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Plant Lipids Science, Technology, Nutritional Value and Benefits to Human Health, 2015: 87-106
ISBN: 978-81-308-0557-3 Editors: Grażyna Budryn and Dorota Żyżelewicz
2.4. Cocoa butter alternative fats
Joanna Oracz, Dorota Żyżelewicz, Grażyna Budryn and Ewa Nebesny
Institute of Chemical Food Technology, Faculty of Biotechnology and Food Sciences, Lodz University
of Technology, Stefanowskiego 4/10 St., 90-924 Lodz, Poland
Abstract. Cocoa butter is a natural and highly valued fat that
contributes to the desirable textural and sensory properties of
chocolate and confectionery products. Thanks to its unique
triglyceride composition cocoa butter is responsible for the most
important qualities of produced chocolate, namely gloss, brittleness,
hardness, and rapid and complete melting in the mouth. The rise in
the price of cocoa butter forced confectioners to seek of cheaper and
more readily available alternative fats derived from various natural
sources. Alternative fats can be divided into three main group by
their application, namely cocoa butter replacers, cocoa butter
equivalents and cocoa butter substitutes. The cocoa butter
alternatives can be produced by blending and/or modifying
vegetable fats. The main processes used in the industry to modify
physico-chemical characteristics of oils and fats are fractionation,
interesterification and hydrogenation.
Introduction
Cocoa beans, seeds of the Theobroma cocao L. tree are the primary raw
material used for the preparation of cocoa, chocolate and other chocolate
products, which are highly valued by consumers around the world. The
Correspondence/Reprint request: Dr. Dorota Żyżelewicz and Joanna Oracz, Institute of Chemical Food
Technology, Faculty of Biotechnology and Food Sciences, Lodz University of Technology, Stefanowskiego 4/10
St., 90-924 Lodz, Poland. E-mail: [email protected], [email protected]
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Joanna Oracz, et al.
dominant constituent of cocoa bean is cocoa fat (50-57%), called cocoa butter
[1,2]. Cocoa butter is a natural fat, very valued for its specific textural
properties and for consisting a carrier of many bioactive compounds [3,4,5].
According to literature data [6,7] the most abundant fatty acids present in
cocoa butter are: stearic acid (C18:0, 29-38%), oleic acid (C18:1, 29-38%)
and palmitic acid (C16:0, 20-26%). Linoleic (C18:2, 2-4%), arachidic (C20:0,
1%), alfa-linolenic (C18:3, 0.1%), palmitoleic (C16:1, 0.25%) and behenic
acids (C22:0, 0.2%) can be also found in cocoa butter [8]. Small quantities of
myristic (C14:0, 0.2-0.3%) and recently discovered in cocoa butter lauric acid
(C12:0, 0.01%) can also be found. The presence of endogenic essential
unsaturated fatty acid, which although not being synthesized in human body,
determine its proper functioning, increases the nutritional value of cocoa
butter. Compounds responsible for desirable properties of cocoa butter are
triacylglycerols. Present in cocoa butter acylglycerols, are symmetrical
triacylglycerols, and they consist around 90% of all triacylglycerols present in
cocoa butter [9]. The most important triacylglycerols of cocoa butter contain
saturated palmitic, stearic acids and mono-unsaturated oleic acid in an sn-2
position are: 1,3-dipalmitoyl-2-oleoyl-glycerol (POP, 15-16%), 1-palmitoyl-3stearoyl-2-oleoyl-glycerol (POS, 35-38%), and 1,3-distearoyl-2-oleoylglycerol (SOS, 23-26%) [10,11,12]. Unsymmetrical triacylglycerols can be
found only in trace amounts [9]. In cocoa butter around 1% of free fatty acids,
0.3-0.5% of diacylglycerols and 0.1% of monoglycerides also can be found
[8]. The unsaponifiable fat fraction of cocoa butter includes plant sterol esters,
which belong to phytosterol compound group. In the biggest quantities
following sterols can be found: sitosterol (12.33 mg/kg), stigmasterol
(6.01 mg/kg), campesterol (1.87 mg/kg) and Δ5-avenasterol (0.61 mg/kg)
[3,4,9]. Furthermore in cocoa butter a presence of vitamin E isomers has been
proven, mainly γ-tocopherol (93.90 mg/kg) with trace amounts of α-tocopherol
(4.20 mg/kg), β-tocopherol (3.70 mg/kg) and tocotrienols (<10 mg/kg)
[4,5,14]. Cocoa butter in solid state is of light-yellow color [15]. Unique
triacylglycerol composition, with simultaneous small amount of
diacylglycerols, cause cocoa butter to possess desired physical properties and
the ability to re-crystalize in a stable crystalline form during technological
processes. Due to these properties cocoa butter is responsible for the most
important qualitative characteristics of chocolate, such as: luster, brittleness,
hardness, and quick and complete melting in the mouth [10].
