Current Opinion in Colloid & Interface Science 12 (2007) 221 – 231

www.elsevier.com/locate/cocis

Structuring of edible oils by alternatives to crystalline fat

Mimma Pernetti 1 , Kees F. van Malssen, Eckhard Flöter, Arjen Bot ⁎
Unilever Research and Development Vlaardingen, Olivier van Noortlaan 120, NL-3133 AT Vlaardingen, The Netherlands
Received 13 July 2007; accepted 18 July 2007
Available online 26 July 2007

Abstract

The structure of many food products is based on networks of crystalline triacylglycerol (TAG) hardstock. These contain high levels of saturated
fatty acids, which are among the factors contributing to cardiovascular diseases. Therefore it would be desirable to have alternative routes to
structure edible oils.
This review starts with general structuring concepts and building blocks which can be found in organic solvents. Subsequently it focuses on the field
of edible oil structuring. Among the alternative structuring agents that have received attention in recent years are mono- and diglycerides, fatty acids, fatty
alcohols, waxes, wax esters, sorbitan esters, and phytosterols. It is found that the most efficient structuring agents form small, preferably non-spherical
particles. Mixing of components often provides superior structuring over use of pure components. Straightforward screening of pure components might
be feasible. However, the number of options provided by mixing requires guided screening, for which understanding of the underlying mechanisms is
essential. Analytical methods helping to characterise oil structuring and elucidate the structuring mechanisms are discussed.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Organogel; Oleogel; Oil gel; Triacylglycerol (TAG, triglyceride); Diacylglycerol (DAG, diglyceride); Monoacylglycerol (MAG, monoglyceride); Fatty
acid; Fatty alcohol; Wax; Sorbitan monostearate (SMS); Lecithin; Sorbitan tristearate (STS); Phytosterol; Oryzanol; Self assembly; Crystallisation

1. Introduction and number of the crystals determine to a large extent the

The most common way to provide texture to the lipid phase
of food products is by including a crystalline triacylglycerol
(TAG) hardstock [1,2]. However, these hardstocks contain
major amounts of saturated fatty acids (SaFa), which are
considered unhealthy since their presence in the diet is among
the factors contributing to cardio-vascular diseases [3,4]. The
edible oil itself can be considered an organic solvent, mainly
consisting of unsaturated TAG. In view of reducing SaFa levels,
as well as finding new texturising properties, there is a broad
interest to find alternatives to the use of these TAG hardstocks,
which form the benchmark for oil structuring.
Saturated TAG hardstocks are widely applied and have been
studied in great detail. The saturated TAGs have a limited
solubility in the oil and upon cooling a hot melt, small crystals
grow and form a network across the liquid. The actual size, shape
⁎ Corresponding author. Tel.: +31 10 460 6449; fax: +31 10 460 6000.
E-mail address: arjen.bot@unilever.com (A. Bot).
1
Present address: GlaxoSmithKline Biologicals, Rue de l'Institut 89, B-1330
Rixensart, Belgium.
1359-0294/$ - see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2007.07.002
mechanical properties of the textured oil. Fast and deep cooling
stimulates the formation of large numbers of very small crystals,
which interact with strong ‘primary’ sintered connections and
weak ‘secondary’ van der Waals bonds between the crystals.
The mechanical network properties and thus the final product
properties, can be tuned by processing via the ratio between
primary and secondary bonds. Exploiting the full range of TAGs
occurring in nature and all possibilities of processing enables the
design of networks with a wide range of firmnesses and melting
profiles [1,2,5,6].
Finding alternatives to these high-SaFa TAG structurants that
provide the same level of performance and versatility is quite a
challenge, especially within the constraints imposed by the
foreseen use in healthy foods. A deep understanding of the
underlying behaviour of structurants in lipid phases is required
to find such alternatives. Some materials have been found to be
able to structure organic solvents, of which edible oil is one. The
specific functionality of such building blocks depends on
solvent, processing and the presence of other ingredients.
Many structuring solutions have been found through serendipity
and have to be optimised empirically. Additional studies to
222 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231
Fig. 1. Illustration of the structuring concepts (microscopic images courtesy of J.C.G. Blonk, Unilever R&D Vlaardingen).
understand underlying mechanisms are essential to allow struc-
turing by design. This is relevant especially since some of the
most interesting systems are built through mixed components.
The present review aims to make a further step towards the
understanding of the structuring mechanism and the design of
new systems. It starts with a broad overview on systems that
have been shown to structure organic phases. Subsequently, it
narrows down and describes in more detail systems that have
been shown to structure edible oil phases. Finally, it describes
the approach that would help to further develop current under-
standing, identifying the most appropriate analytical techniques
to be employed.
