Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics

Journal of Food Engineering xxx (2012) xxx–xxx

Contents lists available at SciVerse ScienceDirect

Journal of Food Engineering journal homepage: www.elsevier.com/locate/jfoodeng

Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics M.H.A. Jahurul a, I.S.M. Zaidul b,⇑, N.A.N. Norulaini c, F. Sahena a, S. Jinap d, J. Azmir b, K.M. Sharif b, A.K. Mohd Omar a,⇑ a

School of Industrial Technology, Universiti Sains Malaysia, Minden, 11800 Penang, Malaysia Faculty of Pharmacy, International Islamic University, Kuantan Campus, 25200 Kuantan, Pahang D/M, Malaysia c School of Distance Education, Universiti Sains Malaysia, Minden, Penang 11800, Malaysia d Centre of Excellence for Food Safety Research (CEFSR), Faculty of Food Science and Technology, Universiti Putra Malaysia, 43400 UPM, Serdang, Selangor, Malaysia b

a r t i c l e

i n f o

Article history: Available online xxxx Keywords: Natural cocoa butter Cocoa butter alternative Fatty acid Triglyceride Cocoa butter properties

a b s t r a c t The current concern for cocoa butter fat as major ingredients of chocolate intake in the World has raised the question of the high price of cocoa butter among all other vegetable fats. Productions of natural cocoa butter fats are decreasing day by day due to the decrease of cocoa cultivation worldwide; moreover, cocoa fruit contains only a little amount of cocoa butter. Therefore, the food industries are keen to find the alternatives to cocoa butter fat and this issue has been contemplated among food manufacturers. This review offers an update of scientific research conducted in relation to the alternative fats of cocoa butter from natural sources. The findings highlights how these cocoa butter alternatives are being produced either by blending, modifying the natural oils or fats from palm oil, palm kernel oil, mango seed kernel fats, kokum butter fat, sal fat, shea butter, and illipé fat. Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction Food industries are keen to find for alternative fats to cocoa butter (CB) from natural matrices that are denoted as cocoa butter replacers (CBRs), cocoa butter equivalents (CBEs), and cocoa butter substitutes (CBSs) fat. CB is a natural fat obtained from cocoa seeds (Theobroma cacao). It is commonly used as an essential major ingredient of chocolate and other confectionary products due to its specific physical and chemical properties. CB is solid at room temperature (below 25 °C) and at body temperature (37 °C) it is liquid. CB mainly consists of palmitic acid (C16), stearic acid (C18:0), Oleic acid (C18:1) and linoleic acid (C18:2) but low amount of lauric acid (C12) and myristic acid (C14). CB can crystallize into several polymorphic forms, having a, c, b0 , and b crystals, with melting points of 17, 23, 26, and 35–37 °C respectively. In the chocolate production, only b crystal is used because it has a high melting point. This crystal structure confers chocolate products an excellent quality in terms of sheen, snap, and smooth texture. In addition, CB exhibits resistance to fat bloom, arising from changes ⇑ Corresponding authors. Tel.: +60 9 571 6687; fax: +60 9 571 6775 (I.S.M. Zaidul), tel./fax: +60 46 585 435 (A.K. Mohd Omar). E-mail addresses: [email protected] (I.S.M. Zaidul), [email protected], [email protected] (A.K.M. Omar).

