anchoring to the surface. Computer simulation steric interaction energy Usteric between two flat plates immersed
has shown that the adsorbed layer structure formed from such a in a 0.1% solution of this multi-block copolymer is shown Fig. 2(a).
multi-block copolymer is influenced by the proportion of sticky The four separate curves of Usteric versus distance d correspond to
segments within the molecule, and also by the arrangement of the
‘stickers’ along the chain (Balazs, Gempe, & Lantman, 1991; Sun,
Peng, Liu, & Hu, 2007). Some real macromolecules can be
adequately described using a polymer chain model having only one
or two sticky anchoring regions. An adsorbed molecule of the
diblock copolymer AeB (with just one sticky type-A region) pref-
erentially adopts the simple trainetail configuration (see Fig. 1(d)).
Under good solvent conditions (for the type-B segments), the
resulting interaction for a pair of closely approaching AeB
copolymer-coated surfaces is purely repulsive. This is highly
favourable for effective steric stabilization. A food biopolymer that
is well approximated by the simple diblock copolymer model is the
milk protein b-casein; in contrast, another milk protein as1-casein
is more successfully modelled as a triblock copolymer (Dickinson,
1998, 2016a; Dickinson, Pinfield, Horne, & Leermakers, 1997). The
adsorption of a triblock copolymer AeBeA (containing two sticky
type-A regions) leads to the traineloopetrain configuration (see
Fig. 1(e)). While repulsion between AeBeA copolymer-coated
surfaces also confers steric stabilization, the resulting colloidal
interaction in this case may become net attractive under certain
conditions (Wijmans, Leermakers, & Fleer, 1994). For a triblock
copolymer with two type-A blocks that are both highly sticky, an
effective surfaceesurface attraction arises from the entropy gain
associated with the configurational change from a single loop on a
single surface to a polymer bridge between two surfaces. Macro-
molecules containing numerous anchoring regions often behave
like simple triblock copolymers. According to the self-consistent-
field calculations of Wijmans et al. (1994), the adsorption of a
simple triblock copolymer AeBeA is qualitatively similar to the
adsorption of a multi-block copolymer containing long blocks,
(AeB)neA (n > 1).
Our discussion so far has concerned linear polymers. But we
know that many carbohydrate polymers possess side-chains, and
that some are composed of long multi-branched chains. The typical
configuration for a branched block copolymer adsorbed on a solid
surface is illustrated schematically in Fig. 1(f). Even though the
branched copolymer may contain just a small proportion of sticky
hydrophobic groups, it can function as a highly effective steric
stabilizer so long as the potential anchoring region is readily Fig. 2. Calculated steric potentials for 0.1% solutions of multiblock copolymers be-
accessible to the surface and can bind sufficiently tightly to cause tween flat plates. The interaction energy Usteric (arbitrary units) is plotted against
permanent copolymer attachment. A high density of dangling hy- distance d between the surfaces (units of monomer lattice size). (a) Linear copolymer
drophilic chains in the gap between two approaching copolymer- (AnBn)x of 512 segments with variable block size: (A) n ¼ 4, (B) n ¼ 8, (C) n ¼ 16, (D)
n ¼ 32. (b) Symmetrical copolymer composed of main multiblock chain of 255 units
coated surfaces produces a strongly repulsive interaction poten- and side-chain of variable size: m ¼ 3 (short dash), m ¼ 15 (dot), m ¼ 31 (solid line),
tial. With just a small part of each copolymer involved in direct m ¼ 47 (dot-dash), m ¼ 63 (long dash). Reproduced with permission from Ettelaie et al.
attachment to the surface, the likelihood of an unfavourable (2003).

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 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13
differing block sizes (n ¼ 4, 8, 16 and 32). The shape of each plotted
curve Usteric(d) is primarily determined by the changing fractions of
the weakly adsorbing type-A anchoring blocks as the two surfaces
come close together (Ettelaie et al., 2003). We can observe that each
curve in Fig. 2(a) has an energy minimum at some separation; as
the block size increases, the depth of the minimum is reduced, and
it moves to larger separations. In terms of the stability behaviour of
bulk colloidal systems with surfaces coated with these same co-
polymers, as the block size increases one could infer a reduced
tendency towards flocculation and hence a greater effectiveness of
the copolymer as a steric stabilizing agent.
How does the addition of a hydrophilic side-chain affect the
form of the steric interaction potential Usteric(d)? To address this
question, Ettelaie et al. (2003) considered a symmetrical model
copolymer of formula (A4B4)15(A4B3)B(B3A4)(B4A4)15 with a hy-
drophilic side-chain Bm attached to the central type-B segment of
its 255-segment multi-block backbone. The hydrophobic type-A
segments are again taken as weakly adsorbing (cAs ¼ e1 kT), and
the type-B segments as non-adsorbing (cBs ¼ 0). The five curves
plotted in Fig. 2(b) correspond to varying side-chain lengths as
defined by m ¼ 3, 15, 31, 47 and 63 (Ettelaie et al., 2003). For the
case of copolymers with short single side-chains, there is a mini-
mum in Usteric(d) at separation distance d ~ 3 (measured in lattice
units). This would imply a tendency towards incipient flocculation
of the corresponding colloidal system, as previously described for
small-block copolymers with no side-chains (Fig. 2(a)). The depth
of this minimum in Usteric(d) diminishes as m increases. And for a
long single side-chain the pair potential becomes entirely positive,
implying a purely repulsive steric force between the polymer-
coated surfaces. The results of these calculations show how a
long hydrophilic side-chain is highly favourable towards steric
stabilization by an adsorbed multi-block copolymer even when the
molecule's multi-block backbone sequence would otherwise imply
flocculating conditions. On the basis of these and related compu-
tational results, one could reasonably believe that the presence of
several extended side-chains on a single adsorbed polymer mole-
cule would be especially advantageous for copolymer steric stabi-
lizing functionality. This is the situation illustrated schematically in
Fig. 1(f).