2. Structuring concepts and building blocks
The structuring of organic phases has received considerable
attention already outside the field of food science. The present
section is aimed at identifying solutions that have been
proposed in this wider context, which has far fewer restrictions
than food applications. Generally, two routes can be found: (i)
dispersion of a foreign phase (small inert particles, crystallised
solids, separated droplets); (ii) specific molecular mechanisms,
such as self-assembly (regularly observed with low-molecular
weight organogelators). These routes provide the “structuring
elements”, which act as building blocks for the three-
dimensional networks that are required to structure oil (see
Fig. 1). The size and shape of the structuring elements and their
interactions will determine the final structure of the product, and
consequently its properties.
2.1. Suspensions and emulsions
A structured product can be obtained by dispersing a large
amount of inert filler particles in the continuous phase. The
building blocks can be solid particles or aqueous droplets. If the
volume fraction exceeds the close packing fraction, mechanical
contact between the particles will result in a network. However,
if the volume fraction of the dispersed phase is lower, aggre-
gation through weak physical bonds or as a result of partial
coalescence is required to ensure an increase in viscosity or
firmness of the product as a whole. In food, one example is
peanut butter, which is composed of about 50% solid non-fat
particles and 50% peanut oil. Its structure is due to the high
amount of dispersed phase and only partially to the amount of
hardstock (only 1–2% triglycerides) [7,8]. The disadvantage of
dispersed systems is that generally a high amount of structurant
needs to be added.
2.2. Networks
Another way to create structure is by using ingredients with
limited solubility, which precipitate during gel formation. The
 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231 223

structuring elements can be macromolecules, such as polymers crystallite networks. The details of self-assembling systems are
or proteins, low molecular weight compounds, such as fatty not well enough understood to predict their structuring ca-
acids, fatty alcohols or TAGs. The interactions between them can pability in advance, and most organogelling systems are found
be of a different nature like covalent bonds, electrostatic forces, by serendipity [30,32]. This is unfortunate, since many of the
hydrogen bridges, van der Waals forces or steric entanglements. most interesting structurant systems consist of mixtures, making
Generally, only a small number of building blocks are required to discovery by chance even more unlikely. Most of the low
create a network. The most common examples of this kind of molecular-weight oil gelators and most of the organic solvents
structure are gels and crystallised fat. Such structures are used in used in these studies are not foodgrade. Nevertheless, this class
different applications, such as pharmaceutics, cosmetics and art of materials is expected to give the most novel and interesting
conservation [9–12]. An example of formation of an undesired examples of oil structuring in the future.
thermoreversible network is the occurrence of wax crystal-
lisation in crude oil [13,14]. In food, lard is an example of a pure 3. Recent development in structuring edible oils
fat crystal network [15–17].
An important sub-class of network-forming agents consists of From the discussion above it is clear that the most interesting
macromolecules. A considerable body of research has been developments take place in structuring with low-molecular
devoted to synthetic polymers, whose chemical structure can be weight molecules. However, properties of organic phases are
modified to a high degree in order to obtain the desired too diverse to translate these findings directly to any non-
properties. Examples include polyvinylalcohols and polysilox- aqueous phase. In the context of food science the interest is
anes with the ability to structure non-aqueous solvents [18], directed to the structuring of edible TAG oils. This introduces a
dendrimers with self-assembling properties to form nano- number of additional restrictions:
composite materials [19], cross-linked synthetic polymers [20],
and amphiphilic polymers with the ability to act simultaneously • TAG oils are far more polar than many of the systems
as structurant of the oil phase and as surfactant at the water–oil discussed typically in the organogelation literature (such as
interface. However, the synthetic nature of these polymers mineral oils, alkanes). This influences the solubility of the
generally prevents any application in foods, and we will consider structuring agents, which implies that many of the examples
these materials to be out of scope for the current review. in the literature will not work in TAG oils (Within the group
Modified biopolymers are of greater interest in the present of TAG oils, a similar situation arises with castor oil, which
context since they are generally foodgrade and some of them are is even more polar than regular vegetable oils and sometimes
already widely used in food industry. They can be modified to allows structuring with other structurants).
fine-tune their chemical properties and structuring potential. For • The ingredients should be usable in foods. In this review, a
example, starch has been modified to produce a material with liberal definition of food grade will be used. Some ingredients
lipophilic characteristics [21]. Cellulose derivatives, such as may have legal concentration restrictions in food formula-
hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hy- tions. Other ingredients are not formally food grade, but
droxyethyl cellulose, have been used to produce oil gels for chemically come very close to common food ingredients
pharmaceutical and cosmetic applications [22,23]. Chitosan can (certain waxes or long-chain fatty alcohols). Such ingredients
be made more hydrophobic by N-acylation with various fatty are included in the present review, if no obvious adverse
acid chlorides [24]. Proteins can be modified by introducing effects are known.