Triacylglycerols in a solid state, also these present in cocoa butter,
show a polymorphism phenomena, which means that they can exist in a
few crystalline forms. Due to this effect, depending on triacylglycerol
composition cocoa fat shows polymorphic properties [16-19]. It can occur
in six various crystalline forms: γ (I), α (II), α+β (III), β' (IV), β 2 (V) and
Cocoa butter alternative fats
89
β1 (VI). Definition of these six forms subjects to two different conventions.
First method, known as Wille and Lutton method defines crystalline forms
of cocoa fat as forms I to VI. The second method is called the Larsson
convention and it uses the letters of Greek alphabet (α, β, γ) or Roman
numeral [16, 20]. In Table 1 polymorphic forms of cocoa fats,
interdependencies between their nomenclature and melting points assigned
to individual forms, are presented [17-21]. Form I is formed during rapid
cooling of cocoa fat in low temperature conditions. This form is very
unstable so it is quickly transformed into a more stable form II. The most
stable forms - V and VI belong to polymorphic forms β. The heterogeneity
of fatty acid composition delays the transformation to the most stable
polymorphic form. From the point of view of industrial use this
phenomena in very unbeneficial [16,22,23]. Due to complex polymorphic
properties cocoa butter requires tempering. This process is performed to
create a sufficient enough number of form β crystals, which will stay stable
for a long time period. However, during storage form V is spontaneously
transformed to form VI. Improperly tempered chocolate mass is also the
cause of fat bloom formation (spontaneous crystallization of unstable fat
forms) [17-19,23]. However, also to high storage temperature causes the
melting of stable polymorphic form and crystallization of unstable forms
on the surface of products. Polymorphic changes influence significantly
rheological properties (consistency, plasticity) and other physical
characteristics of fat, which is why crystalline changes during the whole
production have to be performed in strictly controlled conditions
[17,18,23]. Transformation of one form to another occurs as a result of:
heating, cooling or crystallization from different solvents. Due to the fact
that melting temperature of cocoa fat is significantly higher than most
other plant fats (34-35 °C), it is present in room temperature in a solid state
[5]. Cocoa fat hardness depends mostly on the concentration of SOS and
overall content of symmetrical triacylglycerols. One of the characteristic
properties of cocoa butter is its contractility (even 2%) during
solidification. For food production uses, cocoa butter is obtained only in a
process of cocoa pulp pressing [2,5].
Most manufacturers in the production of chocolate use an appropriately
selected mix of several types of cocoa beans from different geographical
regions in order to achieve a clearly defined profile of flavor and aroma.
Chemical composition and properties of cocoa butter are mostly defined by
the variety of cocoa tree, cropping region, climatic conditions during fruit
development and fruit and cocoa bean processing after harvest [5,23,24].
These differences play a crucial role during production of chocolate
products. Research regarding fat content in cocoa beans revealed that "bulk"
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Table 1. Classification of cocoa butter polymorphic forms.
Wille and Lutton [17]
Ia (17.3)b
II (23.3)
III (25.5)
IV (27.5)
V (33.8)
VI (36.4)
Dimick and Davis [18]
I (13.1)
II (17.1)
III (22.4)
IV (26.4)
V (30.7)
VI (33.8)
Duck [19]
γ (17.0)
α (21.0-24.0)
β'' (28.0)
β' (33)
Vaeck [20]
γ (18.0)
α (23.5)
β'' (28.0)
-
β (34.4)
β (34.5)
a
Crystal form
Melting point [oC]
b
varieties contain more fat than "fine and flavour" varieties. Butter obtained
from cocoa varieties harvested in lower temperatures in more delicate, it
contains high amounts of triacylglycerols and unsaturated fatty acids.
Amount of rainfall during plant development causes an increase of stearic,
oleic and free fatty acids content, however it does not influence the value
of iodine number. The amount of sunlight during cropping increases the
content of palmitic acid and the value of iodine number in cocoa fat. High
value of iodine number is an indicator of a high concentration of
unsaturated fatty acids. Significant differences in the composition of cocoa
butter from Brazilian and Malaysian cocoa beans have been proven.