in the fat in the chocolate during storage. This can be seen as undesirable white or streaky grey-white spots on the chocolate surface. Cocoa butter (CB) is highly appreciated and is expensive compared with all other vegetable fats and oils because of its specific characteristics. Another important reason is that cocoa beans contain low amount of CB fat (Zaidul et al., 2007c). Moreover, cocoa has only been cultivated in a few countries (Hassan et al., 1995; Moreton, 1988). However, many researchers have produced cocoa butter alternative fats either by fractionation and blending or enzymatic interesterification of palm kernel oil (PKO) and palm oil (PO) (Bloomer et al., 1990; Calliauw et al., 2005; Hashimoto et al., 2001; Undurraga et al., 2001; Zaidul et al., 2007c), mango seed fat (Ali et al., 1985; Jiménez-Bermúdez et al., 1995; Kaphueakngam et al., 2009; Lakshminarayana et al., 1983; Solís-Fuentes, 1998), kokum butter (Maheshwari and Reddy, 2005; Reddy and Prabhakar, 1994), Sal fat (Gunstone, 2011; Reddy and Prabhakar, 1989), Shea butter (Olajide et al., 2000), and illipé fat (Gunstone, 2011). The cocoa butter alternatives or cocoa butter replacers (CBRs) are defined as non-lauric fats that could replace cocoa butter either partially or completely in the chocolate or other food products (Kheiri, 1982). The fatty acid compositions of CBRs are similar to that of CB with more or less similar triglycerides structure. It should be cheaper than that of CB. CBRs can be divided into two groups, namely cocoa butter equivalents (CBEs) and cocoa butter substitutes (CBSs). CBEs

0260-8774/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

2

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx

are vegetable fats which have similar physical and chemical characteristics like CB. Therefore, CBEs can be mixed with CB in any amount without changing the behaviour of the final product. The major fatty acids contained in CBEs are palmitic acid, stearic acid and oleic acid, which are similar to that of CB. CBEs are divided into two subgroups, namely cocoa butter extenders (CBEXs) and cocoa butter improvers (CBIs) (Lipp and Anklam, 1998). CBEXs cannot be mixed with CB in every proportion, while CBIs are similar to CBEs, contain higher level of solid triglycerides, and because of this characteristic it is commonly used for improving soft cocoa butters. In this paper the CBEXs and CBIs all are referred to as CBEs. Cocoa butter substitutes (CBSs) are lauric and myristic plant fats (containing lauric and myristic acid) with some physical similarities to CB, but chemically they are completely different. Therefore, they are suitable for wholly replacement of CB. The aim of this review paper is to discuss the various vegetable fats used as proposed or alternatives to cocoa butter in chocolate and other confectionary products. The compatibility of some important properties of the resulting alternative cocoa butter fats such as triglycerides in terms of fatty acid constituents, slip or sharp melting points, solid fat contents, iodine value, acid value and saponification values will also be discussed. 2. Background of cocoa cultivation The generic name of cocoa is Theobroma belonging to the family of Sterculiaceae, also called ‘‘Food of God’’. It contains about 30–50 beans, covered with pulp. About 500 years ago, cocoa beans were originated from Latin America, and within a few years it spread to Europe. From there it was then distributed throughout the World (International Cocoa and Commodities Organisation, ICCO, 2000). In Central America, cocoa was widely cultivated by the Mayas. Mayas and Aztecs were the first to consume cocoa. In the 16th century, the Spanish were the first Europeans to drink cocoa. Spanish people, namely Capuchin friars, successfully grew cocoa in Ecuador in about 1635. In the 17th century, the Europeans began cocoa cultivation widely. France introduced cocoa to St Lucia (1660), the Dominican Republic (1665), Brazil (1677), Guianas (1684), and Grenada (1714); England was growing cocoa in Jamaica by 1670. Later, cocoa was introduced in Africa. The cocoa from Brazil was cultivated in Principe in 1822, Sao Tomé in 1830, Fernando Po in 1854, then in Nigeria in 1874, and Ghana in 1879. From 1925 to 1939, cocoa was introduced in Cameroon. In 1560, the Dutch people first introduced Venezuelan Criollo type cocoa in Southeast Asia and Oceania, in particular, in Celebes and Java. The Criollo type of cocoa from Mexico was introduced into the Philippines by the Spanish in 1614. Cocoa was introduced into Sri Lanka from Trinidad in 1798, from where it spread to Singapore and Fiji in 1880, Samoa in 1883, Queensland in 1886, and Bombay and Zanzibar in 1887. In Malaysia, cocoa was introduced in 1778; In Hawaii in 1831, and in India in the 20th century (Nair, 2010). 3. Cocoa varieties The main varieties of cocoa are Forastero, Criollo, and Trinitario. The unripe pods of Forastero variety are green and yellow during ripening. It gives high yield and takes 5–6 days for fermentation. Forastero variety is the most commonly used, compromising 95% of the world production of cocoa, but the quality is poor. Recently, Brazil and West Africa planted Forastero in large areas. Amelonados is another well-known predominant type of Forastero, traditionally cultivated in West African countries since 19th century. It is self-compatible, shows wide genetic variability and used for breeding in the major cocoa producing countries (FAO, 1977; Nair, 2010). The ripe Criollo pods are red or yellow and seeds are large,

