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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


mechanical properties of the textured oil. Fast and deep cooling
The most common way to provide texture to the lipid phase stimulates the formation of large numbers of very small crystals,
of food products is by including a crystalline triacylglycerol which interact with strong ‘primary’ sintered connections and
(TAG) hardstock [1,2]. However, these hardstocks contain weak ‘secondary’ van der Waals bonds between the crystals.
major amounts of saturated fatty acids (SaFa), which are The mechanical network properties and thus the final product
considered unhealthy since their presence in the diet is among properties, can be tuned by processing via the ratio between
the factors contributing to cardio-vascular diseases [3,4]. The primary and secondary bonds. Exploiting the full range of TAGs
edible oil itself can be considered an organic solvent, mainly occurring in nature and all possibilities of processing enables the
consisting of unsaturated TAG. In view of reducing SaFa levels, design of networks with a wide range of firmnesses and melting
as well as finding new texturising properties, there is a broad profiles [1,2,5,6].
interest to find alternatives to the use of these TAG hardstocks, Finding alternatives to these high-SaFa TAG structurants that
which form the benchmark for oil structuring. provide the same level of performance and versatility is quite a
Saturated TAG hardstocks are widely applied and have been challenge, especially within the constraints imposed by the
studied in great detail. The saturated TAGs have a limited foreseen use in healthy foods. A deep understanding of the
solubility in the oil and upon cooling a hot melt, small crystals underlying behaviour of structurants in lipid phases is required
grow and form a network across the liquid. The actual size, shape to find such alternatives. Some materials have been found to be
able to structure organic solvents, of which edible oil is one. The
⁎ Corresponding author. Tel.: +31 10 460 6449; fax: +31 10 460 6000.
specific functionality of such building blocks depends on
E-mail address: arjen.bot@unilever.com (A. Bot).
solvent, processing and the presence of other ingredients.
1
Present address: GlaxoSmithKline Biologicals, Rue de l'Institut 89, B-1330 Many structuring solutions have been found through serendipity
Rixensart, Belgium. and have to be optimised empirically. Additional studies to
1359-0294/$ - see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2007.07.002
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- Fig. 1). The size and shape of the structuring elements and their
turing by design. This is relevant especially since some of the interactions will determine the final structure of the product, and
most interesting systems are built through mixed components. consequently its properties.
The present review aims to make a further step towards the
understanding of the structuring mechanism and the design of 2.1. Suspensions and emulsions
new systems. It starts with a broad overview on systems that
have been shown to structure organic phases. Subsequently, it A structured product can be obtained by dispersing a large
narrows down and describes in more detail systems that have amount of inert filler particles in the continuous phase. The
been shown to structure edible oil phases. Finally, it describes building blocks can be solid particles or aqueous droplets. If the
the approach that would help to further develop current under- volume fraction exceeds the close packing fraction, mechanical
standing, identifying the most appropriate analytical techniques contact between the particles will result in a network. However,
to be employed. if the volume fraction of the dispersed phase is lower, aggre-
gation through weak physical bonds or as a result of partial
2. Structuring concepts and building blocks coalescence is required to ensure an increase in viscosity or
firmness of the product as a whole. In food, one example is
The structuring of organic phases has received considerable peanut butter, which is composed of about 50% solid non-fat
attention already outside the field of food science. The present particles and 50% peanut oil. Its structure is due to the high
section is aimed at identifying solutions that have been amount of dispersed phase and only partially to the amount of
proposed in this wider context, which has far fewer restrictions hardstock (only 1–2% triglycerides) [7,8]. The disadvantage of
than food applications. Generally, two routes can be found: (i) dispersed systems is that generally a high amount of structurant
dispersion of a foreign phase (small inert particles, crystallised needs to be added.
solids, separated droplets); (ii) specific molecular mechanisms,
such as self-assembly (regularly observed with low-molecular 2.2. Networks
weight organogelators). These routes provide the “structuring
elements”, which act as building blocks for the three- Another way to create structure is by using ingredients with
dimensional networks that are required to structure oil (see 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 [5,6], and their interactions determine the mechanical properties
practice, ingredient cost will be relevant too. of the network [33]. At sufficiently high concentration, the
• The structurants should gel edible oils at chilled and ambient networks are usually relatively firm and their melting behaviour
temperatures (i.e. between 5 and 25 °C) to make them can be tuned by choosing the fatty acid profile for the TAG phase
relevant for food applications. optimally.