Brazilian cocoa butter is rich in unsaturated fatty acids, di- and
triunsaturated triacylglycerols, while Malaysian cocoa butter contains
lower amount of unsaturated fatty acids and consequently lower
concentration of poly-unsaturated triacylglycerols [5,23]. Numerous
studies proved that differences in the composition and ratio of
triacylglycerols have significant influence on the crystallization speed of
cocoa butter [23,24]. It was observed that cocoa butters with higher
amounts of POO, SOO, POS and SOS take longer to crystallize to
polymorphic forms β and β' [25,26].
Reasons for the replacing the cocoa butter with alternatives or substitutes
during recipe preparation and introduction it to production process might be
various: from the desire to increase product quality and reduce production
costs, to the need of production process alteration and creation of new business
value [27-29]. Technological and economic aspects dictate that in
confectionary industry instead of cocoa butter, other plant fats are used [2].
Cocoa butter alternative fats are often divided into three main groups due to
the raw material used in their production as well as physical properties and
similarity to cocoa butter: non-lauric fats which require tempering, non-lauric
fats not requiring tempering and lauric plant fats [9,12].
Cocoa butter alternative fats
91
Cocoa butter alternative fats
Cocoa butter equivalents
First group of cocoa butter alternative fats consist of non-lauric fats
which require tempering [5,8]. They are called cocoa butter equivalents
(CBE), of which a subset constitute cocoa butter improvers (CBI) [9]. These
are non-lauric plant fats, which possess similar chemical and physical
properties as cocoa butter (melting temperature, crystallization temperature,
melting rate, tempering necessity) [8,15,30-32]. These fats consist of
symmetrical, mono-unsaturated triglycerides - POP, POS and SOS. Due to
this composition they can be mixed with cocoa butter equivalents in
practically unlimited proportions [16,33]. Cocoa butter equivalents are
obtained during the process of refining and/or fractionation, which excludes
the possibility of enzymatic modification of triglycerides structure (Table 2)
[9, 29]. They are usually prepared by blending of stearic acid-rich tropical
butters and palm oil mid fractions [32]. Cocoa butter equivalents are mostly
used to decrease production costs, but also to stabilize milk fat or liquid oils
in fillings, increase melting temperature of chocolate and products dedicated
for tropical countries [5]. Alternative fats fulfill in chocolate products a
range of various functions. First of all they limit, depending on the
geographical origin, natural variation of cocoa butter composition. They
stabilize milky chocolates by limiting unbeneficial influence of milk fat on
chocolate softening [6]. Cocoa butter improvers are also characterized by
higher ratio of solid phase in temperature range of 30-35 °C, which causes
them to melt in slightly higher temperature than cocoa butter. Due to this
reason they are also used for production of “tropical chocolate”, which melt
in higher temperature than normal chocolate. The use of equivalent additives
eliminates or prevents temporarily the formation of fat bloom during storage
of products. They also decrease production costs [2,34]. According to EU
directive these type of fats can be used for chocolate production but their
concentration in a final product can’t exceed 5%. According to the Directive
2000/36/EC of the European Parliament and of the Council in EU Member
States, to chocolate products an addition of chosen fat (termed cocoa butter
equivalents - CBEs), different than cocoa butter in a maximal amount of 5%
of overall cocoa mass content, with the condition that the minimal
recommended share of cocoa parts for a product is upheld, can be made [35].
Plant fats, used in a form of individual fats as well as fat mixtures for cocoa
butter equivalent production, are strictly specified and they include: Illipe
butter (Illipe, borneo tallow or tengkawang), palm oil, sal fat, shea butter,
kokum gurgi fat and mango kernel fat [2,10,28].
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Cocoa butter replacers
Among non-lauric cocoa butter alternatives, which do not require
tempering, cocoa butter replacers have to be mentioned (CBR) [33]. Cocoa
butter replacers are physically similar to cocoa butter, but have different
chemical characteristics. These are fats with different fatty acid composition,
as well as completely different structure of triglycerides than cocoa butter.
Due to this reason they mix with cocoa fat only in limited quantities,
however they behave similar to it in final products [33,34]. These replacers
are obtained by hydrogenation and fractionation of plant fats with high
concentrations of C16 and C18 fatty acids [32]. These fats do not require
tempering during technological processing. Cocoa butter replacers can be
used for production of: high-fat cocoa powder and cocoa pulp, coatings,
stuffed bars, nuggats and white chocolate. However, cocoa butter replacers
obtained during hydrogenation process is characterized by high content of
trans fatty acids, mostly oleic acid isomer [34].