get fermented quickly. It is considered as high quality and delicious cocoa beans compared with Forastero, but the yield is found to be poor. It dominated the world cocoa market in the 18th century. The major demerit of Criollo variety is low content of cocoa fat compared with Forastero variety. Moreover, it tends to be less resistant to varieties of diseases that attack the cocoa plants. Only few countries are still producing Criollo beans, among them Venezuela is the largest producer. Trinitario is a hybrid (mix of Criollo with Forastero) high quality variety, has higher yield and is more resistant to diseases than the others (Yanamoto et al., 1995). It was planted in Trinidad and then spread to Venezuela, Ecuador, Cameroon, Samoa, Sri Lanka, Java, and Papua New Guinea. To improve the quality and yield, new cocoa hybrids called Series II hybrids have been developed from crosses between Amazon, Trinitario, and Amelonado genotypes (Adu-Ampomah and Sersah, 1987/1988). These hybrids have already been grown by farmers (Adu-Ampomah, 1996). Currently, these new hybrids are not commercially used, but they will be introduced in the near future. Moreover, the major nutrients such as antioxidants and phenolics level in these hybrids have been well acknowledged by Jonfia-Essien et al. (2008). Furthermore, the authors also reported that the new hybrid beans show significant antioxidant capacities than the traditional beans. The new cocoa hybrids have also been reported to have exhibited resistance to pest damage during storage.

4. Cocoa production The major cocoa beans growing countries in the world are Ivory Coast, Ghana, Indonesia, Cameroon, Nigeria, Brazil, Ecuador, Dominician Republic, and Malaysia, contributing almost 90% of world production (ICCO, 2009/2010; FAO, 2012). The world total cocoa beans productions in season 2007/2008 to 2009/2010 are shown in Table 1. The Global cocoa beans production declined at 3.613 million tonnes in 2009/2010 season, while in 2007/2008 it was 3.752 million tonnes (Table 1). In season 2007/2008 to 2009/ 2010, the cocoa beans production declined by 3% in Africa, while it increased by 1.9% and 1.8% in the Americas and in Asia and Oceania to 14.4% and 17.5% respectively. However, Africa is still the largest cocoa producing region, contributing 68.0% of the total world production followed by Asia and Oceania and the Americas in 2009/2010. In Malaysia, cocoa beans production has also declined gradually. According to the Malaysian Cocoa Board, cocoa beans production in 2011 was 15,000 tonnes, while in 2007 it was 35,180 tonnes (MCB, 2011). The International Cocoa

Table 1 Production of cocoa beans in the World (thousands of tonnes). 2007/2008

2008/2009

2009/2010

2693 1382 729 230 185 166

71.8%

2518 1222 662 250 227 158

69.9%

2458 1242 632 240 190 154

68.0%

America Brazil Ecuador Others

469 171 118 180

12.5%

488 157 134 197

13.5%

522 161 160 201

14.4%

Asia and Oceania Indonesia Papua New Guinea Others

591 485 52 55

15.8%

599 490 59 50

16.6%

633 535 50 48

17.5%

3752

100.0%

3605

100.0%

3613

100.0%

Africa Ivory Coast Ghana Nigeria Cameroon Others

World total

Source: ICCO Quarterly Bulletin of Cocoa Statistics, vol. xxxvi, no. 4, Cocoa year 2009/2010.