benzyl or isopropyl side groups on the amino acid, leading to • In food application, the interest is not addressed at the purest
organogelation in apolar solvents at very low concentration ‘analytical grade’ components, but often at commercial-
(0.2 wt.%) and the formation of thermostable gels [25]. However,
in the subsequent sections it will become clear that the use of Table 1
macromolecules in edible oil structuring is still very rare. The Trivial names for relevant fatty (di)acids. Names for alcohols or other functional
groups can easily be derived from this table
tight restrictions on modifications allowed for food ingredients
make major developments in this field in the near future unlikely. Trivial name Carbon number and unsaturation Systematic name
A second sub-class of networks are those obtained through Lauric acid C12:0 Dodecanoic acid
self-assembly of amphiphilic molecules. The driving force for Myristic acid C14:0 Tetradecanoic acid
Palmitic acid C16:0 Hexadecanoic acid
self-assembly can be weak and specific intermolecular interac-
Stearic acid C18:0 Octadecanoic acid
tions [26], such as molecular resemblance or ionic interaction Arachidic acid C20:0 Eicosanoic acid
[27]. In some cases the amphiphilic molecules produce dispersed Behenic acid C22:0 Docosanoic acid
mesophases, such as micelles, hexagonal phases [28] and cubic Hydroxystearic acid C18:0-OH 12-hydroxy-
phases [29], which will lead to an increase in viscosity of the octodecanoic acid
Ricinelaidic acid C18:1t-OH 12-hydroxy-9-trans-
organic solvent phase. In other cases, these low molecular
octodecenoic acid
weight compounds may form elongated fibre-like or crystal-like Ricinoleic acid C18:1c-OH 12-hydroxy-9-cis-
structures, by non-covalent interactions, joining in three- octodecenoic acid
dimensional networks [11,30,31]. Sometimes the denomination Adipic acid C6-diacid Hexanedioic acid
‘organogel’ is specifically reserved for this type of structured oil, Suberic acid C8-diacid Octanedioic acid
Sebacic acid C10-diacid Decanedioic acid
but in practice it is not always easy to make the distinction with
224 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231
Fig. 2. Schematic representation of a number of structurants for TAG oil phases (not to scale).
grade purity ones, which are more relevant to applications. In
practice, ingredient cost will be relevant too.
• The structurants should gel edible oils at chilled and ambient
temperatures (i.e. between 5 and 25 °C) to make them
relevant for food applications.
Despite these limitations, considerable progress has been
made in this field over the last few years. A rather large number
of systems have been identified that are capable of structuring
TAG oil phases. Combining these results, this review will
outline an overall picture of the requirements for non-TAG
structuring of edible oils.
The subsequent paragraphs will discuss single or mixed
compounds with the ability to gel TAG oil. In most cases, the
trivial names for alkyl groups will be used, but Table 1 provides
the relevant systematic nomenclature. The structurants are listed
below starting from those that are chemically closest to
crystalline TAGs which are mentioned first, down to the ones
that are more different, which are mentioned later. The rationale
behind the classification used can be inferred from Fig. 2.
3.1. TAGs, DAGs and MAGs
3.1.1. Triacylglycerol (TAG or triglyceride)
Structuring with crystalline TAG is the benchmark for edible
oil2 structuring. TAGs rich in saturated or trans-monounsatu-
rated fatty acids have a limited solubility in edible oils, which are
rich in short chain and/or unsaturated fatty acids. The crystalline
TAG forms a network of small crystals in the oil. The size and
shape of the crystals can be controlled by shear and cooling rate
2
Commonly, oil is the liquid TAG phase and fat the solid TAG phase at
ambient temperature.
[5,6], and their interactions determine the mechanical properties
of the network [33]. At sufficiently high concentration, the
networks are usually relatively firm and their melting behaviour
can be tuned by choosing the fatty acid profile for the TAG phase
optimally.
Besides the regular firm network that is usually produced,
TAGs can be used also to make a flowable texture by mixing
high melting and low melting TAGs [34•,35,36]. The high
melting fats directly form stable β crystals that aggregate to
form flocs, but not enough to span the container. Thus, a space-
filling dispersion of crystals is formed. For this type of structure
no alternatives have been found yet.
3.1.2. Diacylglycerol (DAG or diglyceride)
The next member in the family of acylglycerols is DAG,
which received most attention until now for its influence on TAG
crystallisation. Surprisingly little attention has been given to
separate structuring through DAG. Dipalmitin and distearin
form crystallite networks in a relatively similar way as TAGs
(van Malssen and Bot, unpublished data). The gels are slightly
soft compared to TAG crystal networks of similar concentration.