Table 2. Comparison of process for the preparation of cocoa butter equivalent from
selected raw materials [34].
Fat raw material
Origin
Processing
Ingredient
Main TAG
Illipe butter
Shorea stenoptera
None
Fat
SOS, POS
Palm oil
Elaeis guieenis
Two fractionation
Mild fraction
POP
Palm kernel oil
Elaeis guieenis
Two fractionation
Stearin fraction
SOS
Sal fat
Shorea robusta
One fractionation
Stearin fraction
SOS, SOA
Shea butter
Vitellaria paradoxa One fractionation
Stearin fraction
SOS
Kokum butter
Garcinia indica
None
Fat
SOS
Mango seed fat
Mangifera indica
One fractionation
Stearin fraction
SOS, POS
Cocoa butter substitutes
Lauric fats are characterized by a high content of saturated fatty acids,
mostly lauric and myristic acids [5]. Cocoa butter substitutes (CBS) are hard
lauric fats, which similarly to cocoa butter replacers do not need tempering.
These fats are constructed from short-chain trisaturated triacylglycerides,
which causes their chemical properties to be completely different than cocoa
butter, however their physical properties remain similar [33,16,36]. Cocoa
butter substitutes are mainly produced from palm kernel oil and coconut fat
[5,37]. For cocoa butter substitutes production all main methods of fat
modification are used: hydrogenation, fractionation, and interesterification.
Cocoa butter alternative fats
93
These are used as single modification methods or as a compilation of two of
all three of them. These processes are used to increase fat hardness and
obtain a melting profile similar to cocoa butter [16]. The use of cocoa fat
substitutes is dictated mainly by the following reasons: easy production
process, low production costs, high availability of raw materials and good
stability of final products during storage. Due to the fact that hydrogenated
fractions of coconut and palm kernel oils crystallize directly into a stable
polymorphic form β', these fats do not require the performance of tempering
process [16]. However, due to the considerable differences in chemical
composition of cocoa butter and cocoa butter substitutes, the miscibility of
these fats is low. Lauric fats, which contain trilaurin the main TAG, do not
constitute a good protection barrier from moisture. Furthermore, as a result
of hydrolysis with the use of a fatsplitting lipase enzyme, free fatty acids are
released (mainly lauric acid), which leads to the creation of unpleasant soapy
flavor [5,31,38,39]. Hydrogenated cocoa butter substitutes possess few
unbeneficial properties, especially nutritional. They contain noticeable
amounts of trans fatty acids and medium-chain saturated fatty acids, which
increase the level of LDL cholesterol fraction and decrease the HDL
fraction. Cocoa butter substitutes have an excellent thick consistency and
similarly to cocoa butter they melt in the mouth, causing a pleasant cool
feeling, which is why they are used in the production of chocolate, chocolate
bars and coatings. Non-hydrogenated cocoa butter substitutes are used in the
production of healthy food, because they are considered to be natural fats
(without any modifications) [5,16,36-39]. More beneficial properties as well
as economic and technological aspects of products made with the use of
cocoa butter replacers cause an increasing interest in their use during food
production. So much interest in fact, that their content in chocolate products
often exceeds allowed amount, which causes a product to be recognized as
forged [2]. The use of a fat different than cocoa or its replacers, forces
producers to put an adequate information on a packaging of final products
[35]. Because of this legislation, detection of plant fats other than cocoa
butter in chocolate products is gaining more and more interest.
Natural sources of cocoa butter alternative fats
Palm oil and palm kernel oil
Oil palm (Elaeis guieenis) is a tropical perennial species belonging to
the Arecaceae family, in the order of Arecales [40,41]. At the moment oil
palm is the highest yielding oil crop and remains the most popular source of
edible oil among all plant fats. Fruit cluster can consist of even 2,000 fruits
the size of pigeon eggs. Two types of oil can be obtained from the oil palm
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fruit; palm oil (extracted from the mesocarp) and palm kernel oil (extracted
from the kernel), both with different chemical composition and properties
[41,42]. Palm oil is obtained from the mesocarp layer of the palm fruits by
steam treatment (initial sterilization), which leads to the deactivation of
enzymes responsible for fat hydrolysis [41,43,44]. Palm kernel oil is
obtained as a result of mechanical pressing, previously dried and milled hard
palm kernels separated from fat pericarp. Fat obtained this method has light
color – white to light yellow, and is similar to coconut fat. The fibrous pulp
of the palm fruit has a fat content of 30-70%, while the palm kernel contains
about 40-50% fat [2,41-44]. The main fatty acids in palm oil are palmitic
acid (44.1%), oleic acid (39.0%) and linoleic acid (10.6%) [27,45,46]. The
proportion of unsaturated fatty acids was similar than the saturated fatty
acids. The palm kernel oil contain mainly lauric acid (48-52%), myristic acid
(15-17%), and oleic acid (14-15%) [2,44]. The palm oil is rich in 1,3dipalmitoyl-2-oleoyl-glycerol (POP, 26%), 1-linoleoyl-2-oleoyl-3-palmitoylglycerol (LOP, 24%), 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP, 17%),
1,2,3-trioleoyl-glycerol (OOO, 4%), and contain small amounts of 1palmitoyl-3-stearoyl-2-oleoyl-glycerol (POS. 3%) and 1-stearoyl-2,3dioleoyl-glycerol (SOO, 3%) [27], while palm kernel oil contained a wide
range of medium chain triacylglycerols.