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx

Organization (2009/2010) reported that weather has a great impact on the cocoa beans production. de Magalhães et al. (2011) reported that about 71% of the cocoa consumed around the world comes from the Africas, especially from Ivory Coast, Ghana and Nigeria. In the last decade, the consumption of cocoa has increased while its production has been declining day by day (Jonfia-Essien et al., 2008). 5. Cocoa butter extraction method Presently, several methods are employed for the extraction of cocoa butter from mass or liquor, or from other sources including hydraulic press, mechanical press, screw presses, supercritical fluid extraction (SFE), and solvent extraction method (Asep et al., 2008; Nair, 2010). Recently, Nair (2010) reported that the hydraulic press and screw presses are not successful methods for the extraction of cocoa butter. Moreover, the major demerits of hydraulic press, mechanical press, screw presses, and solvent extraction methods are (a) they require high temperature that affects nutritional quality of the cocoa butter, (b) they are heat sensitive labile natural compounds, and (c) they contain toxic solvent left in the final products which have diverse adverse human health effects (Hultin, 1994; Staby and Mollerup, 1993). Solvent extraction with hexane has been widely used to extract the cocoa butter as well as fats and oils from the oil-contained sources. However, there is an increasing concern of the health and safety hazards associated with the use of organic solvents, while expression by hydraulic method often introduces contaminants into the cocoa butter that must be removed later. Greater concern over the disposal of such toxic organic solvents and their effect on the environment has led to a move towards cleaner extraction method such as supercritical fluid extraction (SFE). In comparison with conventional extraction methods, supercritical fluid extraction (SFE) is feasible in terms of quality product and has the potential to produce higher yields and a good quality cocoa butter replacers blends (Zaidul et al. 2006; Zaidul et al. 2007a, c). The most recent advances and commercial applications of SFE in food science, natural products, by-product recovery, pharmaceutical and environmental sciences have been published in extensive reviews (Herrero et al., 2010; Sahena et al., 2009). The SFE is a method of choice for the extraction and fractionation of edible natural fats and oils from various sources. Over the last 20 years, SFE has been well acknowledged as a promising alternative to organic solvent extraction method in the field of natural fats and oils. The major merits of SFE method are lack of solvent residue left in the final products and better retention of valuable components (Asep et al., 2008; Herrero et al., 2006; Norulaini et al., 2009; Zaidul et al., 2007a, 2007b, 2007c). Carbon dioxide is used as a solvent due to its nontoxic, non-flammable, inexpensive, and clean solvent which offers great opportunities for complex separation problem. Meanwhile, several studies have been carried out for the extraction of cocoa butter from cocoa liquor and shell by SFE using supercritical carbon dioxide (SC-CO2) at different temperatures and pressures (Asep et al., 2008; Li and Hartland, 1992, 1996; McHugh and Krukonis, 1994; Rossi, 1996). The studied pressure and temperature range from 15 to 40 MPa and 40 to 80 °C. The yield of cocoa butter extracted with SC-CO2 at 30–40 MPa and 50–80 °C depend on the degree of disruption of lipid bearing cells reported by Rossi (1996), McHugh and Krukonis (1994). At higher pressure, the yield of cocoa butter was reported to be higher and temperature range being studied. Moreover, in their study, the triglycerides in terms of fatty acid compositions of extracted cocoa butter were within the required range and retained the aroma of the residue. Recently, Asep et al. (2008), Rossi (1996), Li and Hartland (1996) studied the effect of cosolvent such as ethanol on SC-CO2 extraction of cocoa butter. Their results showed that addition of