Besides the regular firm network that is usually produced,
Despite these limitations, considerable progress has been TAGs can be used also to make a flowable texture by mixing
made in this field over the last few years. A rather large number high melting and low melting TAGs [34•,35,36]. The high
of systems have been identified that are capable of structuring melting fats directly form stable β crystals that aggregate to
TAG oil phases. Combining these results, this review will form flocs, but not enough to span the container. Thus, a space-
outline an overall picture of the requirements for non-TAG filling dispersion of crystals is formed. For this type of structure
structuring of edible oils. no alternatives have been found yet.
The subsequent paragraphs will discuss single or mixed
compounds with the ability to gel TAG oil. In most cases, the 3.1.2. Diacylglycerol (DAG or diglyceride)
trivial names for alkyl groups will be used, but Table 1 provides The next member in the family of acylglycerols is DAG,
the relevant systematic nomenclature. The structurants are listed which received most attention until now for its influence on TAG
below starting from those that are chemically closest to crystallisation. Surprisingly little attention has been given to
crystalline TAGs which are mentioned first, down to the ones separate structuring through DAG. Dipalmitin and distearin
that are more different, which are mentioned later. The rationale form crystallite networks in a relatively similar way as TAGs
behind the classification used can be inferred from Fig. 2. (van Malssen and Bot, unpublished data). The gels are slightly
soft compared to TAG crystal networks of similar concentration.
3.1. TAGs, DAGs and MAGs
3.1.3. Monoacylglycerol (MAG or monoglyceride)
3.1.1. Triacylglycerol (TAG or triglyceride) MAGs are among the rare components that can structure both
Structuring with crystalline TAG is the benchmark for edible lipid [37,38••,64] and aqueous phases [39–42]. MAGs are
oil2 structuring. TAGs rich in saturated or trans-monounsatu- thought to form reversed bilayers in TAG oils [37,38••], Ojijo
rated fatty acids have a limited solubility in edible oils, which are et al. showed that mixtures of monopalmitin and monostearin
rich in short chain and/or unsaturated fatty acids. The crystalline form networks under quiescent cooling in olive oil at low con-
TAG forms a network of small crystals in the oil. The size and centrations [37,38••]. Faster cooling provides gels with higher
shape of the crystals can be controlled by shear and cooling rate firmness, but generally lower elastic modulus. Staged crystal-
lisation could explain this phenomenon: at low cooling rates, the
2
Commonly, oil is the liquid TAG phase and fat the solid TAG phase at first crystallising MAGs form a ‘backbone’ network, on which
ambient temperature. the remaining MAG deposit subsequently; at high cooling rates,
M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231 225

numerous fine crystals are formed in a single crystallisation step. Possibly, a similar explanation involving large but unconnected
In terms of primary and secondary bonds the balance might shift dispersed aggregates is applicable here.
towards stronger primary bonds at lower cooling rates and more Oils with a considerable amount of free hydroxyl-groups
numerous secondary bonds at higher cooling rates. Crystal- (sesame oil, DAG oil) could not be gelled. This suggests that
lisation in stages leads to more weak spots, increasing firmness hydrogen bonding is important in these systems.
failure, whilst increasing resistance to small deformations. Derivatised fatty acids with additional hydroxyl or methyl
The application of shear at or above the gel point for groups were investigated by Daniel and Rajasekharan [47••].
quiescent crystallisation leads to finer homogeneous gels at The single hydroxyl group in 12-hydroxystearic acid is found to
lower temperatures. This suggests that shear disturbs the initial be the most efficient in enhancing gelation. Short dicarboxylic
stage of crystallisation for example by modifying the meso- acids (adipic, suberic and sebacic acid) were found to structure
phases present above the melting temperatures of the crystallites much better than their mono-carboxylic counterparts and with
[37]. relatively high melting points (80 to 145 °C).