Raw palm oil possesses characteristic red-orange color, which is a result
of a high content of carotenoids and chlorophylls, present mainly in oil from
young fruit [48]. Palm oil, both raw (red) and refined, contains significant
amounts of tocochromanols, among which α-tocopherol and tocotrienols
(α-T-3, β-T-3, γ-T-3, δ-T-3) can be distinguished 18 19 20 21 [48]. In red palm
oil mostly tocotrienols can be found. α-Tocopherol and tocotrienols content,
due to incomparable quality of palm oils, is very diverse and varies from 6001000 mg/kg of oil [49]. In unsaponifiable palm oil fraction sterols in an
amount of 326-627 mg/kg of oil can also be found. They include cholesterol
(2.2-6.7%), 5-avenasterol (0-2.8%), 7-stigmasterol (0-2.8%) and
7-avenasterol (0-4%) [50]. Palm oil extracted from pulp of oil palms is used
mostly in food production industry. Palm oil constitute the cheapest alternative
of cocoa fat in comparison to other plant fats. Commercial success of palm oil
results from its low cost and the possibility of versatile uses in various
branches of food industry, including the oil itself and fractions obtained from
it: olein and stearin. Due to a specific consistency, resulting from the big
content of saturated fatty acids, palm oil is willingly used as a substitute of
expensive cocoa butter, without the need of hydrogenation [9,15]. This allows
to limit very harmful for health trans isomers of fatty acids in food products.
Hydrogenated and/or fractionated palm oils are also used for manufacturing
special fats with strictly specified criteria, such as: cocoa butter equivalents,
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Cocoa butter alternative fats
cocoa butter replacers, fats for chocolate coatings or fats for candy production
[51,52,53]. Oil obtained from palm kernels is very similar to coconut oil (ca.
72% of fatty acids are saturated) and is the main raw materials used in
production of cocoa butter substitutes. Palm kernel oil is often used is various
modifications, such as fractionation, hydrogenation, interesterification or
mixing with fats with different physical properties. This oil is widely used as a
suitable raw material in fillings [9,15,51-54]. Typical fatty acid and
triacylglycerol contents of cocoa butter and natural source of its alternatives
are presented in Table 3 and Table 4.
Table 3. Fatty acid compositions of cocoa butter and selected raw materials suitable
for use in cocoa butter alternative fats production [6-8,44,45,55,59,67,70].
Typical content (%)
Fat raw material
Cocoa butter
Illipe butter
Palm oil
Palm kernel oil
Sal fat
Shea butter
Kokum butter
Mango seed fat
Trace, <0.5%
C12:0
C14:0
C16:0
C18:0
C18:1
C18:2
C18:3
C20:0
Tracea
Trace
48
Trace
Trace
Trace
2
1
16
Trace
Trace
Trace
25
20
44
8
5
4
2
8
35
42
4
2
44
41
57
38
35
36
45
15
40
47
40
45
3
4
10
3
2
5
1
7
Trace
Trace
1
Trace
Trace
1
1
Trace
Trace
4
Trace
2
Illipe butter
Illipe butter (Borneo tallow) is derived from the nuts of the tropical trees
(Shorea stenoptera) of the family Dipterocarpaceae that grows in the forests of
Java, Borneo, the Philippines, Malaysia and Sumatra [2,9]. The Illipe seeds
contains 40-60% natural pale-green color. Illipe butter consists mainly palmitic
acid (18-21%), oleic acid (34-37%), and stearic acid (39-46%) [55]. This fat is
composed of three main triacylglycerides, such as POP (7-9%), POS (24-35%)
and SOS (42-45%) [2,56]. The melting point of Illipe butter is 37-38 °C [57].