3. Emulsifying properties of three hydrocolloid ingredients
3.1. Hydrophobically modified starch
For more than half a century, starch modified with octenyl
succinic anhydride (OSA) has been used industrially as a food ad-
ditive for emulsification, stabilization and encapsulation
(Sweedman, Tizzotti, Scha €fer, & Gilbert, 2013). The formation of
OSA starch involves the esterification reaction between a dicar-
boxylic acid anhydride and a small fraction of the hydroxyl groups
on carbons 2, 3 and 6 of the glucose units of the carbohydrate
polymer chain. A numerical parameter routinely used to define the
material chemically is the degree of substitution (DS), i.e. the
average number of octenyl succinate derivatives per glucose unit.
Processing conditions that affect the degree of substitution include
factors such as pH, reaction time/temperature, and starch concen-
tration (Liu et al., 2008). The structural and functional character-
istics of OSA starch are further influenced by natural variations in
polymeric chain length and amylose/amylopectin ratio, as deter-
mined by the botanical source of the parent starch (He, Song, Ruan,
& Chen, 2006; Song, Zhao, Li, Fu, & Dong, 2013; Sweedman, Hasjim,
Sch€afer, & Gilbert, 2014) and the plant's growing conditions (Alvani,
Qi, Tester, & Snape, 2011). Commercially available samples of OSA
starch, with typical DS values in the range 0.01e0.03, are commonly
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5
based on corn or maize starch, especially the waxy maize variety
(Sweedman et al., 2013).
The impressive emulsifying behaviour of OSA starch derived
from potato and barley sources was demonstrated by Nilsson and
Bergenståhl (2006, 2007). Depending on the hydrodynamic con-
ditions during emulsification, and also on the individual ingredient
properties (DS value, molar mass), it was found that the adsorbed
amount at the emulsion droplet surface could be rather wide
ranging (from 1 to 2 mg m2 to >10 mg m2). These OSA starch
samples were demonstrated to be surface-active at the macro-
scopic triglycerideewater interface, although the reported values of
interfacial pressure (at a solution concentration of 100 mg l1) were
rather modest (just 2e3 mN m1) (Nilsson & Bergenståhl, 2007).
Higher interfacial pressures at the tolueneewater interface (up to
~10 mN m1) have been reported by Prochaska, Kedziora, Le Thanh,
and Lewandowicz (2007) for solutions of OSA potato starch
(DS ¼ 0.01).
Despite having the capability to lower the interfacial tension
further than other kinds of chemically modified starches, the
overall efficiency of adsorption of OSA starch is still relatively poor
(Prochaska et al., 2007). The adsorption efficiency is defined as the
minimum bulk phase concentration required to form a saturated
interface. Although OSA starch can adsorb at the oilewater inter-
face to produce a densely packed surface layer, the complete
saturation of the interface requires the presence of a high hydro-
colloid concentration in the bulk aqueous phase. That is to say, for
the same total interfacial area created, the required emulsifier/oil
ratio has to be substantially higher than that required with, for
instance, a small-molecule surfactant or a food protein. However,
once the state of full surface saturation has been reached, the
droplets coated with OSA starch remain highly stable with respect
to flocculation and coalescence. In comparison with an emulsion
stabilized electrostatically by a monolayer of globular protein (e.g.
following emulsification with whey protein isolate), steric stabili-
zation by a thick OSA starch layer produces an oil-in-water emul-
sion that is more resilient to changes in key environmental
conditions such as temperature, pH and ionic strength (Chanamai &
McClements, 2002; Charoen et al., 2011; Mao, Yang, Xu, Yuan, &
Gao, 2010; Qian, Decker, Xiao, & McClements, 2011; Tesch,
Gerhards, & Schubert, 2002).
Native starch is a branched polydisperse homopolymer of
glucose having limited water solubility. Two kinds of poly-
saccharides are involved: amylose, a polymer of moderately high
molecular weight (~106 Da) containing just a few long branches,
and amylopectin, a more rigid macromolecule of very high mo-
lecular weight (107e108 Da) with numerous short branches (Mua &
Jackson, 1997). The number of glycoside residues in native starch
polymer molecules can therefore range from several hundred
(amylose) to many tens of thousands (amylopectin). However, the
degree of polymerization in OSA starch is typically lower than that
in the original native starch: the high-molecular-weight fraction of
some OSA starch samples is degraded during processing by enzy-
matic or acid hydrolysis treatments (Hong, Li, Gu, Wang, & Pang,
2016; Li et al., 2014; Tizzotti, Sweedman, Schaefer, & Gilbert,
2013), and there is also mechanically-induced polymer chain
disruption during emulsification (Nilsson, Leeman, Wahlund, &
Bergenståhl, 2006). As most of the available commercial samples
of OSA starch are based on botanical sources containing a high
proportion of amylopectin, it would appear from empirical expe-
rience that amylopectin is the main component responsible for the
ingredient's interfacial functionality. In the turbulent flow of the
high-pressure homogenizer, there is rapid convective mass trans-
port of these big molecules to the newly created oilewater interface
(Nilsson, Leeman, Wahlund, & Bergenståhl, 2007). And once a
saturated interfacial layer of OSA starch has been formed, three key
6 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13
structural attributes of the amylopectin molecule all contribute to
its steric stabilization effectiveness d its large molecular size, its
high backbone rigidity, and its extensive chain branching (Dokic,
Dokic, Dapcevic, & Krstonosic, 2008; Sweedman et al., 2013).
The role of chain branching in relation to the stabilizing
behaviour of hydrophobically modified starch has been recently
analysed using the ScheutjenseFleer self-consistent-field theory
(Ettelaie, Holmes, Chen, & Farshchi, 2016). The authors have
compared the behaviour of two disordered polysaccharide models
each containing 1890 saccharide units: a linear amylose-like poly-
mer and branched amylopectin-like model. Whereas the amylose-
like polymer is assumed to be a flexible linear chain, the hypo-
thetical amylopectin-like polymer has 31 branch points with a
degree of polymerization of 30 units between the branch points.