During weeks of storage with temperature cycling, the Although the crystal structure of pure fatty acids is known
firmness of these networks increases, whilst the melting onset for a long time [50,51], there is little mentioning of which
decreases [38••]. Since no increase in crystallinity is observed, polymorph is present in gelled oil. Schaink et al. reported that
the changes could be explained by a reorganisation of the net- stearic acid structures sunflower oil by means of rather thick
work building blocks, for example by strengthening of primary crystals and XRD patterns indicating an orthorhombic structure
bonds due to the dynamic equilibrium of dissolved MAG in the similar to β′-type TAG crystals [52]. Wright and Marangoni
oil, as can be observed in TAG networks too [5]. reported the molecular ordering of the ricinelaidic acid crystal-
lites in oil to be quite similar to the one in neat ricinelaidic acid,
3.2. Fatty acids, fatty alcohols, waxes, and sorbitan alkylates but the packing seems slightly more compact in the organogel
[48••].
3.2.1. Fatty acids (FA)
Fatty acids, and especially fatty acid salts (i.e. soaps), have 3.2.2. Fatty alcohols
served as the prototype for structuring of oil phases. Here we Gandolfo et al. found that the fatty alcohols palmityl, stearyl,
will not consider the soaps (e.g. Tamura et al. [43]), as their arachyl and behenyl alcohol provide firmness to sunflower oil at
application lays more in the personal care area, rather than in concentrations above ∼ 2% at 5 °C [46 • ]. Daniel and
foods. Elliger et al. were the first who mentioned the oil struc- Rajasekharan investigated the gelation of sunflower oil by
turing potential of 12-hydroxystearic acid in a study on the means of even longer fatty alcohols, with chain lengths in the
thickening of peanut butter [44]. For many years this remained range of 22–30 [47••]. These ingredients structure the oil at
the prime example of edible oil structured by a fatty acid, and is concentrations of 3–4%. The gel melting temperature increases
still subject of investigation [45]. from 40–45 °C for behenyl alcohol to 55–60 °C for tricontanol.
Gandolfo et al. investigated palmitic, stearic, arachidic and In oils that are relatively rich in saturated fatty acids (soy bean
behenic acid, and established oil structuring ability in sunflower oil or olive oil vs sunflower oil or rapeseed oil) a synergistic
oil above ∼ 2% at 5 °C [46•]. Daniel and Rajasekharan effect between the oil and the fatty alcohols is observed [46•].
investigated an even wider range of fatty acids, showing that the Schaink et al. demonstrated that stearyl alcohol structures the
amount required to structure oil does not decrease much further oil by means of quite thick crystals and with an orthorhombic
with chain lengths up from 31 [47••]. One can hypothesize that packing and orthogonal chain stacking [52].
the amount of solids is more or less constant for these chain
lengths. The melting temperature of the gels goes up from about 3.2.3. Waxes and wax esters
40 to 70 °C. Daniel and Rajasekharan showed that the structuring
Structuring is possible with trans-monounsaturated fatty acids potential of saturated wax esters (behenic acid esterified with
as well. Wright and Marangoni confirmed the gelation of 14–22 chain length alcohols) in TAG oil is similar to their fatty
rapeseed oil with at least 0.5% of ricinelaidic acid, the trans- acid counterparts [47].
unsaturated counterpart of 12-hydroxystearic acid [48••,49]. Toro-Vazquez et al. [53] established the oil structuring prop-
Transparent gels were formed with 0.5–1% structurant in canola erty of candelilla wax in safflower oil at concentrations of ∼1%
oil, suggesting gel building blocks with small dimensions and higher [53]. Candelilla wax consists mainly of C29–C33 odd
compared to the wavelength of visible light. Microscopy confirms length alkanes, and has food grade status in special applications.
