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Current Opinion in Colloid and Interface Science 8 (2003) 365–370

Egg yolk protein gels and emulsions


V. Kiosseoglou*
Laboratory of Food Chemistry and Technology, School of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece

Abstract

Egg yolk remains a key ingredient of a number of food products. Yet, its main functional properties, e.g. emulsifying ability
and gel structure formation, upon heating, have not attracted the attention of too many researchers specializing in the area of food
colloids. It is not surprising then that there have been only very few major advances in the field over the period of the last few
years. These are discussed in the present review and include recent research findings on competitive adsorption between yolk
protein constituents at emulsion oil–water interfaces, and also on the relationship between yolk particle supermolecular structure
disorganization and the rheological properties of yolk-based emulsions and gel-network structures.
䊚 2003 Elsevier Ltd. All rights reserved.

Keywords: Yolk proteins; Adsorption; Gel formation; Rheological properties; Low density lipoproteins; Granules

1. Introduction subject are rare. Kiosseoglou w1x reviewed yolk chem-


istry and functionality, while structure network formation
Hen’s egg yolk can be found in a number of food by yolk, upon heating, was examined in a review by
products such as mayonnaise and salad dressings, in Woodward w2x covering egg gelation. Both reviews
general, bakery products and cakes, custard, etc., being appeared some 10 or so years ago. Paraskevopoulou and
an ingredient of high nutritional value with unique Kiosseoglou w3x very recently reviewed the functionality
sensory characteristics and excellent functionality. Thus, of yolk protein concentrates prepared by extracting
the preparation and stability of yolk-based products cholesterol and other lipids. A recent review on egg
depend to a large extent on yolk constituent ability, protein, both of albumen and yolk, was published by
either to adsorb at oyw interfaces and form a strong and Mine w4●x. The present work focuses on some aspects
cohesive film around oil droplets that stabilizes them of yolk functionality related to the role of isolated major
against coalescence, in the case of foods appearing in yolk fractions such as plasma (LDL and livetins) and
the form of emulsions (e.g. mayonnaise), or to interact, granules (HDL and phosvitin) in the stabilization of
following heat treatment, and form network structures oyw emulsions or in gel network formation. Emphasis
exhibiting viscoelasticity in products such as creams and is placed on the functional behaviour of yolk proteins
omelet. During the preparation of certain products, e.g. since, as it appears from recent research findings, they
cakes, yolk constituents may have to function as emul- are the dominant yolk constituents in determining the
sifiers and foaming agents as well as network structure
material’s functional properties. The majority of proteins
formers. Cake batter is a mixed colloidal system of an
in yolk are organized into micellar and granular struc-
emulsion, a foam and a suspension that, during baking,
tures together with polar and non-polar lipid molecules.
is transformed into a solid foam, the cake, exhibiting
Yolk functionality appears to depend on the type of
unique textural characteristics.
Although, however, yolk is a key ingredient of many particle supermolecular structure (micellar or granular),
food systems, its functional properties have not received and also on the extent of structural disorganization
the attention they deserve, possibly due to the material’s brought about by treatments such as pasteurization or
complicated composition and structure. Reviews on the lipid extraction. One aspect of yolk functionality, there-
fore, that deserves attention is the effect of the degree
*Tel.: q30-231-0-997834; fax: q30-231-0-997779. of supermolecular structure disorganization, and this
E-mail address: kiosse@chem.auth.gr (V. Kiosseoglou). point will also be discussed in the review.

1359-0294/03/$ - see front matter 䊚 2003 Elsevier Ltd. All rights reserved.
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366 V. Kiosseoglou / Current Opinion in Colloid and Interface Science 8 (2003) 365–370