Both these look-alike OSA starch polymers are assumed to have the
same degree of substitution (DS ¼ 0.033), each having exactly 63
hydrophobic groups per chain. The adsorption energy of an OSA
side-chain group is set at cAs ¼ e12 kT, corresponding to 1.5 kT for
every CH2 group in the side-chain. All other non-modified
saccharide units, including branch points, are taken to be non-
adsorbing (cBs ¼ 0).
Calculated pair potentials for adsorbed layers of these amylose-
like or amylopectin-like polymers of identical molecular weight are
displayed in Fig. 3. The estimated energy of interaction between the
surfaces of a pair of micron-sized oil droplets coated with one or
other of the two model polymers is plotted against separation
distance. This calculation of the colloidal interaction energy by
Ettelaie et al. (2016) takes account of the attractive van der Waals
interaction between the droplets as well as the self-consistent-field
contribution from the overlap of the adsorbed polymer layers.
Predicted pair potentials for both model polymers are consistent
with a quasi-equilibrium state of colloidal stability: that is, there is
strong repulsion between the polymer-coated surfaces for separa-
tion distances less than ~10 nm. With oil droplets of this size, the
predicted shallow minima (~2 kT) at larger separations
(15e25 nm) are considered to be small enough to be readily
overcome by Brownian motion or weak applied shear forces. For
these two idealized OSA starch polymers of identical molecular
weight and the same DS value, Fig. 3 indicates that the adsorbed
layer formed by the linear polymer (amylose) is of longer range and
Fig. 3. Comparison of colloidal interactions induced by the adsorption of linear and
branched OSA-starch polymers of the same molecular weight (~105 Da) and degree of
substitution (DS ~ 0.03). The calculated interaction potential between a pair of oil
droplets (diameter 1 mm) is plotted against surface-to-surface separation. Mediated
interactions are calculated for a dilute bulk solution of amylose-like polymer (dashed
line) or amylopectin-like polymer (solid line). Reproduced with permission from
Ettelaie et al. (2016).
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it decays more slowly with separation. However, this notional
advantage of the linear polymer is more than offset by its inferred
propensity to cause bridging flocculation, as indicated by the
presence of an energy minimum for the amylose-like polymer at a
separation of ~6 nm. The bridging feature is absent for the branched
amylopectin-like polymer, whose pair potential is increasingly
strongly repulsive at close separations (Ettelaie et al., 2016). Of
course, for any real OSA starch ingredient, the much greater average
molecular weight of the amylopectin component means that the
bulkier branched polymers will be spatially more dominant at the
interface than the linear polymers. Therefore, in reality, one expects
the repulsive range of the steric interaction of the amylopectin
component of OSA starch to extend out to larger relative separa-
tions than implied by the idealized predictions of Fig. 3. To sum-
marize this theoretical analysis of these look-alike OSA starch
polymers, we can say that it confirms our previously inferred
expectation that the preferred molecular architecture for effective
emulsion stabilization is that of a bulky copolymer with extensive
chain branching.
Like most hydrocolloids, OSA starch is heterogeneous in
composition. The ingredient is polydisperse, not only in terms of its
molecular weight distribution, but also in its extent of chain
branching. This means that, during and after emulsification, there
must be some competition between the various adsorbing species
for occupancy of the oilewater interface, resulting presumably in a
mixed biopolymer interface (Dickinson, 2011). An interesting
observation from the analysis of Ettelaie et al. (2016) is the pre-
diction of an enhancement in effectiveness of steric stabilization as
a consequence of the coexistence of linear and branched polymers
in the adsorbed layer. That is to say, a mixed layer of amylose-like
and amylopectin-like polymers appears capable of generating a
steric interaction of longer repulsive range than is achievable with
either component alone at the same overall bulk concentration. A
somewhat analogous type of interfacial synergism was previously
predicted by Parkinson, Ettelaie, and Dickinson (2005) for a model
adsorbed layer containing both globular and disordered protein-
like polymers as a way of explaining experimental stability data
for emulsions made from mixed milk proteins (Parkinson &
Dickinson, 2004, 2007).
Historically speaking, a major industrial motivation behind the
development of OSA starch as a food emulsifier has been its com-
mercial promotion as a viable replacement for gum arabic (Schultz,
2010; Tan, 2004). Despite the lack of any obvious compositional
similarity between OSA starch and gum arabic, it seems pertinent
here to examine in detail what essential structural features they
might have in common.
3.2. Gum arabic
Gum arabic is a tree gum exudate. The natural raw material is
derived predominantly from the Acacia senegal species, although
commercial samples routinely contain gums from other tree spe-
cies, most notably Acacia seyal (Williams & Phillips, 2009). Gum
arabic has a unique status amongst food technologists as the
traditional hydrocolloid emulsifying agent of the food industry. In
particular, it is considered to be the ‘gold standard’ of beverage
emulsion manufacture (Piorkowski & McClements, 2014; Schultz,
2010).
In terms of overall composition, gum arabic is a heterogeneous
complex polysaccharide containing a small amount of nitrogenous
material that cannot be recovered by purification. Most of the ni-
trogen content is associated with a high-molecular-weight fraction
(10e30% of the total gum) which is considered to be mainly
responsible for its interfacial functionality in emulsions (Dickinson,
Galazka, & Anderson, 1991b; Randall, Phillips, & Williams, 1988).