3.1.3. Monoacylglycerol (MAG or monoglyceride)
MAGs are among the rare components that can structure both
lipid [37,38••,64] and aqueous phases [39–42]. MAGs are
thought to form reversed bilayers in TAG oils [37,38••], Ojijo
et al. showed that mixtures of monopalmitin and monostearin
form networks under quiescent cooling in olive oil at low con-
centrations [37,38••]. Faster cooling provides gels with higher
firmness, but generally lower elastic modulus. Staged crystal-
lisation could explain this phenomenon: at low cooling rates, the
first crystallising MAGs form a ‘backbone’ network, on which
the remaining MAG deposit subsequently; at high cooling rates,
 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231
numerous fine crystals are formed in a single crystallisation step.
In terms of primary and secondary bonds the balance might shift
towards stronger primary bonds at lower cooling rates and more
numerous secondary bonds at higher cooling rates. Crystal-
lisation in stages leads to more weak spots, increasing firmness
failure, whilst increasing resistance to small deformations.
The application of shear at or above the gel point for
quiescent crystallisation leads to finer homogeneous gels at
lower temperatures. This suggests that shear disturbs the initial
stage of crystallisation for example by modifying the meso-
phases present above the melting temperatures of the crystallites
[37].
During weeks of storage with temperature cycling, the
firmness of these networks increases, whilst the melting onset
decreases [38••]. Since no increase in crystallinity is observed,
the changes could be explained by a reorganisation of the net-
work building blocks, for example by strengthening of primary
bonds due to the dynamic equilibrium of dissolved MAG in the
oil, as can be observed in TAG networks too [5].
3.2. Fatty acids, fatty alcohols, waxes, and sorbitan alkylates
3.2.1. Fatty acids (FA)
Fatty acids, and especially fatty acid salts (i.e. soaps), have
served as the prototype for structuring of oil phases. Here we
will not consider the soaps (e.g. Tamura et al. [43]), as their
application lays more in the personal care area, rather than in
foods. Elliger et al. were the first who mentioned the oil struc-
turing potential of 12-hydroxystearic acid in a study on the
thickening of peanut butter [44]. For many years this remained
the prime example of edible oil structured by a fatty acid, and is
still subject of investigation [45].
Gandolfo et al. investigated palmitic, stearic, arachidic and
behenic acid, and established oil structuring ability in sunflower
oil above ∼ 2% at 5 °C [46•]. Daniel and Rajasekharan
investigated an even wider range of fatty acids, showing that the
amount required to structure oil does not decrease much further
with chain lengths up from 31 [47••]. One can hypothesize that
the amount of solids is more or less constant for these chain
lengths. The melting temperature of the gels goes up from about
40 to 70 °C.
Structuring is possible with trans-monounsaturated fatty acids
as well. Wright and Marangoni confirmed the gelation of
rapeseed oil with at least 0.5% of ricinelaidic acid, the trans-
unsaturated counterpart of 12-hydroxystearic acid [48••,49].
Transparent gels were formed with 0.5–1% structurant in canola
oil, suggesting gel building blocks with small dimensions
compared to the wavelength of visible light. Microscopy confirms
the formation of thin (birefringent) fibrils [48••].
Rheological assessment of the gels confirms that these are
strong gels except at very low concentrations. Simple power-
law scaling rules can be formulated for these systems, but the
description is not universal over the whole time and temperature
range. It is possible to create a thickened but not gelled phase
with ricinelaidic acid in unrefined sesame oil [48••]. These
systems bear some rheological similarity to the mixed high- and
low-melting TAGs described by Higaki et al. [34•,35,36].
225
Possibly, a similar explanation involving large but unconnected
dispersed aggregates is applicable here.
Oils with a considerable amount of free hydroxyl-groups
(sesame oil, DAG oil) could not be gelled. This suggests that
hydrogen bonding is important in these systems.
Derivatised fatty acids with additional hydroxyl or methyl
groups were investigated by Daniel and Rajasekharan [47••].
The single hydroxyl group in 12-hydroxystearic acid is found to
be the most efficient in enhancing gelation. Short dicarboxylic
acids (adipic, suberic and sebacic acid) were found to structure
much better than their mono-carboxylic counterparts and with
relatively high melting points (80 to 145 °C).
Although the crystal structure of pure fatty acids is known
for a long time [50,51], there is little mentioning of which
polymorph is present in gelled oil. Schaink et al. reported that
stearic acid structures sunflower oil by means of rather thick
crystals and XRD patterns indicating an orthorhombic structure
similar to β′-type TAG crystals [52]. Wright and Marangoni
reported the molecular ordering of the ricinelaidic acid crystal-
lites in oil to be quite similar to the one in neat ricinelaidic acid,
but the packing seems slightly more compact in the organogel
[48••].
3.2.2. Fatty alcohols
Gandolfo et al. found that the fatty alcohols palmityl, stearyl,
arachyl and behenyl alcohol provide firmness to sunflower oil at
concentrations above ∼ 2% at 5 °C [46 • ]. Daniel and
Rajasekharan investigated the gelation of sunflower oil by
means of even longer fatty alcohols, with chain lengths in the
range of 22–30 [47••]. These ingredients structure the oil at
concentrations of 3–4%. The gel melting temperature increases
from 40–45 °C for behenyl alcohol to 55–60 °C for tricontanol.