2. Yolk protein gelation

Yolk coagulation or gelation, as a result of heating, is


an important functional property of the ingredient in the
preparation and texture modification of food products
such as sauces, creams, cakes, omelet, confectionery,
etc. Gel network structure formation by yolk is attributed
to its constituent protein denaturation, leading to molec-
ular interactions and the development of a hard and
rubbery structure w5x. Although the general theoretical
model, regarding gel network formation in the case of
heated protein solutions w6x, can be adopted to describe
the mechanism of yolk protein gelation, one should bear
in mind that yolk is not a pure protein solution, but
rather a dispersion of particles (LDL micelles and HDL
granules), where the neutral triglycerides are buried in
the particle interior, while the proteins dominate the
particle surface and in this way stabilize the system w3x.
The gelation of yolk, therefore, can be envisaged as a
process of particle destabilization brought about by
denaturation, upon heating, of particle-stabilizing yolk Fig. 1. Development of G9, following heating to 75 8C and cooling to
protein molecules, leading to an interparticle network 5 8C, as a function of protein concentration for spray dried yolk (h)
formation. The system in this respect resembles that of and for yolk protein concentrates prepared by extraction with etha-
nolywater (d) or petroleum etheryethanol (m). Sample lipid content:
a protein-stabilized concentrated emulsion that gels fol- spray dried yolk: 60%, extracted with ethanolywater: 32.2%, extracted
lowing heat treatment. with petroleum etheryethanol: 6.5% (wyw). Frequency: 1.5 Hz; strain:
Apolipoproteins of LDL micelles appear to dominate 0.2 (from Ref. w9x).
the process of yolk gelation. As reported by Anton et
al. w7●●x similar gelation patterns were followed by a 20, exhibit higher fracture stress values w11x probably
yolk plasma solution and liquid yolk, while the granules as a result of excluded volume effects andyor surfac-
exhibited a completely different behaviour and were less tant–apolipoprotein interactions. A similar behaviour
effective as gel network formation agents. This differ- was also observed for pure proteins such as b-lactoglob-
ence in behaviour, according to the authors, should be ulin by Dickinson and Hang following addition of Tween
the result of the more labile nature of LDL micelles and w12x.
of the ease with which micellar apolipoprotein and The presence of native yolk lipids or fat incorporated
livetin molecules denature at relatively low temperatures. in the form of emulsified oil droplets appears to influ-
Granular proteins, on the other hand, are less sensitive ence the yolk gel rheological properties but in a different
to heat, a behaviour attributed to their more globular way. Yolk protein concentrates having a relatively high
structure and to complexes between high density apoli- lipid content produce gel networks at low protein con-
poprotein molecules and phosvitin in the granular struc- centrations and full-fat spray-dried yolk forms weak gels
ture w8x. even at very low protein levels (1.9% wyv) suggesting
Heat treatments similar to those applied during spray- that the yolk lipid molecules are somehow involved in
drying may also destabilize particle supermolecular gel structure formation w9x (Fig. 1). Emulsified oil
structure leading yolk dispersions in water to exhibit droplets of an average size of 1 mm, on the other hand,
‘weak’ gel properties. A similar behaviour was observed act as inactive fillers of egg yolk gels. A plausible
for yolk protein concentrates obtained by lipid extraction explanation of this effect is that the LDL micelles of
of yolk w9x. The ‘weak’ gel network at room tempera- plasma that dominate the gelation process of yolk and
tures, where physical forces dominate protein interac- their apolipoproteins, which are over-represented at the
tions, turns into a real gel, probably due to protein oil–water interface, as a result of their flexibility, cannot
denaturation and the development of covalent disulfide be involved in cross-links to enhance protein–oil droplet
forces between interacting molecules w10x. interactions due to orientation of their hydrophobic
Another aspect of yolk protein gelation behaviour that groups towards the oil phase w7●●x.
deserves attention is the way it is modulated by the
presence of low-molecular weight compounds, particu- 3. Yolk proteins at oyw interfaces
larly emulsifiers. Yolk protein gelation is influenced by
hydrophilic surfactants such as Tween and gels produced The preparation and long-term stability of food emul-
upon heating of spray-dried yolk, in presence of Tween sions such as mayonnaise, salad creams and egg-based
V. Kiosseoglou / Current Opinion in Colloid and Interface Science 8 (2003) 365–370 367