 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13
The solid gum readily dissolves in water to give polyelectrolyte
solutions of low viscosity and a pH around 4.5. There is some
rheological evidence for self-association of the molecules in
aqueous solution (Sanchez, Renard, Robert, Schmitt, & Lefebvre,
2002). However, due to the exceptionally compact arrangement
of its constituent macromolecules and their associated low hy-
drodynamic molecular volume, gum arabic solutions exhibit close
to Newtonian flow behaviour at gum concentrations up to
25e30 wt%. This important functional characteristic enables the
ingredient to be employed as an effective emulsifying agent at high
gum/oil ratios.
The detailed composition of the gum has been established
chromatographically. Separation by gel permeation chromatog-
raphy with refractive index detection has revealed two distinct
fractions: a main component (peak 1) comprising about 90% of the
total sample (~2.5  105 Da for Acacia senegal) and a minor
component (peak 2, ~1e2  106 Da) comprising the remainder
(Williams & Phillips, 2009). A further minor component (peak 3)
composed of protein-rich material (~2  105 Da) was revealed by
chromatographic UV detection to constitute around 1 wt% of the
total gum. The carbohydrate polymers corresponding to all three
absorbance peaks have a galactose-linked main chain. There is
extensive chain branching via galactose and arabinose, with
rhamnose and glucuronic acid residues terminating some of the
branches (Williams, Phillips, & Stephen, 1990; Williams, Phillips,
Stephen, & Churms, 2006). Based on electron microscopy and
small-angle neutron scattering, it has been established that the
main arabinogalactan component (AG) (peak 1) has a thin disc-like
structure (radius 6.5 nm) (Sanchez et al., 2008). The material cor-
responding to peak 2, with a protein content of ~10%, is known as
the arabinogalactaneprotein complex (AGP). The inferred
morphology of this complex, as illustrated schematically in Fig. 4, is
a compact ‘wattle-blossom’ structure (radius ~36 nm) with disc-
like carbohydrate blocks (~4  104 Da) linked to a polypeptide
Fig. 4. Schematic representation of the ‘wattle blossom’ model of the arabinoga-
lactaneprotein complex (AGP) of gum arabic. The postulated structure consists of a
main polypeptide chain with intermittent attachments of short arabinose side-chains
(AAA) and large blocks of highly branched carbohydrate. Reproduced with permission
from Mahendran et al. (2008).
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7
chain (~250 residues) through both serine and hydroxyproline
residues (Connolly, Fenyo, & Vandevelde, 1988; Mahendran,
Williams, Phillips, Al-Assaf, & Baldwin, 2008; Osman, Menzies,
Williams, Phillips, & Baldwin, 1993). There also exists in the liter-
ature an alternative structural description of the AGP complex
known as the ‘twisted hairy rope’ model (Alftre n, Pen~ arrieta,
Bergenståhl, & Nilsson, 2012; Qi, Fong, & Lamport, 1991). The ma-
terial corresponding to peak 3, having a protein content of 20e50%,
is known as the glycoprotein component (GP). Its proteinaceous
region has a substantially different amino-acid sequence from that
of the AG and AGP components; and, unlike the other fractions, it is
not degraded by proteolytic enzymes.
There is a broad scientific consensus that the presence of a small
proportion of covalently bound protein (~2 wt% of Acacia senegal) is
responsible for conferring surface activity to gum arabic at the
oilewater interface, thereby enabling the ingredient to generate
stabilizing macromolecular films of substantial viscoelasticity
(Dickinson, 1988; Dickinson, Murray, & Stainsby, 1988; Elmanan,
Al-Assaf, Phillips, & Williams, 2008; Erni et al., 2007). Once estab-
lished at the oilewater interface, the gum arabic adsorbed layer is
characterized by surface shear rheological behaviour that is highly
resilient to dilution of the bulk aqueous phase (Dickinson, Elverson,
& Murray, 1989). The experimental investigation of several
different Acacia gum species with widely variable nitrogen contents
(0.1e7.5%) has suggested a strong correlation between the amount
of proteinaceous material in the material and its functional prop-
erties at the oilewater interface (Dickinson & Euston, 1991;
Dickinson, Murray & Stainsby, 1988; Dickinson, Murray, Stainsby
& Anderson, 1988). Nevertheless, the overall protein content is
not necessarily the overriding factor controlling the gum's surface
activity or the mechanical properties of its interfacial film. Also of
considerable importance to its interfacial functionality is the dis-
tribution of the proteinaceous material between low- and high-
molecular-weight entities, as well the protein's structural accessi-
bility within the AGP complex for adsorption at the oilewater
interface.
Gum arabic is recognized to be a reliable emulsifier of essential
oils in the presence of added colouring agents under conditions of
low pH and moderately high ionic strength (Tan, 2004). As with
OSA starch, oil-in-water emulsions based on gum arabic can be
stabilized over a wide range of pH, temperature and ionic strength
(Chanamai & McClements, 2002; Charoen et al., 2011). A recent
comparison of emulsification properties determined at high and
low pH values suggests that the ratio of acidic to basic amino acids
plays an important role in relation to the gum's interfacial func-
tionality (Ma, Bell, & Davis, 2015). An especially attractive attribute
of gum arabic to the soft drink manufacturer is the ability to sta-
bilize the flavour oil emulsion as both a concentrate (~20 vol% oil)
and after extensive dilution (say 100 times). Aside from the occa-
sional inconvenience of intermittent supply, its main commercial
disadvantage as an emulsifying agent is that it is regarded as being
a relatively expensive ingredient. This is because of the high gum/
oil ratio (~1:1) that is typically needed to generate uniform fine
droplets (mean diameter ≪ 1 mm) (McNamee, O'Riordan, &
O'Sullivan, 1998; Nakauma et al., 2008). This required usage level
corresponds to a much higher emulsifier concentration than that
typically needed, for instance, with a milk protein ingredient
(typically ~1:10 protein/oil ratio). The relative inefficiency of gum
arabic as an emulsifying agent is a consequence of the fact that only
the protein-containing entities of the mixed ingredient are directly
involved during emulsification (Randall et al., 1988; Ray, Bird,
Iacobucci, & Clark, 1995). Indeed, when the gum's covalently
bound protein is deliberately degraded with a proteolytic enzyme,
there is substantial loss of emulsification efficiency. Nevertheless,
8 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13
the protein content alone is not to be regarded as the single
definitive indicator of the effectiveness of the interfacial function-
ality of Acacia gums. Samples of gum arabic possessing the same
overall protein content (~2%) have been found to exhibit wide
variability in their emulsifying properties (Dickinson, Galazka, &
Anderson, 1991a).