In oils that are relatively rich in saturated fatty acids (soy bean
oil or olive oil vs sunflower oil or rapeseed oil) a synergistic
effect between the oil and the fatty alcohols is observed [46•].
Schaink et al. demonstrated that stearyl alcohol structures the
oil by means of quite thick crystals and with an orthorhombic
packing and orthogonal chain stacking [52].
3.2.3. Waxes and wax esters
Daniel and Rajasekharan showed that the structuring
potential of saturated wax esters (behenic acid esterified with
14–22 chain length alcohols) in TAG oil is similar to their fatty
acid counterparts [47].
Toro-Vazquez et al. [53] established the oil structuring prop-
erty of candelilla wax in safflower oil at concentrations of ∼1%
and higher [53]. Candelilla wax consists mainly of C29–C33 odd
length alkanes, and has food grade status in special applications.
The work by Toro-Vazquez emphasised mainly thermodynamic
properties, and less details of the structuring mechanism.
3.2.4. Sorbitan monostearate (SMS)
SMS forms viscous dispersions in edible oils. The viscosity
increases with increasing concentration until a gel is formed. The
threshold concentration depends on the specific oil; 10% SMS
gives a firm opaque gel in vegetable oil [54]. Although most
attention has been focussed on organic phases other than TAG
226 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231
oils, it seems that gelation involves the formation of tubular
vesicles [55] just above the melting point of the SMS in the
organic phases, which shows most agreement with the TAG oil.
Murdan et al. suggest that the surfactant molecules are organised
as inverse bilayers in the tubules [54]. The tubular vesicles can
associate to form an opaque three-dimensional network. These
gels are thermoreversible and melt at ∼ 40 °C.
3.3. Structuring mixtures
From TAG structuring, it is known that mixtures of
ingredients can outperform pure hardstocks. Potential synergis-
tic effects in non-TAG structuring mixtures are therefore of
considerable interest.
3.3.1. Fatty acids + fatty alcohols
Long-chain fatty acids and fatty alcohols cannot only
structure edible oils by themselves, but also in combination
[46•,52]. Upon quiescent cooling, these systems form homo-
geneous, opaque gels consisting of a particle dispersion at
concentrations above ∼ 2% of the structurants. The strain at
breaking is ∼ 10% [52]. The gels are observed for mixtures in
which the fatty alcohol and the fatty acid have the same chain
length (16 to 22), and in mixtures of stearic acid with fatty
alcohols of different chain length (16 to 22). It is expected that
other chain lengths, not yet studied, will also result in gelled oil.
An interesting aspect of these systems is the synergistic
effect for the firmness at specific acid:alcohol ratios. Specifi-
cally around 30% stearic acid + 70% stearyl alcohol mixtures,
firmness is much higher than at other ratios with the same
overall level of structurants [46•,52]. Microscopic evidence
suggests that this mixture forms the smallest crystals, as has
been confirmed by images of needle-like crystals in gels [52].
Gandolfo et al. explained the synergistic effect through an
Fig. 3. Rheological profile of 50:50 STS:lecithin mixture, 12% in oil. Polarised light micrographs A: mixture at 60 °C, B: after cooling to 30 °C, C: after cooling at 5 °C
(the total image width is 460 μm).
increased nucleation rate due to a reduction in the interfacial
energy of the nuclei [46•]. Schaink et al. demonstrated through
XRD that for the 3:7 ratio very small crystals of a different
crystal packing are formed [52]. The crystallographic short
spacings suggest a packing similar to a TAG β-polymorph.
3.3.2. Lecithin + sorbitan tristearate (STS)
STS shows some molecular similarity to TAGs, the glycerol
backbone being replaced by sorbitan (see Fig. 2). In TAG oil STS
forms regularly shaped crystals that melt at ∼40 °C. Neither STS
nor lecithin structures TAG oil by themselves. Addition of STS
and lecithin to a TAG oil at ratios between 40:60 and 60:40 leads to
the formation of fine, needle-shaped crystals. X-ray diffraction
shows that lecithin does not affect the crystal structure. The
needles still consist of STS and the lecithin mainly changes the
morphology of the crystals [56••]. In addition, rheological
measurements in Fig. 3 seem to prove that the lecithin helps to
create a weak interaction between the crystals, STS crystals them-
selves having no tendency to aggregate (Pernetti and Hartmann,
unpublished data). The mixture forms a gel at concentrations
above ∼4%. The gel is shear sensitive and collapses above 20 °C,
though like other organogels it is perfectly thermoreversible.