Illipe butter it is highly stable towards oxidation. The triacylglycerides
composition of Illipe butter is closely similar to that of cocoa butter, which is
why it can be used directly as cocoa butter equivalent [2,9,58].
Sal fat
Sal fat is derived from the nuts of the sal tree (Shorea robusta gaertn f.)
found in India, Malaysia, Borneo, Java, and Philippines [2]. The sal nuts
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Joanna Oracz, et al.
kernels contain approximately 19 to 20% of oil. The main fatty acids of the
sal fat are palmitic (5%), stearic (44%), oleic (40%), linoleic (2%) and
arachidic acids (4%) [59]. This fat contains approximately 42% of 1,3distearoyl-2-oleoyl-glycerol (SOS), 11% of 1-palmitoyl-3-stearoyl-2-oleoylglycerol (POS), 16% of 1-stearoyl-2,3-dioleoyl-glycerol (SOO), 13% of 1stearoyl-2-oleoyl-3-arachidoyl-glycerol (SOA), 3% of 1,2,3-trioleoylglycerol (OOO) and 4% of 1,2-dipalmitoyl-3-arachidoyl-glycerol (AOO)
and minor amounts of other triglycerides [58]. Sal fat has a low levels of
unsaponifiable matter (0.6-1.3%) that is rich in sterols (600-4300 mg/kg)
and tocopherols (100 mg/kg). The melting point of sal fat is 30-36 °C.
Fractionated sal fat can be used for the production of a cocoa butter
equivalents [2].
Shea butter
Shea butter is obtained from the nut of Vitellaria paradoxa
(C.F. Gaertn) and also called Butyrospermum parkii L. tree indigenous to
mainly in the West African and sub-saharan African region. Shea kernel is
characterized by high oil content, around 50%, with melting point of 32-45 °C
[58,60,61]. Conventional shea oil extraction is carried out by organic
solvent extraction. The shea butter is composed mainly of palmitic (4-8%),
oleic (33-50%) stearic (41-58%) and linoleic acids (4-8%) [62, 63, 64]. Its
main triglycerides are SOS (40-42%), SOO (26%), POS (5-6%), SOL
(5%), SLS (5%), and OOO (6%) [58,65]. Shea butter has one of the
highest unsaponifiable matter of any natural fat. Because the shea butter
containing high levels of SOS can be used to improve the heat stability of
chocolate [2,56,61]. However, this fat contains elevated level of SOO,
which considerably softens the oil, therefore shea butter needs to be
fractionated to obtain a stearin fraction suitable for cocoa butter equivalent
production [12].
Kokum kernel fat
Kokum kernel fat is a hard, solid phase fat with a light-yellow color and
mild aroma [66]. It is obtained from kernels of an evergreen kokum tree
(Garcinia indica), cultivated in several parts of India [67,68]. The ripe
kokum fruit is spherical and deep purple in color, and with five to eight large
seeds [67]. Kokum seed contains about 40-50% of fats, that are rich sources
of stearic (50-60%) and oleic acids (36-40%) [67]. This fat is composed of
symmetrical triglycerides, mainly 1,3-distearoyl-2-oleoyl-glycerol (SOS,
72%). Kokum kernel fat is characterized by high melting temperature,
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Cocoa butter alternative fats
ranging from 38 to 42 °C [58,67]. This fat does not need fractionation for
use in cocoa butter equivalent formulation, and after refining kokum kernel
fat may be directly used in chocolate. Fractionation of the kokum fat gives a
very high level of stearin fractions, which were useful for chocolate filling or
chocolate coating [56]. The triglyceride compositions and other physicochemical properties of kokum kernel fat make it a valuable fat, which can be
used as an improver to increase the hardness of chocolate, inhibits fat bloom
and decreases the tempering time [2,34].
Mango seed fat
Mango seed fat is obtained from seeds of Mangifera indica L. tree
fruits, which is grows in tropical regions of the world, mainly in central
regions of India, as well as is found in Brazil, Mexico, Pakistan, China and
Indonesia [2,68]. It is received as a result of pressing, previously dried and
milled hard kernel separated from fat pericarp. The kernel contains
between 7% and 15% fat, with the melting point of 34-43 °C. Mango seed
fat is a rich sources of palmitic, stearic and oleic acids [2,58,69,70,71]. The
major triglycerides contained in this fat are 10-16% of POS, 25-59% of
SOS, 1-9% of POP, 23% of SOO, 5% of POO, 4% of SOA and 5% of
OOO [65,72]. The mango seed fat contains 1-3% of phospholipids, 1-2%
of unsaponifiable matter, and approximately 10 g/kg of total sterols. Based
on the triglyceride compositions, mango seed fat is comparable to that of
natural cocoa butter and is a valuable raw material for cocoa butter
equivalent production [68].