The large overall molecular size of the AGP entities and the
branched character of their polysaccharide chains are two key
structural factors that appear highly favourable towards the pro-
vision of effective steric stabilization through the formation of a
thick adsorbed layer. Fig. 5 shows a sketch of the inferred structural
character of the gum arabic interfacial layer according to the widely
accepted ‘wattle blossom’ model (Evans, Ratcliffe, & Williams,
2013; Islam, Phillips, Sljivo, Snowden, & Williams, 1997). The hy-
drophobic polypeptide chains of the AGP molecules are the sticky
regions that anchor the macromolecules to the oilewater interface,
and the compact arrangement of blocks of branched carbohydrate
chains provides a strong steric barrier against droplet flocculation
and coalescence. The relatively high adsorbed amount determined
experimentally on limonene oil droplets (5e6 mg m2) has been
interpreted as indicative of some multilayer adsorption (Evans
et al., 2013). Since gum arabic is a polyelectrolyte, we can plau-
sibly envisage the possibility, under pH conditions where many of
the glucuronic acid groups are ionized (pH > 4), of significant
intermolecular association within the adsorbed layer. In addition,
charged groups are expected to make a direct electrostatic contri-
bution to the repulsive interdroplet pair potential. However, the
zeta potentials reported for acidic beverage emulsion formulations
are generally of a rather modest magnitude (in the range from e 10
to 20 mV) (Jayme, Dunstan, & Gee, 1999; Ray et al., 1995). So it
seems reasonable to assume that any contribution from electro-
static stabilization is of no more than secondary importance.
By applying the simple principle of “giving Nature a helping
hand” (Phillips, 2008a), a new generation of ingredients has been
developed based on mechanistic knowledge of the biological origin
of the variable functionality of different batches of native gum
arabic (Williams & Phillips, 2009). During normal tree growth in
the Sudan, the average molecular mass of the exuded gum arabic
increases from ~2.5  105 Da (after 5 years) to ~4.5  105 Da (after
15 years), and the proportions of protein and high-molecular-
weight AGP fraction also increase over same time period (Idris,
Williams, & Phillips, 1998). It appears that the underlying
Fig. 5. Sketch of the adsorbed layer structure of gum arabic at the oilewater interface
according to the widely accepted ‘wattle blossom’ model.
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biological process initially involves the formation of sub-units of
low molecular mass and reduced protein content. Later on, as the
acacia tree grows, these sub-units associate into larger AGP ag-
gregates. By designing and optimizing physical processes to accel-
erate and enhance this natural aggregation mechanism, Professor
Phillips and his collaborators have developed a series of ‘Supergum’
products (Al-Assaf, Katayama, Phillips, Sasaki, & Williams, 2003;
Phillips, 2008a). In essence, the patented ‘Supergum’ maturation
technology involves a thermal treatment of the raw dry gum under
strictly controlled conditions of temperature and humidity. By
inducing functionally significant changes in the distribution of
proteinaceous components and carbohydrate sub-units, the emul-
sifying performance of the gum material becomes substantially
enhanced following the thermal maturation process. With respect
to its overall chemical composition and inherent molecular archi-
tecture, however, the industrially matured gum is considered to be
‘identical’ to that of native gum arabic (Phillips, 2008a).
3.3. Pectin
Pectin belongs to a family of heterogeneous polysaccharides
located in the primary cell wall of plants. It is traditionally used in
the food industry as a gelling agent under acidic conditions and at
high sugar contents (Endress, 2009; Voragen, Pilnik, Thibault,
Axelos, & Renard, 1995). Whereas interest in the emulsification
properties of pectin has a fairly long history (Lotzkar & Maclay,
1943), it is only in recent times that it has gained acceptance as
an effective emulsifying agent and emulsion-stabilizing agent (Alba
& Kontogiorgos, 2016; Ngouemazong, Christiaens, Shpigelman, van
Loey, & Hendrickx, 2015). In particular, due to its widespread
availability and regulatory acceptability, sugar beet pectin has often
been put forward as the obvious natural replacement for gum
arabic in beverage emulsions (Schultz, 2010). Certainly, in well-
defined model systems at pH ¼ 3, sugar beet pectin can be suc-
cessfully used to prepare fine uniform emulsion droplets (diameter
~0.5 mm) at a much lower bulk emulsifier concentration than is
required with gum arabic (Nakauma et al., 2008). But unfortunately
these pectin-stabilized emulsions exhibit poorer stability on long-
term storage than the equivalent gum arabic formulations. To
date, then, in practical situations, pectin is yet to find widespread
industrial application as an emulsifying agent due to “its limited
ability to stabilize emulsions with sufficient robustness in the hard
world of beverage emulsions” (Phillips, 2008a).
Current usage applies the term ‘pectin’ to a group of hetero-
polysaccharides having a backbone composed mainly of D-gal-
acturonic acid bonded with a(1 / 4) glycosidic linkages (Alba &
Kontogiorgos, 2016). Pectin's diversity of polysaccharide structure
arises from wide variations in molecular weight distribution and
extent of esterification, and in the size, nature, and degree of
branching of its neutral side-chains. Further structural modifica-
tions arise as a consequence of chemical and enzymatic trans-
formations during the extraction process (Christiaens et al., 2016).