the formation of thin (birefringent) fibrils [48••]. The work by Toro-Vazquez emphasised mainly thermodynamic
Rheological assessment of the gels confirms that these are properties, and less details of the structuring mechanism.
strong gels except at very low concentrations. Simple power-
law scaling rules can be formulated for these systems, but the 3.2.4. Sorbitan monostearate (SMS)
description is not universal over the whole time and temperature SMS forms viscous dispersions in edible oils. The viscosity
range. It is possible to create a thickened but not gelled phase increases with increasing concentration until a gel is formed. The
with ricinelaidic acid in unrefined sesame oil [48••]. These threshold concentration depends on the specific oil; 10% SMS
systems bear some rheological similarity to the mixed high- and gives a firm opaque gel in vegetable oil [54]. Although most
low-melting TAGs described by Higaki et al. [34•,35,36]. 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 increased nucleation rate due to a reduction in the interfacial
vesicles [55] just above the melting point of the SMS in the energy of the nuclei [46•]. Schaink et al. demonstrated through
organic phases, which shows most agreement with the TAG oil. XRD that for the 3:7 ratio very small crystals of a different
Murdan et al. suggest that the surfactant molecules are organised crystal packing are formed [52]. The crystallographic short
as inverse bilayers in the tubules [54]. The tubular vesicles can spacings suggest a packing similar to a TAG β-polymorph.
associate to form an opaque three-dimensional network. These
gels are thermoreversible and melt at ∼ 40 °C. 3.3.2. Lecithin + sorbitan tristearate (STS)
STS shows some molecular similarity to TAGs, the glycerol
3.3. Structuring mixtures backbone being replaced by sorbitan (see Fig. 2). In TAG oil STS
forms regularly shaped crystals that melt at ∼40 °C. Neither STS
From TAG structuring, it is known that mixtures of nor lecithin structures TAG oil by themselves. Addition of STS
ingredients can outperform pure hardstocks. Potential synergis- and lecithin to a TAG oil at ratios between 40:60 and 60:40 leads to
tic effects in non-TAG structuring mixtures are therefore of the formation of fine, needle-shaped crystals. X-ray diffraction
considerable interest. shows that lecithin does not affect the crystal structure. The
needles still consist of STS and the lecithin mainly changes the
3.3.1. Fatty acids + fatty alcohols morphology of the crystals [56••]. In addition, rheological
Long-chain fatty acids and fatty alcohols cannot only measurements in Fig. 3 seem to prove that the lecithin helps to
structure edible oils by themselves, but also in combination create a weak interaction between the crystals, STS crystals them-
[46•,52]. Upon quiescent cooling, these systems form homo- selves having no tendency to aggregate (Pernetti and Hartmann,
geneous, opaque gels consisting of a particle dispersion at unpublished data). The mixture forms a gel at concentrations
concentrations above ∼ 2% of the structurants. The strain at above ∼4%. The gel is shear sensitive and collapses above 20 °C,
breaking is ∼ 10% [52]. The gels are observed for mixtures in though like other organogels it is perfectly thermoreversible.
which the fatty alcohol and the fatty acid have the same chain
length (16 to 22), and in mixtures of stearic acid with fatty 3.3.3. Phytosterols + oryzanol
alcohols of different chain length (16 to 22). It is expected that A group of materials not containing any long fatty acid
other chain lengths, not yet studied, will also result in gelled oil. chains was studied by Bot and Agterof [57••] and consists of
An interesting aspect of these systems is the synergistic mixtures of γ-oryzanol and phytosterols (e.g. cholesterol,
effect for the firmness at specific acid:alcohol ratios. Specifi- dihydrocholesterol, β-sitosterol and stigmasterol). The ratio is
cally around 30% stearic acid + 70% stearyl alcohol mixtures, not critical, but optimal molar ratios are approximately 1:1.
firmness is much higher than at other ratios with the same These gels probably belong to the wider class of cholesterol-
overall level of structurants [46•,52]. Microscopic evidence based organogels [58]. About 2–4% of structurant is required to
suggests that this mixture forms the smallest crystals, as has form a gel at 5 °C. The gels have a slippery surface, but are quite
been confirmed by images of needle-like crystals in gels [52]. firm under compression: At 5–10% structurant, their mechan-
Gandolfo et al. explained the synergistic effect through an ical properties approach those of a block of fat.