Table 4. Comparison of typical compositions of tree main triacylglyceride of cocoa
butter to selected raw materials suitable for use in cocoa butter alternative fats
production. [2,9-12,56,58,65,68].
Typical content (%)
Fat raw material
Cocoa butter
Illipe butter
Palm oil
Palm kernel oil
Sal fat
Shea butter
Kokum butter
Mango seed fat
POP
POS
SOS
16
7
26
Trace
1
Trace
Trace
5
37
35
3
11
6
5
13
26
45
42
42
72
42
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Joanna Oracz, et al.
Modification techniques to produce cocoa butter alternatives
The vegetable fats produced from plant raw materials or do not always
meet all the requirements of food technologists, dietitians and consumers.
That is why they are often subjected to processes modifications which allow
them to obtain desired properties (proper plasticity, melting temperature,
crystalline form or chemical composition). Cocoa butter alternative fats can
be obtained from plants or vegetable fats by blending, fractionation,
hydrogenation, and chemical or enzymatic interesterification. All
aforementioned modification methods are most commonly used to change
chemical, physical and sensory properties of fats have specific applications
[8-11,13,66,67].
Blending
Mechanical mixing is one of the oldest methods of fat modification.
Obtained product after this alteration is often of better quality than the initial
raw material. Most cocoa butter alternatives are prepared by blending
natural raw materials or vegetable fats contain the same triacylglycerols but
in different ratios compared to cocoa butter. In this process a selected fats
and their fractions are mixed together to obtain triacylglycerols composition
of which resembles the composition of cocoa butter. Palm oil is mainly the
source of palmitic acid, weather the Illipe butter, sal fat, shea butter, kokum
gurgi fat and mango kernel fat are rich in symmetrical triacylglycerols with
stearic acid being the most prevalent fatty acid. The cocoa butter equivalent
are produced by blending a middle melting fraction from palm oil (PMF),
which contains high concentration of POP, with Illipe butter and high
melting point fraction of shea fat and sal stearin, which are rich in POS and
SOS. This is why various types of equivalents are received by mixing
precise proportions of palm oil with other exotic fats. If middle melting
fraction from palm oil is blended with Illipe and shea fat, a cocoa butter
equivalent is obtained with the same amount of SOS triacylglycerols, but
more POP and less POS will be present in the mixture compared to cocoa
butter [2,9,34].
Fractionation
Fractionation is performed to divide initial fat into two or more
fractions, differing in melting temperature values of the triacylglycerols
composing the oil [28,66]. In this process, the fat is melted and then cooled
to produce crystals. The two main methods are used for fractionation fats:
Cocoa butter alternative fats
99
dry and solvent fractionation. The dry fractionation involves selective
crystallization of the high melting triglycerides followed by filtration,
without solvent [73]. Whereas, solvent fractionation process consists the
crystallization of a desired fraction from oil dissolved in an organic solvent,
usually hexane or acetone [31]. Fractionation is used during the production
of a fraction of palm oil designed and used as cocoa butter equivalent.
Because of its triglyceride composition which includes substantial quantities
of both low and high melting point triglycerides, palm oil can readily be
crystallized by controlled cooling and separated into a low melting fraction
(palm olein), and a high melting fraction (palm stearin) [34]. Palm oil middle
melting fraction can be obtained by further fractionation of the olein fraction
[56]. The stearin fractionation of middle melting fraction from palm oil is
hard middle melting fraction from palm oil and is often used in chocolate
and other confectionery products [74,75].
Hydrogenation
Another modification method used for changing chemical properties of
lipids is hydrogenation. This method involves addition of hydrogen to the
double bonds of unsaturated fatty acids. The aim of this process is to
transform fat and oil into products with better physicochemical properties:
better plasticity, harder consistency (increasing the melting temperature of
fat) and bigger resistance to oxidation. Hydrogenation is a catalytic reaction.
The metal catalyst used at the time was nickel, which is provided to the
reaction on a carrier, due to its easier removal from the mixture after
hydrogenation process completion. Hydrogenation is a selective reaction - a
saturation of fatty acids with higher content of unsaturated bonds takes place
first. Poly-unsaturated fatty acids are more reactive than mono-unsaturated
fatty acids, which guarantees that they are hydrogenated first [76,77,78].