The most abundant component, homogalacturonan (HG), corre-
sponding to ~65% of the total material, is a linear homopolymer of
~200 galacturonic acid units. Depending on the plant species, some
of the carboxyl groups of HG are esterified with methyl groups and/
or acetyl groups. By convention, samples with extents of methyl
esterification below or above 50% are described, respectively, as low
methyl-esterified (LM) or high methyl-esterified (HM). Pectin is
therefore a polyelectrolyte with a charge distribution that is
dependent on the degree of esterification and on the arrangement
of the methyl and acetyl residues along the chain. The HG polymer
molecules may experience some depolymerization or de-
esterification during acidic extraction of the native material and
its subsequent processing (thermal, mechanical, enzymatic).
 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13
Another type of modification involves replacement of methoxyl
groups with amide groups.
Rhamnogalacturonan I and II (RG-I and RG-II) are two other
classes of pectic polymers corresponding, respectively, to 20e35%
and ~10% of the total pectin cell wall material. The polysaccharide
backbone of RG-I is composed of repeating disaccharide units of
rhamnoseegalacturonic acid (Voragen et al., 1995). The minor
component RG-II has a structure like a piece of the HG backbone
(7e9 units) with four heteropolymeric side-chains attached (Caffall
& Mohnen, 2009). Due to its diverse range of short and polymeric
side-chains, RG-I is the most branched and structurally heteroge-
neous of the pectic polysaccharides. In contrast to the ‘smooth’
character of the HG homopolymer, the RG-I polymer is commonly
referred to as ‘hairy’ because of its numerous lateral side-chains.
The chemical composition and the heterogeneous branched
structure of the RG-I side-chains are found to vary considerably
from source to source. In the case of sugar beet pectin, some of the
side-chains are esterified with ferulic acid (Rombouts & Thibault,
1986).
Owing to its inherent heterogeneity, and the intricate variations
in composition and molecular structure possessed by samples from
different natural sources, the mechanistic origin of pectin's func-
tionality is less clearly established than for OSA starch or even gum
arabic. Chemical analysis of a pectin sample invariably reveals the
presence of some protein, either as a contaminant or an intrinsic
part of the material. The amount of protein detected depends on
the extraction conditions and the botanical source d it is as low as
just 1% for apple pectin, but higher for citrus pectin (~3%) and sugar
beet pectin (>5%). The presence of bound proteinaceous moieties
acting as hydrophobic groups adsorbing at the oilewater interface
is considered to be the main origin of the surface activity and
emulsifying properties of sugar beet pectin (Funami et al., 2007;
Siew & Williams, 2008; Siew, Williams, Cui, & Wang, 2008;
Williams et al., 2005) and depolymerized citrus pectin (Akhtar,
Dickinson, Mazoyer, & Langendorff, 2002; Leroux, Langendorff,
Schick, Vaishnav, & Mazoyer, 2003). Consistent with this interpre-
tation is the detection of a greater concentration of protein at the
oilewater interface than in the continuous phase of these pectin-
stabilized emulsions. The existence of discrete entities of pro-
teinepectin complex has been established directly by atomic force
microscopy (Fishman et al., 2015; Kirby, MacDougall, & Morris,
2008). Furthermore, it has been found that enzymatic degrada-
tion of the protein component of sugar beet pectin leads to a sub-
stantial reduction in its interfacial activity and its emulsifying
capacity (Chen, Qiu et al., 2016; Funami et al., 2007). As well as the
overall proportion of protein, two other molecular factors are
presumed to affect pectin interfacial functionality: the distribution
of the hydrophobic residues along the polypeptide chain, and the
accessibility of the protein component for adsorption at the oile-
water interface during emulsification.
Various alternative explanations for the emulsifying character of
pectin derived from a range of different sources have recently been
critically assessed (Alba & Kontogiorgos, 2016; Ngouemazong et al.,
2015). In particular, there is a general recognition of the role of
potentially adsorbing hydrophobic residues on the carbohydrate
polymer in the form of methyl and acetyl groups, and also, in the
case of sugar beet pectin, the phenolic groups of ferulic acid.
Reducing the molecular weight of citrus pectin by limited acid
hydrolysis produces an enhancement in interfacial activity and a
consequent reduction in average emulsion droplet size (Akhtar
et al., 2002; Leroux et al., 2003). Nevertheless, it appears that the
degree of methylation may have only a minor effect on pectin's
emulsifying properties (Akhtar et al., 2002; Chen, Fu & Luo, 2016;
Schmidt, Schmidt, Kurz, Endress, & Schuchmann, 2015b), whereas
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9
evidence for the contribution of acetyl groups to pectin interfacial
functionality is possibly a little more compelling (Dea & Madden,
1986; Schmidt, Koch et al., 2015): for instance, an increase in
acetylation degree enhances the emulsification behaviour of citrus
pectin. On the other hand, the deacetylation of sugar beet pectin
does not lead to any significant reduction in its emulsifying ca-
pacity, suggesting that the presence of acetyl groups is not essential
for its interfacial functionality (Leroux et al., 2003). More
convincingly, perhaps, there is strong evidence for the role of
phenolic groups in the emulsifying properties of sugar beet pectin,
since measurements of adsorbed fractions show considerable
enrichment in ferulic acid as well as in protein (Siew & Williams,
2008). Hence, one may reasonably infer that some kind of ferulic
acidearabinogalactaneprotein complex plays a key mechanistic
role in the emulsifying properties of sugar beet pectin (Chen, Fu
et al., 2016). However, the lack of any significant correlation be-
tween the overall ferulic acid content and the amount of adsorbed
pectin has been interpreted to imply that the protein content is a
more important indicator of emulsifying capability than the
phenolic ester content (Funami et al., 2011).