3

cosolvent improve the efficiency of the cocoa butter extraction. By adding cosolvent such as ethanol (20–25%, w/w), the solubility of cocoa butter increased and maximum yield was also reported by Asep et al. (2008) and Li and Hartland (1992). 6. Health benefits of natural cocoa consumption Cocoa is the most important and popular drink crop around the world, after coffee and tea. It is widely used as a main ingredient in chocolate. It has been well acknowledged that the alkaloid known as theobromine responsible for the stimulating effect is present in cocoa (Nair, 2010). Cocoa beans are a rich source of phenolic phytochemicals and also contain much higher levels of total phenolics (611 mg of gallic acid equivalents, GAE) and flavonoids (564 mg of epicatechin equivalents, ECE) per serving (Lee et al., 2003). Cocoa and its products are also the natural sources of antioxidants. A cocoa product such as chocolate is the source of dietary antioxidants and may be effective for cardiovascular disease (Keen et al., 2005; Kris-Etherton and Keen, 2002; Steinberg et al., 2003). Polyphenols have been extensively studied due to their beneficial health effects such as anti-carcinogenic, anti-atherogenic, anti-inflammatory, anti-microbial, anti-ulcer, anti-thrombotic, immune modulating, vasodilatory and analgesic. Several researchers have identified and measured the polyphenolic compounds present in cocoa, among which catechins-catechin: epicatechin; gallocatechin and epigallocatechin; procyanins; anthocyanins; and flavone and flavonol glycosides such as luteolin-7-O-glucoside and quercetin-3-Oarabinoside, theaflavin and resveratrol, are most important due to their possible beneficial role as chemopreventive agents based on their antioxidant activities (Jonfia-Essien et al., 2008; Lee et al., 2003; Sanchez-Rabaneda et al., 2003; Wollgast and Anklam 2000; Zumbe, 1998). 7. Composition of natural cocoa butter Cocoa butter obtained from cocoa beans and on dry weight basis accounts for 50–57% and is responsible for the melting properties of chocolate (Steinberg et al., 2003). Staphylakis and Gegiou (1985) determined the level of sterols in particular, methylsterols, desmethylsterols and triterpenes in the cocoa butter. In another study, Erickson and Weissberger (1983) found vitamin E such as b-tocopherol, a-tocopherol and c-tocopherol in cocoa butter. In their study, the b-tocopherol was found in higher amount followed by tocopherol and c-tocopherol. Glycerol-1,3-dipalmitate-2-oleate (POP), glycerol-1-palmitate-2-oleate-3-stearate (POS) and glycerol-1,3-distearate-2-oleate (SOS) are the three main triglycerides account for 92–96% of total lipid composition of cocoa butter (Asep et al., 2008; D’Alonzo et al., 1982; Davis and Dimick, 1989; Lehrian and Keeney, 1980; Lipp and Anklam, 1998; Lipp et al., 2001). Among these three triglycerides, POS is the major leading triglyceride component present in cocoa butter with range 42.5–46.4% yield followed by SOS (27.8–33.0%) and POP (18.9–22.6%) (Asep et al., 2008). The major fatty acids of cocoa butter are palmitic acid (C16) 25–33.7%, Stearic acid (C18:0) 33.7–40.2%, oleic acid (C18:1) 26.3–35% and linoleic acid (C18:2) 1.7–3% which contribute about 98% of the total fatty acid (Asep et al., 2008; Bracco, 1994). The fatty acid compositions of cocoa butter differ depending on the country of origin. The key fatty acid compositions of cocoa butter from different countries are shown in Table 2. 8. Natural cocoa butter and its physicochemical properties The cocoa seeds are referred to as cocoa beans consist about 85% cotyledon (nib) and 15% shell. The nibs contain about 55% fat. The nibs ground to a paste are called cocoa liquor or mass, some are directly used in chocolate. Cocoa beans are natural oil

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

4

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx

Table 2 The major fatty acid composition (%) of natural cocoa butter produced from various countries. Country