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).
M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231 227

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
Fig. 4. An He–Ne laser beam shining through a transparent β-sitosterol+γ-oryzanol influence of processing and selected ingredients.
organogel. The gel has been taken out of its container and is quite firm and self- The mechanical properties of the network determine its po-
supporting. 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-
The gels are transparent, as is illustrated in Fig. 4. This plied. Studies of the underlying texturing mechanisms require
implies that the gel building blocks are considerably smaller more advanced techniques like Transmission and Scanning
than the wavelength of visible light. The oil + structurant Electron Microscopy (TEM, SEM), Atomic Force Microscopy
mixture is easily supercooled without gel formation and some (AFM), X-ray scattering and combinatorial techniques, which are
mechanical disturbance seems necessary to form firm gels. often less widely available. Analytical methods necessary to
Probably the building blocks are pronounced non-spherical, e.g. obtain good quality data on chemical sample composition, al-
thin fibrils. Such fibrils are observed for many of the though very important, are beyond the scope of this review.
cholesterol-based organogels [58].
A molecular energy minimisation calculation (Fig. 5) 4.1. Mechanical properties
suggests that the γ-oryzanol and β-sitosterol molecules dock
their sitosterol units on top of each other, with the ferulic acid In practice, edible oils are structured to provide products with
moiety of the γ-oryzanol sticking out. The stacking on a specific consistency and firmness. Until now, in most papers on
molecular scale does not predict how many of these molecules oil structuring, mainly three types of rheological measurements
assemble, but the slight wedge shape of the stacked molecules have been used, next to visual assessment. These techniques are
would leave room for a curved supramolecular structure. Such commonly available and widely applied. A texture analyzer
curvature would be consistent with the formation of fibrils. It is using a cylindrical probe (e.g. [46•]) gives a fast characterisation,
still unclear, however, whether the crystalline fibrils would form but is not suitable for a more fundamental analysis of the me-
directly from the solution, or rather via an intermediate tubular chanical network properties. Small deformation rheology yield-
micelle. ing storage and loss moduli [56••,57••] is more suitable for
comparisons between different materials [60]. In the end, how-
3.4. Protein structuring ever, large deformation studies involving amongst others the
plasticity of the structured oil and the ability to reform after
An interesting and completely alternative approach to oil shearing are more relevant to the application [57••]. In combi-
structuring was taken by Romoscanu and Mezzenga [59••]. nation, these studies give a proper fingerprint of the obtained gel.
They produced a space-filling emulsion of very monodisperse Rheological properties can also be used to assess the stability
protein-stabilised droplets and subsequent cross-linked the of the microstructure during storage or during temperature
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
Fig. 5. Proposed stacking of sitosterol and oryzanol molecules, based on a crude
reversibility of the process is better for very pure oils, and less energy minimisation calculation (RM Hermant, Unilever R&D, unpublished
for e.g. virgin olive oil. This is explained by the occurrence of data). An H-bridge can be formed near to the arrow, resulting in slightly wedge
interdroplet cross-linking in the emulsion based on less pure oil. 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 provides information on underlying ordering of the molecules
contribute to the identification of recrystallisation or reorgani- and on the preferred growth directions of the crystal. Crystal
sation phenomena in the structurant network, or be used to structures also reveal polymorphism, the existence of various
construct phase diagrams. A careful analysis of all rheological solids from the same material, but with different physical
data (as a function of temperature, concentration, applied strain, properties. Standard X-ray powder diffraction is the most
etc.) in combination with results of other techniques may help to suitable method to identify crystal structure or polymorph.
answer questions concerning the cross section of fibres, the type Although methods like DSC, NMR and IR have also been used
and structures of the junction zones, and the microscopic failure to identify polymorphism, this is only possible when that
mechanism of the gel. particular system is very well known.