As with other hydrocolloid emulsifiers, once the constituent
polymeric entities are strongly anchored to the oilewater interface,
the long-term stability is provided by repulsive steric interactions
between the adsorbed pectin layers on different emulsion droplets
(Gromer, Penfold, Gunning, Kirby, & Morris, 2010). An overview
analysis of the available evidence has led to the suggestion that, for
the robust maintenance of stability, the constituent pectin poly-
mers should have molar masses in the range 1e2  105 g mol1, and
there should be a substantial proportion of RG-I polymer chains
(Alba & Kontogiorgos, 2016). The repulsive steric interactions are
assumed to be enhanced by the presence of neutral sugar side-
chains along the hairy RG-I polysaccharide chain backbone. The
steric stabilizing ability of sugar beet pectin can be further
enhanced by inserting ferulic acid cross-links using the oxidative
enzyme laccase (Jung & Wicker, 2012).
As a consequence of the ionization of carboxyl groups on
smooth HG polymers, a contribution from electrostatic stabilization
in pectin-containing emulsions is to be expected. For any particular
pectin sample, the charge distribution along the chain is deter-
mined by the fraction of methyl groups and their degree of
‘blockiness’. Depending on the detailed molecular structure, there
is also the possibility of multilayer adsorption as a consequence of
attractive electrostatic interactions between negatively charged
galacturonic acid groups and positively charged protein residues
(Siew et al., 2008). The relative contribution of these electrostatic
effects is obviously dependent on the pH and the ionic strength of
the aqueous medium. At pH values well below 3.5 (the pKa of
galacturonic acid), the uncharged polymer chains can readily self-
associate, thereby allowing more of the hydrophobic groups to
locate themselves in close proximity to the oilewater interface.
This supposedly leads to a thicker and denser adsorbed layer with a
greater capacity for steric stabilization (Alba, Sagis, & Kontogiorgos,
2016; Castellani, Al-Assaf, Axelos, Phillips, & Anton, 2010). The
molecular configuration of the adsorbed pectin polymer in this
low-pH environment is illustrated schematically in Fig. 6(a). Under
less acidic solution conditions (pH > 3.5), electrostatic repulsion
between the anionic carboxylic acid groups causes the polymer
chains to extend further from the emulsion droplet surface, as
illustrated in Fig. 6(b). According to Alba and Kontogiorgos (2016),
the macromolecular configuration shown in Fig. 6(b) is not so
effective in preventing droplet coalescence owing to the reduced
number of hydrophobic groups attached to the surface and hence
the correspondingly greater likelihood of spontaneous polymer
desorption.
10 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13

Fig. 6. Idealized illustration of the effect of pH on pectin adsorbed layer structure at the surface of an oil droplet. (a) At lower pH (<3.5) the protonation of the carboxylate anions
generates a compact configuration of adsorbed chains with many hydrophobic groups in close proximity to the oilewater interface. (b) At higher pH (>3.5) electrostatic repulsion
between negatively charged carboxylate ions leads to an extended layer of adsorbed chains with fewer hydrophobic groups in contact with the interface. Label P denotes a
proteinaceous region. Reproduced with permission from Alba and Kontogiorgos (2016).

4. Concluding remarks
Reviewing the emulsifying properties of food hydrocolloids, an
attempt has been made here to address the underlying mechanistic
question d how do they do it? We have outlined some basic
principles of polymer adsorption and have assessed the accumu-
lated evidence relating to three practically relevant case studies.
Two alternative and apparently conflicting interpretations have
emerged.
Answer 1: Interfacial functionality arises from the hydrocolloid's
capacity to form a dense protective adsorbed layer of large
branched copolymer molecules. In order to confer effective
long-term steric stabilization on the dispersed emulsion drop-
lets, the adsorbed hydrocolloid has to possess a sufficient pro-
portion of accessible hydrophobic groups to enable its polymer
chains to remain permanently attached to the oilewater
interface.
Answer 2: Each hydrocolloid ingredient is unique in terms of its
biological origin, its compositional variability, and its complex
polymeric structure. Accordingly each ingredient confers inter-
facial functionality in its own special way.
We believe that both these answers are true. That is to say, a
common generic mechanism applies, but with rather intricate
macromolecular variations. Reconciliation of the two alternative
answers may seem more straightforward and logical when we
recognize that, while the functionality of an ingredient like chem-
ically modified starch is in part a product of human design, the
emulsifying properties of gum arabic and pectin are merely the
accidental consequences of biological variation. Even for these
‘accidental’ hydrocolloid emulsifiers, however, there is the oppor-
tunity for the food scientist “to give nature a helping hand” through
the use of controlled thermal processing (Phillips, 2008a) or some
other physical treatment such as high pressure processing (Ma
et al., 2015).
The long-term steric stabilization of an emulsion droplet re-
quires an appropriate balance between attractive and repulsive
forces d strong attraction between the droplet surface and some
small part of the adsorbed polymer, and strong repulsion between
the rest of the polymer and equivalent chains on other droplets.
Their large molecular size makes hydrocolloids especially suited to
this stabilizing role. Furthermore, the wide diversity of contribu-
tions to biological function in the original plant sources is consis-
tent with the presence on these biopolymers of a range of different
hydrophobic groups potentially available for attachment to oile-
water interfaces. Two main categories of anchoring species have
been clearly identified: (i) hydrophobic groups attached to certain
glycosidic residues along the carbohydrate chains (i.e. octenyl,
methyl, acetyl, phenolic, etc.), and (ii) short regions of covalently
bound protein or polypeptide. Beyond the case studies highlighted
in this article, one can readily find other instances in the scientific
literature of the involvement of these same two categories of
surface-anchoring species. For instance, in analogy with OSA starch,
the incorporation of hydrophobic alkyl side-chains has been re-
ported to confer much enhanced emulsifying properties on the
predominantly hydrophilic cellulose-based polymer hydrox-
yethylcellulose (Sun, Sun, Wei, Liu, & Zhang, 2007). Furthermore, in
analogy with gum arabic (and pectin), the mechanistic role of
bound protein has been regularly implicated in the interfacial
functionality of a wide range of naturally occurring hydrocolloids,
e.g., fenugreek gum (Brummer, Cui, & Wang, 2003), soy soluble
polysaccharide (Nakamura, Yoshida, Maeda, Furuta, & Corredig,
2004, 2006), mesquite gum (Roman-Guerrero et al., 2009), gum
ghatti (Al-Assaf, Amar, & Phillips, 2008; Kang, Guo, Phillips, & Cui,
2014), corn fibre gum (Yadav, Cooke, Johnston, & Hicks, 2010),
durian seed gum (Amid & Mirhosseini, 2012) and basil seed gum
(Hosseini-Parvar, Osano, & Matia-Merino, 2016; Naji-Tabasi &
Razavi, 2016; Osano, Hosseini-Parvar, Matia-Merino, & Golding,
2014). The reader should also be made aware of the less well
established hypothesis of Yadav, Igartuburu, Yan, and Nothnagel
(2007) that bound lipid species make a predominant contribution
to gum emulsification activity.