Ivory Coast Ghana Indonesia Brazil Ecuador Malaysia

Fatty acids

References

Stearic acid

Oleic acid

Palmitic acid

Linoleic acid

36.9 36.69–37.6 36.88–37.3 33.3–33.8 34.62–36 36–37.4

32.9–33 32.7–32.99 33.06–34.3 34.5–36.5 34.6–34.91 33.5–34

25.8–26.6 25.3–25.46 24.1–25.13 25.1–27.9 25.2–25.6 24.9–26

2.6–2.8 2.51–2.8 2.5–2.7 3.5–3.6 2.6–3.04 2.6–3.0

seeds like palm kernel, groundnut, sesame seed, or any other oilseeds. Processing of cocoa beans for getting the fats or oils is not same like other oilseed due to the unique physico-chemical properties of cocoa beans, especially the fats (Adeyeye et al., 2010). The physico-chemical compositions of cocoa beans and the characterization of cocoa matrix are greatly influenced by processing method reported by many researchers in the literature (Amin et al., 1997, 1998, 2002; Hoskin and Dimick, 1984, 1994; Jinap, 1994; Puziah et al., 1998). The properties of cocoa butter fat are the properties of the mixture of triglycerides. Cocoa butter fat which is commercially available fat contains significantly higher amount of saturated acids, leading to triglycerides of POS, SOS, and POP. Due to such types of triglycerides in cocoa butter, it confers the short melting behaviour which is appreciated by consumers. CB has relatively low and sharp melting point which range from 27 to 35 °C. At room temperature, cocoa butter is hard and brittle and its hardness depends on the solid fat content (SFC) and it might be 0% just above 37 °C temperature. Furthermore, the nature of crystalline lattice also renders the hardness/consistency of the cocoa butter fat (Kheiri, 1982). The other physiochemical properties of cocoa butter such as iodine value (IV) and saponification value (SV) are shown in Table 3. Iodine values have great impact on oil quality; it indicates the degree of unsaturation in the fat or oil. Typically, at room temperature fats are liquid because of the higher unsaturated fatty acid components, while it is solid at lower unsaturated fatty acid components. Chaiseri and Dimick (1989) reported that the higher iodine value contribute to the softness of cocoa butter. They also stated that higher iodine value content CB is softer than the lower iodine value content CB. The commercial CB from different countries show different iodine value that range from 34.40 to 38.65. The saponification value indicates that the average chain length of fatty acid present in fat. If the saponification value of the fat is high, then the chain length of fatty acid will be shorter, and vice versa. The acid value (AV) is defined as the weight in milligrams of potassium hydroxide necessary to neutralize the free fatty acid present in 1 g of fat and it is used to quantify the free fatty acids

Table 3 Chemical characteristics of commercial cocoa butters from different countries (Chaiseri and Dimick, 1989). Country

Iodine value

Saponification value

Bolivia Brazil Colombia Ecuador Peru Costa Rica Dominican Republic Mexico Panama Ivory Coast Nigeria Malaysia

36.02 37.46 36.56 36.68 37.94 36.64 36.72 35.79 36.86 35.54 37.33 34.74

195.43 195.07 195.75 195.85 195.92 195.27 194.92 193.72 196.71 193.58 193.62 194.36

Davis and Dimick (1989) and Lipp and Anklam (1998) Spangenberg and Dionisi (2001) and Lipp and Anklam (1998) Spangenberg and Dionisi (2001) and Lipp and Anklam (1998) Lehrian and Keeney (1980) and Lipp and Anklam (1998) Spangenberg and Dionisi (2001) and Lipp and Anklam (1998) Kheiri (1982) and Lipp and Anklam (1998)