3.3.3. Phytosterols + oryzanol
A group of materials not containing any long fatty acid
chains was studied by Bot and Agterof [57••] and consists of
mixtures of γ-oryzanol and phytosterols (e.g. cholesterol,
dihydrocholesterol, β-sitosterol and stigmasterol). The ratio is
not critical, but optimal molar ratios are approximately 1:1.
These gels probably belong to the wider class of cholesterol-
based organogels [58]. About 2–4% of structurant is required to
form a gel at 5 °C. The gels have a slippery surface, but are quite
firm under compression: At 5–10% structurant, their mechan-
ical properties approach those of a block of fat.
 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231
Fig. 4. An He–Ne laser beam shining through a transparent β-sitosterol+γ-oryzanol
organogel. The gel has been taken out of its container and is quite firm and self-
supporting.
The gels are transparent, as is illustrated in Fig. 4. This
implies that the gel building blocks are considerably smaller
than the wavelength of visible light. The oil + structurant
mixture is easily supercooled without gel formation and some
mechanical disturbance seems necessary to form firm gels.
Probably the building blocks are pronounced non-spherical, e.g.
thin fibrils. Such fibrils are observed for many of the
cholesterol-based organogels [58].
A molecular energy minimisation calculation (Fig. 5)
suggests that the γ-oryzanol and β-sitosterol molecules dock
their sitosterol units on top of each other, with the ferulic acid
moiety of the γ-oryzanol sticking out. The stacking on a
molecular scale does not predict how many of these molecules
assemble, but the slight wedge shape of the stacked molecules
would leave room for a curved supramolecular structure. Such
curvature would be consistent with the formation of fibrils. It is
still unclear, however, whether the crystalline fibrils would form
directly from the solution, or rather via an intermediate tubular
micelle.
3.4. Protein structuring
An interesting and completely alternative approach to oil
structuring was taken by Romoscanu and Mezzenga [59••].
They produced a space-filling emulsion of very monodisperse
protein-stabilised droplets and subsequent cross-linked the
proteins at the droplet interface (either by protein denaturation
or by chemical cross-linking with glutaraldehyde). After
addition of some glycerol (0.5%), the emulsions were allowed
to dry. This lead to the formation of a high internal phase
emulsion (HIPE), which created a ‘foam’ of protein lamella in a
continuous oil phase. The resulting gel is transparent. The
frequency dependence of the elastic properties of the gel is
weak, in agreement with strong gel behaviour. The ‘melting’
behaviour of the gels is quite unique: the droplets can be
redispersed on rehydration, as the droplets dissociate again. The
reversibility of the process is better for very pure oils, and less
for e.g. virgin olive oil. This is explained by the occurrence of
interdroplet cross-linking in the emulsion based on less pure oil.
227
4. Research techniques for future studies
Most effort in the field of alternative oil structuring until now
aimed at screening potential structurants, and establishing the
microstructure and the thermal and mechanical properties of the
structured oil. Such efforts could be intensified, for example by
introducing high throughput screening approaches. However, the
sheer number of combinations of potential structurants makes this
approach futile without some form of guidance. Therefore, more
attention should be spent on identifying the common underlying
mechanisms and assembly dynamics in order to progress under-
standing in this field to a level that allows a priori design of
structures. The essential questions address network formation and
influence of processing and selected ingredients.
The mechanical properties of the network determine its po-
tential for use in applications. Until now, mainly two types of
rheological measurements have been used, next to visual assess-
ment. These techniques are commonly available and widely ap-
plied. Studies of the underlying texturing mechanisms require
more advanced techniques like Transmission and Scanning
Electron Microscopy (TEM, SEM), Atomic Force Microscopy
(AFM), X-ray scattering and combinatorial techniques, which are
often less widely available. Analytical methods necessary to
obtain good quality data on chemical sample composition, al-
though very important, are beyond the scope of this review.
4.1. Mechanical properties
In practice, edible oils are structured to provide products with
specific consistency and firmness. Until now, in most papers on
oil structuring, mainly three types of rheological measurements
have been used, next to visual assessment. These techniques are
commonly available and widely applied. A texture analyzer
using a cylindrical probe (e.g. [46•]) gives a fast characterisation,
but is not suitable for a more fundamental analysis of the me-
chanical network properties. Small deformation rheology yield-
ing storage and loss moduli [56••,57••] is more suitable for
comparisons between different materials [60]. In the end, how-
ever, large deformation studies involving amongst others the
plasticity of the structured oil and the ability to reform after
shearing are more relevant to the application [57••]. In combi-
nation, these studies give a proper fingerprint of the obtained gel.
Rheological properties can also be used to assess the stability
of the microstructure during storage or during temperature
Fig. 5. Proposed stacking of sitosterol and oryzanol molecules, based on a crude
energy minimisation calculation (RM Hermant, Unilever R&D, unpublished
data). An H-bridge can be formed near to the arrow, resulting in slightly wedge
shaped stack.