There has been an ongoing trend in the food sector towards the
use of ‘natural’ emulsifiers (Dickinson, 1993; Ozturk & McClements,
2016). In accordance with perceived consumer preference, it is
increasingly the manufacturer's ultimate strategy that the pro-
cessing of ingredients intended for eventual human consumption
should not involve any chemically induced modification. In
contrast, traditional types of physical processing like heating and
drying are generally considered to be acceptable. An indirect
consequence of the discovery of the mechanistic role of bound
protein in the functionality of gum arabic has been the steadily
growing interest in proteinepolysaccharide complexes as novel

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http://dx.doi.org/10.1016/j.foodhyd.2017.01.025
 E. Dickinson / Food Hydrocolloids xxx (2017) 1e13
ingredients for emulsion stabilization. Most notably, the attention
of food researchers has been directed towards emulsifying in-
gredients based on Maillard-type proteinepolysaccharide conju-
gates (Dickinson, 2009a, 2015b; Evans et al., 2013; Lee et al., 2016).
These covalent conjugates are typically prepared by the controlled
heat treatment of binary mixtures of protein þ polysaccharide
under conditions of low water activity (Kato, Sasaki, Furuta, &
Kobayashi, 1990). In analogy with the AGP complex of gum
arabic, the essential concept lying behind the preparation of the
Maillard-type conjugate is the formation of an amphiphilic pro-
teinepolysaccharide copolymer (or, more realistically, a heteroge-
neous mixture of such copolymers) with the capability to anchor
strongly at the oilewater interface through its proteinaceous
element, and furthermore, once having become so attached, to
provide effective steric stabilization through its bulky hydrophilic
polysaccharide component. Where covalent conjugates have a clear
advantage over electrostatic proteinepolysaccharide complexes is
their ability to maintain permanent macromolecular structural
integrity over a wide range of pH and electrolyte conditions
(Dickinson, 2008; Evans et al., 2013; Liu, Ma, Gao, & McClements,
2017; Semenova & Dickinson, 2010).
In contrast to our esteemed colleagues working in laboratories
of synthetic chemistry or polymer physics, the food scientist/
technologist is limited to the living natural world for the supply of
polymer-based ingredients. Having evolved to perform a specific
functional role in some individual biological niche, the natural
macromolecular material has a tendency to be intrinsically com-
plex in its composition and molecular architecture. In the words of
Professor Glyn Phillips, “natural polymers are never uniform or
simple; their functionality depends on more than one structural
feature” (Phillips, 2008a). In the context of interfacial functionality,
one apparent consequence of this compositional ‘messiness’ is that
the adsorption efficiency of the hydrocolloid is substantially lower
than that normally found with a conventional synthetic surfactant
or a peptide-based emulsifier (Adjonu, Doran, Torley, & Agboola,
2014). In practice, what this means is that a higher concentration
of the emulsifying ingredient is required to make an oil-in-water
emulsion of similar average droplet size. Once prepared, however,
the hydrocolloid-stabilized emulsion is typically more resilient to
subsequent environmental changes. This enhanced resilience is
especially evident under the severe demands of commercial
emulsion product formulation d namely, the potentially disturbing
effects of thermal processing, pH adjustment, and elevated salt
content, and the requirement for physico-chemical compatibility
with other ingredients such as flavours and colour additives.
Let us end on a more speculative note. Regarding compositional
messiness and structural complexity, we might reasonably be
tempted to assert that the existence of a complicated mixture of
heterogeneous and polydisperse macromolecules within a single
hydrocolloid ingredient ought not to be entirely detrimental to its
interfacial functionality. Indeed, on the contrary, there is much
empirical and anecdotal evidence to support the view that the
compositional and structural messiness of a macromolecular
ingredient should be regarded as a positive flexible attribute. Such a
tentative hypothesis would be broadly consistent with intuitive
theoretical insight which suggests that, so long as the constituents
remain soluble, and are not prone to extensive aggregation or
gelation, the presence of a mixture of macromolecular entities
which differ in shape, size and composition should be beneficial for
rapid development of an adsorbed stabilizing layer during emul-
sification. Moreover, a heterogeneous system of polymers having
different extents of chain branching could well be imagined to lead
to a structured mixed layer which is optimized for long-term
emulsion stability. The predictions of the self-consistent-field cal-
culations of Ettelaie et al. (2016) highlighted in this article would
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http://dx.doi.org/10.1016/j.foodhyd.2017.01.025
11
appear to provide some modest support and justification for this
intuitive interpretation.
Without any doubt, there is much research still to be done to
resolve some of the outstanding issues raised in this article. We
trust that those who will take on the challenge of involving
themselves in this future work can be inspired by the steady
worthwhile progress made so far. Especially noteworthy in this
latter regard are the many contributions from Professor Glyn
Phillips and his illustrious band of international collaborators.
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