Microscopy helps to identify particle sizes, which have a The molecular build up of crystalline particles can be
direct effect on perceived mouthfeel in systems that do not melt disclosed using X-ray diffraction (XRD). Unfortunately,
in the mouth. Like with most imaging techniques, it has the risk crystal structure determination requires single crystals that
of creating artefacts during sample preparation. Creation of the are much larger than the typical crystals of lipids. The second
structured oil in the instrument circumvents this issue for fresh option is x-ray powder diffraction (XRPD). And although
samples, but for adulterated samples this is not always an powder structure determination is rapidly developing [62], it
option. Moreover, special microscope designs permit visualisa- requires high-resolution data, preferably from a synchrotron
tion of structural evolution under shear and temperature change source. In systems where combinations of structurants are
(Pernetti and Hartmann, unpublished data). used, XRD may reveal whether mixed crystals provide synergy
[52] or that each component forms its own particles [56••].
4.2. Thermodynamic properties Unfortunately there are currently no adequate techniques to
study the very first step in forming solids, the nucleation.
The thermal properties of structured oils not only disclose Although DSC and especially ultrasound allow the identifica-
information on temperature stability and melting point, but also tion of small particles in low concentrations, the techniques are
on the cooling sensation perceived during consumption. As insufficiently sensitive to particles of the size of critical nuclei
with the rheological data, it can be used for creating phase [63]. Combinations like DSC-XRD boost the understanding of
diagrams. It helps to understand the kinetic and thermodynamic growth mechanisms. A next step forward should come from
nature of the processes involved, such as melting enthalpy and improved XRD sensitivity at low concentrations.
activation energy for the start of crystallisation or gelling.
The amount of solids needed to achieve a certain firmness 4.3.2. Morphology of building blocks and bridging elements
may be taken as a measure for the efficiency of the structuring One length scale up from the molecules, the shape and size of
agent, and reflects in part the microstructure of the oil gel. the building blocks becomes of interest. In some cases with very
Differential Scanning Calorimetry (DSC) data is regularly used small crystalline particles, XRD line broadening can be used for
as an indicator for the amount of solids. The overall net energy a 3D mapping of crystal morphology [52]. On top of that,
flow is recorded on a very small sample. It is less suited for micro-strains in the crystals may be disclosed.
measuring very slow processes or processes involving very little More information is obtained through microscopy, as for
heat transfer. Due to sample size effects and polymorphism, this example it was used by Wright and Marangoni to confirm the
technique is prone to artefacts, especially at very low amounts formation of thin birefringent fibrils [48••]. Studies of the un-
of structurants. For the determination of solid TAG in oil, the derlying texturing mechanisms require more advanced techni-
AOCS has recommended the NMR method [61]. As a note of ques like Scanning or Transmission Electron Microscopy (SEM,
caution, it should be realised that the low-resolution NMR TEM), Atomic Force Microscopy (AFM), X-ray scattering and
technique will require adequate calibration when used for non- combinatorial techniques, which are often less widely avail-
TAG solids. Moreover, the NMR technique is the most reliable able. Cryo-TEM and -SEM are not strictly quantitative tech-
in the mid to high percentage solids region, whereas the lower niques, but they allow the determination of the structure of the
concentration range is usually the most interesting in the context building blocks in oil gels. It also is most suitable for direct
of oil structuring. The NMR method is sensitive to fluctuations investigation of the bridging elements in a network, provided
of temperature and this should seriously be taken into account the appropriate sample preparation techniques are used [45]. In
when setting up measurements. Measurement of solids as a most other techniques, the properties of the building blocks
function of temperature may be very helpful as a tool to optimise obscure those of the bridging elements and indirect conclusions
melting profiles in these oil gels, a subject that has not been based on various techniques like rheology + XRD have to be
investigated much yet. drawn [56•• ].