228 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231
cycling. Studies as a function of time and temperature can
contribute to the identification of recrystallisation or reorgani-
sation phenomena in the structurant network, or be used to
construct phase diagrams. A careful analysis of all rheological
data (as a function of temperature, concentration, applied strain,
etc.) in combination with results of other techniques may help to
answer questions concerning the cross section of fibres, the type
and structures of the junction zones, and the microscopic failure
mechanism of the gel.
Microscopy helps to identify particle sizes, which have a
direct effect on perceived mouthfeel in systems that do not melt
in the mouth. Like with most imaging techniques, it has the risk
of creating artefacts during sample preparation. Creation of the
structured oil in the instrument circumvents this issue for fresh
samples, but for adulterated samples this is not always an
option. Moreover, special microscope designs permit visualisa-
tion of structural evolution under shear and temperature change
(Pernetti and Hartmann, unpublished data).
4.2. Thermodynamic properties
The thermal properties of structured oils not only disclose
information on temperature stability and melting point, but also
on the cooling sensation perceived during consumption. As
with the rheological data, it can be used for creating phase
diagrams. It helps to understand the kinetic and thermodynamic
nature of the processes involved, such as melting enthalpy and
activation energy for the start of crystallisation or gelling.
The amount of solids needed to achieve a certain firmness
may be taken as a measure for the efficiency of the structuring
agent, and reflects in part the microstructure of the oil gel.
Differential Scanning Calorimetry (DSC) data is regularly used
as an indicator for the amount of solids. The overall net energy
flow is recorded on a very small sample. It is less suited for
measuring very slow processes or processes involving very little
heat transfer. Due to sample size effects and polymorphism, this
technique is prone to artefacts, especially at very low amounts
of structurants. For the determination of solid TAG in oil, the
AOCS has recommended the NMR method [61]. As a note of
caution, it should be realised that the low-resolution NMR
technique will require adequate calibration when used for non-
TAG solids. Moreover, the NMR technique is the most reliable
in the mid to high percentage solids region, whereas the lower
concentration range is usually the most interesting in the context
of oil structuring. The NMR method is sensitive to fluctuations
of temperature and this should seriously be taken into account
when setting up measurements. Measurement of solids as a
function of temperature may be very helpful as a tool to optimise
melting profiles in these oil gels, a subject that has not been
investigated much yet.
4.3. Elucidation of structuring mechanisms
4.3.1. Crystallinity and crystal structure
On molecular level, solids have an amorphous, mono-
crystalline or multi-crystalline nature, which can be determined
using polarised light microscopy. The crystal morphology
provides information on underlying ordering of the molecules
and on the preferred growth directions of the crystal. Crystal
structures also reveal polymorphism, the existence of various
solids from the same material, but with different physical
properties. Standard X-ray powder diffraction is the most
suitable method to identify crystal structure or polymorph.
Although methods like DSC, NMR and IR have also been used
to identify polymorphism, this is only possible when that
particular system is very well known.
The molecular build up of crystalline particles can be
disclosed using X-ray diffraction (XRD). Unfortunately,
crystal structure determination requires single crystals that
are much larger than the typical crystals of lipids. The second
option is x-ray powder diffraction (XRPD). And although
powder structure determination is rapidly developing [62], it
requires high-resolution data, preferably from a synchrotron
source. In systems where combinations of structurants are
used, XRD may reveal whether mixed crystals provide synergy
[52] or that each component forms its own particles [56••].
Unfortunately there are currently no adequate techniques to
study the very first step in forming solids, the nucleation.
Although DSC and especially ultrasound allow the identifica-
tion of small particles in low concentrations, the techniques are
insufficiently sensitive to particles of the size of critical nuclei
[63]. Combinations like DSC-XRD boost the understanding of
growth mechanisms. A next step forward should come from
improved XRD sensitivity at low concentrations.
4.3.2. Morphology of building blocks and bridging elements
One length scale up from the molecules, the shape and size of
the building blocks becomes of interest. In some cases with very
small crystalline particles, XRD line broadening can be used for
a 3D mapping of crystal morphology [52]. On top of that,
micro-strains in the crystals may be disclosed.
More information is obtained through microscopy, as for
example it was used by Wright and Marangoni to confirm the
formation of thin birefringent fibrils [48••]. Studies of the un-
derlying texturing mechanisms require more advanced techni-
ques like Scanning or Transmission Electron Microscopy (SEM,
TEM), Atomic Force Microscopy (AFM), X-ray scattering and
combinatorial techniques, which are often less widely avail-
able. Cryo-TEM and -SEM are not strictly quantitative tech-
niques, but they allow the determination of the structure of the
building blocks in oil gels. It also is most suitable for direct
investigation of the bridging elements in a network, provided
the appropriate sample preparation techniques are used [45]. In
most other techniques, the properties of the building blocks
obscure those of the bridging elements and indirect conclusions
based on various techniques like rheology + XRD have to be
drawn [56•• ].