During hydrogenation, beside the addition of hydrogen to double bonds
in the fatty acid chain, also some double bonds may be moved or/and
transformed from cis to trans configuration. Due to decrease of nutritional
value of final products takes place due to depletion of essential unsaturated
fatty acids and formation of trans isomers during partial hydrogenation of
fat, the industry needs to find alternatives to hydrogenated fats [9,34].
Interesterification
Interesterification can be used as an alternative to hydrogenation, with
particular reference to eliminating the formation of trans fatty acids. The
technique is effective and can be used for modifying the physicochemical
100
Joanna Oracz, et al.
characteristics of oils and fats. Interesterification causes a distribution of the
fatty acids within and between the triacylglycerols. As a result of fat
interesterification the structure and composition of triacylglycerols is altered,
however the fatty acid composition remains unchanged, which means that,
beneficial for health, fatty acids are biologically active after this treatment
[11,66]. Depending of the catalyst used during interesterification, two types
of this reaction are distinguished: chemical and enzymatic. The most
commonly used catalyst during chemical interesterification is sodium
methanol, while enzymatic interesterification is performed with the use of
lipase enzymes with specific activities [69].
Enzymatic interesterification is one of the modification methods, which has
several advantages over other chemical catalysts, namely lower energy
consumption, absence of isomerization by products, and better control of
products [15]. This selective method allows to alter the distribution of fatty acids
in triacylglycerols, with simultaneous protection of biologically significant fatty
acids. This allows to produce new triacylglycerols, using mild reaction
conditions, without the loss of valuable compound and without releasing harmful
side-products. The use of lipase enzymes with specific activity toward specific
ester bonds in triacylglycerols, allows to obtain products with precisely planned
structure [35]. One of the fats, which is often modified with aforementioned
methods is milk fat, due to its significance for human nutrition. Characteristic
composition and distribution of fatty acids in milk fat results in it being easily
digestible by human organism, including newborns and children. During this
modification method the native fatty acids of milk fat remain intact [11,66].
Interesterification of high-oleic sunflower oil with stearic acid with the use of
immobilized lipase from Rhizupus miehei will result in receiving of solid phase
fraction (SOS), which when mixed with palm oil gives a final product of cocoa
butter equivalent. Other possible solutions for meeting this goal are the use of
genetically modified plants (e.g. oil composition of specific rape varieties is
identical to cocoa fat) or microbiological cultures - Single Cell Oil (some yeast
or algae species in certain conditions are able to accumulate in its cells up to
60% of oil, with the same chemical composition as cocoa butter) [15,30,56,79].
For example, cocoa butter alternative fats have been obtained through enzymatic
interesterification of palm oil mid-fraction using sn-1,3-specific lipases [15,79].
However, apply the method of the enzymatic interesterification for production of
cocoa butter alternative is not permitted within the European Union.
Determination of alternatives fats in cocoa butter and chocolate
In recent years quite few research studies, regarding detection and
determination of plant fats added to cocoa butter and chocolate, were
Cocoa butter alternative fats
101
performed [8,10,14,80-84]. Technological and economic aspects cause that
instead of cocoa butter alternative fats are more and more often used in
confectionary industry. The more alternative fats composition is similar to
cocoa butters, the more difficult it is to differentiate one from another. Mutual
property of those fats is a steep profile of solid phase content, however their
chemical composition can be quite different [81,82]. The presence of cocoa
butter replacer and cocoa butter substitute fats in cocoa fat can be identified on
the basis of fatty acid composition (content of C12:0 in CBS or trans isomers
in CBR). Cocoa butter equivalent fats have similar structure as cocoa fat,
which makes it difficult to identify then in cocoa butter. However, it can be
performed by the analysis of fatty acids and triglycerides with the use of liquid
gas chromatography (GLC) and high-performance liquid chromatography
(HPLC) [29,83,84]. The knowledge of fatty acids and sterols profile, allows to
identify fat alternatives in products, thus confirming or denying their
adulteration. Cocoa butter equivalent addition to cocoa butter can be also
confirmed by analysis of minor fats constituents, such as sterols, sterol
degradation products and terpens [33]. For example cholesterol presence in
chocolate might indicate that palm oil was used for product preparation. High
and unstable price of cocoa butter, its often uneven quality, need for tempering
(bringing product to a suitable temperature to facilitate formation of the
product), high production costs and variable melting properties, lead producers
to use cocoa butter alternatives during production.
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