sauces and creams depend to a significant extent on egg LDL concentration, a result that emphasizes the role of
yolk constituent ability to aid in the reduction of protein–lipid interactions in the development of
interfacial tension between the two phases, resulting in adsorbed yolk lipoprotein films around the oil droplets.
a fine dispersion and form an adsorbed film around the Most of the research papers published in the last 1–
oil droplets that offers protection against coalescence 5 years stressed the importance of micellar apolipopro-
and ultimate phase separation during prolonged storage. teins in the development of adsorbed films around the
The composition and fine structure of adsorbed pure oil droplets of yolk-based emulsions, along with other
protein films, the interfacial rheological properties and yolk proteins (livetins, granular apolipoproteins and
their influence on colloidal stability have been the phosvitin) w21,22x although there is one paper w23x
subject of considerable debate over the last two decades, reporting that granular lipovitellines are the main com-
and although some progress has been achieved in this ponents found at the interface in spite of the granule
area there are still many points that require clarification, low solubility, under low ionic strength conditions.
one of them being the connection between the adsorbed Since, however, yolk protein adsorption at oyw inter-
film properties with the stability of the bulk systems faces depends on parameters such as pH and NaCl
w13x. This situation becomes even more complicated in concentration, homogenization conditions, etc., it is not
the case of egg yolk proteins, which constitute a very surprising that the relative contribution of yolk protein
diverse mixture of molecules differing both in structure constituents to the formation of adsorbed films may
and flexibility. Furthermore, approximately 90% of these differ as stressed by LeDenmat et al. in a recent paper
proteins are organized into supermolecular structures w24●●x. Granular protein adsorption in oyw emulsions
exhibiting marked differences in size, structure stability depends heavily on pH, and emulsions of pH 4 exhibit
and composition. a higher protein surface load than that of pH 7 or 9.
Melnikov w14●●x applied dynamic drop tensiometry to This was attributed to lipoprotein dimer formation at the
determine the kinetics of yolk adsorption at the oyw acidic pH w25x. Compared with phosvitin, granule lipo-
interface and the viscoelastic modulus as they are proteins are more surface active and displace the former
influenced by the solution pH. His observation shows more effectively at neutral pH than at pH 4.0, a fact
that interfacial tension reaches a minimum at pH values that emphasizes the importance of phosvitin negative
close to the isoelectric region of yolk proteins, which charge in determining its affinity to the oyw interface
was also reported in a previous study by Anton and w26x. According to Anton et al. w27x, granules may
Gandemer w15x, a fact that points to the role of protein adsorb either in their native form or after disruption,
charges in determining yolk protein adsorption. Accord- following NaCl addition. Disrupted granules are more
ing to Melnikov, however, the pH does not appear to effective in producing finer and more homogeneous
influence the viscoelasticity of egg yolk interfacial films. emulsions.
Egg yolk constituent adsorption at the oyw interface One interesting aspect of yolk protein adsorption is
occurs in a step-wise manner indicating that substantial their tendency to displace other proteins of a more
molecular interactions, rearrangements and partial globular nature from the interface. Thus, yolk proteins
replacement of various protein fractions may take place being highly surface active can very effectively displace
leading to modification of film structure and viscoelas- milk proteins from emulsion interfaces. Both whey
ticity. This was expected since, when the components proteins w28●x and caseinate w29x may be displaced by
of a diverse mixture of proteins, differing in molecular LDL or granule lipoproteins in emulsions, depending on
structure and flexibility, compete for space at oyw the nature of oil phase. This is attributed to the high
interface with low-molecular weight surface-active mol- penetrating ability of yolk lipoprotein molecules.
ecules such as phospholipids and cholesterol, competi- Finally, cholesterol removal from yolk may influence
tive adsorption will take place, that requires time for the lipoprotein adsorption behaviour. Thus, cholesterol
equilibrium to be reached. extraction from LDL results in thicker adsorption films
Yolk LDL micelles, due to their rather unstable nature, around the oil droplets of emulsions, due to apoprotein
are easily disorganized when they come into contact aggregation w30x. The adsorption behaviour of low-in-
with oil droplet surfaces, and their apolipoprotein con- cholesterol yolk depends on the method of lipid extrac-
stituents adsorb and spread readily at the interface aided tion and was attributed to structural changes of yolk
in this by their high structure flexibility w16,17●,18–20x. proteins brought about by the extraction process w31x.
According to Mine w17●x, preferential adsorption occurs
between the micellar protein constituents, and as a result 4. Stability and rheology of egg yolk emulsions
of this three LDL-polypeptides (64, 43 and 19 kDa) do
not adsorb at all at the interface. Additionally, phospho- Properties of protein-based emulsions such as long-
lipid and cholesterol adsorption depends on LDL con- term stability and rheological behaviour and texture are
centration with the ratio of phosphatidylcholine over intimately related to interactions taking place among
phosphatidyl-ethanolamine increasing with increasing adsorbed protein molecules either within the interfacial
368 V. Kiosseoglou / Current Opinion in Colloid and Interface Science 8 (2003) 365–370