One should be aware that sometimes the used technique
influences the morphology, crystallisation and polymorphism,
especially when small amounts of sample are sandwiched
between glass or polyethylene layers, or when the solvent has to
be removed like in some EM applications. New developments
circumventing artefacts [45] and the destructive nature of the
sample taking would be welcome.
 M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231
4.4. Modelling structuring
Establishing the composition and structure of the links
between the building blocks of the network seems currently out
of experimental reach. To answer questions in this field, one
should probably revert to modelling techniques. At low
structurant concentrations, fractal models seem appropriate
[33]. In systems with higher concentration, which are the most
interesting for the final application, the fractal flocs become so
small that the fractal approach seems less useful. In these
systems, modelling based on sintering-type models seems more
appropriate (Schaink and van Malssen, unpublished data).
5. Conclusions and outlook
Currently most oil structuring systems are found through
serendipity or at best via screening exercises. This does not
allow a detailed understanding of the underlying mechanisms
and therefore it hinders the construction of desired structuring
systems. However, evaluating the discussed systems, a few
aspects stand out that might help the design of the optimal
systems.
First of all, the great majority of systems contain long
hydrocarbon chains, usually saturated or trans mono-unsaturat-
ed fatty acid groups. Apparently, these systems can order in a
way similar to TAGs, based on saturated fatty acids. The
examples in many cases contain stearic acid moieties or their
derivatives, and structuring seems based on the orientational
ordering of the hydrocarbon chains. However, as with TAG
structuring, it is likely that crystallisation of these systems will
also be possible with shorter or longer chain variants. In TAG
structuring, such modifications allow subtle changes in melting
profile of the structured oil, combined with subtle changes in
structuring effectiveness. Longer chains tend to have more
structuring potential per gram of material compared to shorter
chains. Further investigation of how these subtle variations in
the amounts and chain length of structurants modify thermal
and structural properties of structured oil systems seems of
interest.
The backbone connecting any fatty acids is apparently not
essential. Glycerol can be replaced by sorbitan, the backbone
can even be left out (structuring with pure fatty acids). The
number of fatty acid chains is apparently not essential:
structuring with TAGs, DAGs and MAGs is possible. The
prime requirement is the incomplete solubility of the structurant
in the TAG oil. It is seems likely that certain phospholipids or
sorbitan dialkylates will show an ability to structure TAG oils
too, provided that they are sufficiently insoluble too. A specific
aspect of systems based on the solubility of the structurant is
their thermoreversibility, which makes them appealing for some
applications.
The structurant should form small and preferably non-
spherical building blocks, in order to have a high specific
surface to form network connections. In this context, fibrillar
networks are most useful. Some systems form such small
particles naturally, as for fibril-forming systems. However, other
systems depend on kinetics to form such small particles. This is
229
for example the case for crystallising fat. It seems that in some
cases crystal habit modifiers have a very beneficial effect, and
some of the mixed structurant systems seem to be based on this
effect.
Two systems that seem to fall outside class of crystallite
networks are the ricinelaidic acid in canola oil at low
concentrations and the phytosterols + γ-oryzanol system. They
stand out because of their transparency, which was explained by
the formations of fibrils. Possibly, these fibrils are formed
because the components form a mesophase (e.g. tubular vesicles
[55]) before crystallising. In principle, structuring using fibrils
is a very efficient way to achieve firmness.
Finally, the system introduced by Romoscanu and Mezzenga
[59•• ] really falls outside the above classification. Here
structuring is not achieved by the formation of a network of
crystallised lipid-like material, but by dense packing of protein-
stabilised emulsion droplets and subsequent drying. The protein
at the surface of the droplets forms a network with ‘strong gel’
characteristics.
Although the present review addressed systems that show the
ability to structure pure oils, this feat is insufficient achieve-
ment in food applications. Of even greater interest is the struc-
turing of oil-continuous emulsions (and in specific cases water-
continuous emulsions), as many food products are emulsions.
Unfortunately, this will not be a straightforward application of
the present findings on oil structuring. Many of the systems
considered in this review contain structurants with the ability to
act as surfactants. The presence of interfaces, as in emulsions,
will interfere with the creation of building blocks as required
for oil structuring. Therefore, in most cases it will not be trivial
to translate these structuring options to emulsions, and refor-
mulation of the systems will be required.
Acknowledgements
This research is partially supported by a Marie Curie
Fellowship through the European Community programme
“Industry host" under contract number MCFH-2001-00857 and
by Casimir programme CIS4002. The authors thank Dr H.M.
Schaink for fruitful discussions and his contribution to Fig. 1.
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