One should be aware that sometimes the used technique
4.3. Elucidation of structuring mechanisms influences the morphology, crystallisation and polymorphism,
especially when small amounts of sample are sandwiched
4.3.1. Crystallinity and crystal structure between glass or polyethylene layers, or when the solvent has to
On molecular level, solids have an amorphous, mono- be removed like in some EM applications. New developments
crystalline or multi-crystalline nature, which can be determined circumventing artefacts [45] and the destructive nature of the
using polarised light microscopy. The crystal morphology sample taking would be welcome.
M. Pernetti et al. / Current Opinion in Colloid & Interface Science 12 (2007) 221–231 229

4.4. Modelling structuring for example the case for crystallising fat. It seems that in some
cases crystal habit modifiers have a very beneficial effect, and
Establishing the composition and structure of the links some of the mixed structurant systems seem to be based on this
between the building blocks of the network seems currently out effect.
of experimental reach. To answer questions in this field, one Two systems that seem to fall outside class of crystallite
should probably revert to modelling techniques. At low networks are the ricinelaidic acid in canola oil at low
structurant concentrations, fractal models seem appropriate concentrations and the phytosterols + γ-oryzanol system. They
[33]. In systems with higher concentration, which are the most stand out because of their transparency, which was explained by
interesting for the final application, the fractal flocs become so the formations of fibrils. Possibly, these fibrils are formed
small that the fractal approach seems less useful. In these because the components form a mesophase (e.g. tubular vesicles
systems, modelling based on sintering-type models seems more [55]) before crystallising. In principle, structuring using fibrils
appropriate (Schaink and van Malssen, unpublished data). is a very efficient way to achieve firmness.
Finally, the system introduced by Romoscanu and Mezzenga
5. Conclusions and outlook [59•• ] really falls outside the above classification. Here
structuring is not achieved by the formation of a network of
Currently most oil structuring systems are found through crystallised lipid-like material, but by dense packing of protein-
serendipity or at best via screening exercises. This does not stabilised emulsion droplets and subsequent drying. The protein
allow a detailed understanding of the underlying mechanisms at the surface of the droplets forms a network with ‘strong gel’
and therefore it hinders the construction of desired structuring characteristics.
systems. However, evaluating the discussed systems, a few Although the present review addressed systems that show the
aspects stand out that might help the design of the optimal ability to structure pure oils, this feat is insufficient achieve-
systems. ment in food applications. Of even greater interest is the struc-
First of all, the great majority of systems contain long turing of oil-continuous emulsions (and in specific cases water-
hydrocarbon chains, usually saturated or trans mono-unsaturat- continuous emulsions), as many food products are emulsions.
ed fatty acid groups. Apparently, these systems can order in a Unfortunately, this will not be a straightforward application of
way similar to TAGs, based on saturated fatty acids. The the present findings on oil structuring. Many of the systems
examples in many cases contain stearic acid moieties or their considered in this review contain structurants with the ability to
derivatives, and structuring seems based on the orientational act as surfactants. The presence of interfaces, as in emulsions,
ordering of the hydrocarbon chains. However, as with TAG will interfere with the creation of building blocks as required
structuring, it is likely that crystallisation of these systems will for oil structuring. Therefore, in most cases it will not be trivial
also be possible with shorter or longer chain variants. In TAG to translate these structuring options to emulsions, and refor-
structuring, such modifications allow subtle changes in melting mulation of the systems will be required.
profile of the structured oil, combined with subtle changes in
structuring effectiveness. Longer chains tend to have more Acknowledgements
structuring potential per gram of material compared to shorter
chains. Further investigation of how these subtle variations in This research is partially supported by a Marie Curie
the amounts and chain length of structurants modify thermal Fellowship through the European Community programme
and structural properties of structured oil systems seems of “Industry host" under contract number MCFH-2001-00857 and
interest. by Casimir programme CIS4002. The authors thank Dr H.M.
The backbone connecting any fatty acids is apparently not Schaink for fruitful discussions and his contribution to Fig. 1.
essential. Glycerol can be replaced by sorbitan, the backbone
can even be left out (structuring with pure fatty acids). The References and recommended reading•,••
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••
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