tion. Spray-dried yolk produces emulsions exhibiting


higher viscoelasticity compared to those of native yolk
w36x. According to Moros et al. w37x, the spray-drying
process of a low-in-cholesterol yolk confers a marked
gel-like behaviour to the product, which in turn influ-
ences the viscoelasticity of 70% oyw emulsions. Fur-
thermore, thermal treatment of highly flocculated yolk
emulsions results in an enhancement of viscoelastic
parameter values, provided that emulsion breakdown is
avoided. Egg yolk stabilized emulsions are, however,
less susceptible to emulsion gel enhancement compared
with milk protein systems w38x. This difference in
behaviour was attributed to the fact that at 67 8C, which
was the maximum temperature reached, yolk proteins
were not expected to become further denatured since
most of them require higher temperatures to exhibit
structure alterations.

5. Conclusions
Fig. 2. Influence of pH andyor NaCl addition on average droplet size
and creaming ‘delay period’ of yolk emulsions (10% corn oil, 1% Adsorption at oil–water interfaces of emulsion oil
yolk). Numbers in parenthesis are ‘delay periods’ expressed in min droplets or molecular denaturation, upon heating, leading
(from Ref. w10x). to gel network structure formation, are the key functional
properties of yolk proteins depending, among other
film or between neighbouring oil droplets w32x. Concen- factors, on yolk particle (LDL micelle and granule)
trated yolk emulsions, such as full-fat mayonnaise, are supermolecular structure disorganization brought about
practically stable against creaming over storage periods by surface forces, salt addition or processes such as
of years, due to close oil droplet packing and deforma- homogenization, spray-drying, pasteurization or lipid
tion that prevent droplet movement and serum separa- extraction. LDL micelles and granules, due to their
tion. The rheological properties of this system depend differences in composition and structure, exhibit a totally
heavily on the size of the oil droplets as well as on oil different behaviour upon adsorption, or heating and
volume fraction w33x, although other parameters, such gelation, leading to the appearance of phenomena such
as the concentration and structure of yolk proteins, as competitive adsorption between their constituent pro-
should also have a significant effect on mayonnaise teins in emulsions and mixed gel structure formation,
rheology w34x. Less concentrated yolk emulsions, such respectively. Recent research findings emphasize the
as salad creams and sauces, tend to cream on storage dominant role of LDL micellar proteins either in emul-
and have to be stabilized with the aid of polysaccharides sion formation and stabilization or in gel network
such as xanthan gum. These systems, in contrast to structure development. Granular proteins, on the other
biopolymer gels, exhibit phase angle, d, values between hand, appear to play a secondary role in these systems
98 and 128 indicating a structure heavily dependent on although one should keep in mind that their behaviour
yolk protein content and structure as well as on oil is modulated by the state of the granular structure. Once
droplet size w35x. granules are disorganized, their constituent proteins are
Stability against creaming of yolk-based emulsions liberated and take part in interfacial film formation and
with a low oil fraction, in the absence of polysacchar- emulsion stabilization as well as in gel structure devel-
ides, appears to be largely determined by steric interac- opment, in a more efficient way. Further research is
tions due to adsorbed LDL apolipoproteins w24●●x. needed, however, to clarify their role both in emulsions
Granular proteins may also adsorb at the oyw interface and in gels. Yolk is one of a number of ingredients
of yolk emulsions, along with LDL and enhance the found in food products. Due to interactions with other
stability of the system, provided the granular structure food biopolymers such as proteins of animal or plant
is disorganized by the addition of 0.6 M NaCl and origin, its functional performance could be modulated.
bridging flocculation, due to intact adsorbed granules is In creams where yolk may be used along with milk,
prevented w10x (Fig. 2). yolk proteins appear to displace whey proteins and
As was pointed out above, the structure of yolk casein from oil surfaces due to their more flexible
particles influences the rheology of yolk-stabilized emul- structure. In products such as cakes and confectionery,
sions. Yolk structure alterations may take place as a interactions of yolk proteins with other biopolymers
result of processes such as spray-drying or lipid extrac- such as egg white proteins, gluten or added surfactants
V. Kiosseoglou / Current Opinion in Colloid and Interface Science 8 (2003) 365–370 369

are bound to determine the product structure and textural tic properties of interfacial egg yolk films: a dynamic drop
properties. Research in this area is very difficult to tensiometry study. Colloid Surface B: Biointerfaces
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