present in fats or oils. The cloud point (Cp) is related to the unsaturation of oil, that is, the unsaturation of oil is higher, when its Cp is low. 9. Alternative sources of cocoa butter Many researches has been carried out for the production of CBRs, CBEs and CBSs from various natural sources. All of these are obtained from fats of natural plant, such as PKO, PO, mango seed fat, kokum butter, sal fat, shea butter, illipé butter, soya oil, rape seed oil, cotton oil, ground nut oil, and coconut oil. Replacing the cocoa butter either partially or wholly with other natural fats has been investigated due to the technological and economical advantages. These methods include chemical or enzymatic fractionation or supercritical carbon dioxide (SC-CO2) extraction of fats and their blends from various sources. 9.1. Cocoa butter from palm kernel oil (PKO) and palm oil Palm fruits (Elaeis guineensis) contains about 45% palm kernel which is a by-product of the palm oil industries. On a wet basis, palm kernels contain about 45–50% oil which is called palm kernel oil (PKO). Although palm oil and PKO are obtained from the mesocarp layer and from the kernel of the same palm fruits, they vary greatly in their characteristics and properties (Zaidul et al., 2007a). Palm oil, PKO and their products are the main export commodities of Malaysia, which contribute significantly to its national income. Conventionally, palm oil and PKO are extracted by solvent extraction method. These methods are time consuming, costly, and used organic solvents, which are not permitted in food. To overcome the solvent extraction method and to get good quality Palm oil and PKO, a group of researchers have extracted these oils using supercritical carbon dioxide extraction method (Hassan et al., 2000; Norulaini et al., 2004; Omar et al., 1998; Zaidul et al., 2007a, 2007b). PKO is a rich source of lauric acid, C12 (48.3%) and other major fatty acids such myristic acid, C14 (15.6%), and oleic acid, C18:1 (15.1%). The level of fatty acids such as lauric (C12) and myristic (C14) are present in cocoa butter as trace or very low amount while the amount of palmitic (C16), stearic (C18:0), and oleic (C18:1) acids are high. On the other hand, palm kernel oil contains a high level of C12 constituent but low in C18:0 and C18:1 constituents compared with cocoa butter. Although PKO contains high level of lauric and myristic acid, it is widely used as a suitable raw material in confectionery (Pantzaris and Ahmad, 2001). To produce cocoa butter replacer’s blend components, Zaidul et al. (2006) successfully fractionated the palm kernel oil to reduce its C12 content and increase C18:0 and C18:1 constituents using the supercritical carbon dioxide extraction (SC-CO2) method. About 28% of C12 yield was reduced in fraction 4, while 31% of C18:1 constituent increased in yield which is closer to the fatty acid composition of cocoa butter. The authors extracted PKO into four fractions and observed that at higher temperature (80 °C) the total PKO yield increased with

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

5

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx

increasing pressure. At higher pressure 48.3 MPa and temperature 80 °C, the highest yield reported was 99.6%. They reported that the highest level of short chain fatty acid such as C8, C10 and C12 constituents was found in fraction 1, while longer chain fatty acid such as C16, C18:0 and C18:1 constituents were seen in fraction 4. The lower melting point was reported in fraction 4 than in other fractions studied. The authors fractionated PKO to produce triglycerides in terms of fatty acid constituents that could be used in cocoa butter replacer’s blend. In another study, Zaidul et al. (2007c) produced cocoa butter replacer’s by blending supercritical carbon dioxide (SC-CO2) extracted PKO fractions with conventionally extracted palm oil and commercial C18:0 and C18:1 constituents at various ratios. They also fractionated PKO into four fractions using supercritical carbon dioxide (SC-CO2) and are thus called f-PKO-1, f-PKO-2, f-PKO-3 and f-PKO-4. To obtain cocoa butter replacer’s, the authors blended the f-PKO-3 and f-PKO-4 fraction as a blending components (denoted as low lauric and high oleic acid constituents) with palm oil and commercial fatty acids such as C18:0 and C18:1 constituents at different ratios and labeled as blends 1–10. The fatty acid constituents of different blends of f-PKO-3, f-PKO4, PO, commercial C18:0 and C18:1 are shown in Table 4. In both blends (f-PKO-3 and f-PKO-4) 1–10 low levels of C8 and C10 were found while large amounts of the longer chain fatty acid such as C16, C18:0, C18:1 and C18:2 were reported which are closer to that of commercial CB. The authors reported that increasing the amount of f-PKO (f-PKO-3 and f-PKO-4), more than 50% increased shorter chain fatty acid and decreased longer chain fatty acid constituents. Moreover, their results showed that the physiochemical properties like slip melting point, solid fat content, iodine value, saponification value and acid value of blends 2–10 were closer to that of commercial CB. Many other researchers have produced cocoa butter substitutes from the fractionation of palm kernel oil in the literature (Calliauw et al., 2005; Hashimoto et al., 2001). Calliauw et al. (2005) developed a two-stage dry static fractionation method for the fractionation of PKO. They also studied single-stage static fractionation method. When both methods were compared, the major advantage of the two-stage method was that it produces a higher yield of good quality palm kernel stearin and reduces the additional hydrogenation that would be advantageous for the production of cocoa butter like fat. By using this method, they produced cocoa butter substitute from PKO without hydrogenation. They also reported that about 30% of palm kernel stearin produced by the two-stage process needs to be hydrogenated for use as cocoa butter substitute. Ali (1996) produced CBEs by blending sal fat with co-fractionated palm oil. Their results showed that the triglyceride

composition and solidification characteristics were similar to that of the Malaysian cocoa butter. They also reported that the co-fractionation method increases the compatibility between CBE triglyceride components. Due to the absence of any waxy taste, trans fatty acids and low level of linoleic acid in palm oil mid-fraction (PMF), Samsudin and Rahim (1996) used it in white chocolate formulation. Two types of palm oil mid-fraction (PMF I, a commercial sample and PMF II, from a laboratory-scale acetone fractionation of PMF I) and Malaysian cocoa butter were used in white chocolate formulation. They investigated the effect of the tempering process and bloom resistance of the produced white chocolate products. They found that the tempering time to produce a well-tempered chocolate using PMF I was longer than that using PMF II, while the time to produce a well-tempered cocoa butter chocolate increased with increasing tempering temperature. The modification of fats through interesterification reactions catalyzed by enzyme has been widely studied since 1980s. It is a method which has several advantages (lower energy consumption, absence of isomerization by products, and better control of products) over the conventional methods of the chemical interesterification (Undurraga et al., 2001). Many researchers produced CBEs through enzymic interesterification of palm oil mid-fraction in the literature (Bloomer et al., 1990; Undurraga et al., 2001). To produce CBEs, Bloomer et al. (1990) studied the interesterification reaction of palm oil mid-fraction using lipase enzyme as catalysts. They studied the purity of the product and the influence of the solvent concentration on the reaction rate at different temperatures. Their results showed that the solvent concentration and temperature have great effect on the reaction rate. The optimum temperature was 40 °C and the solvent concentration was between 1 and 1.15 g of solvent/gram of substrate reported in that study. They also showed that above this temperature the rate of interesterification reduced and the product purity decreased with increase of solvent. In another study, Undurraga et al. (2001) produced CBEs through enzymatic interesterification of PMF with stearic acid in a solvent free system using Novo lipase Lipozyme™ as a catalyst. Their study was performed in batch and in a continuous packed bed reactor. They investigated the effect of different parameters such as stearic acid-PMF ratio, enzyme-substrate ratio, and humidity of the enzyme preparation on productivity. Their results showed that the highest specific productivity obtained in shake flask was 0.0393 g/Batch Interesterification Unit (BIU) h at a stearic acid–PMF ratio of 1.6 and enzyme–substrate ratio of 23 BIU/g. On the other hand, the highest mass productivity observed was 1.54 g/g h, using an enzymic load of 73 BIU/g in the continuous

Table 4 Fatty acid constituents for blends 1–10 (referred to f-PKO-3 and f-PKO-4 as a blend component) and commercial CB (Zaidul et al., 2007c). f-PKO-3 Blend number

1 2 3 4 5 6 7 8 9 10 CBa a

f-PKO-4 Fatty acid constituents (%)

Blend number

C8

C10

C12

C14

C16

C18

C18:1

C18:2

0.1 0.1 0.1 0.2 0.3 0.3 0.4 0.4 0.5 0.5 0.0

0.1 1.1 1.1 0.2 0.3 0.3 0.4 0.4 0.5 0.5 0.0

1.8 3.6 5.1 7.2 9.0 10.8 12.6 14.3 16.1 17.9 Trace

1.3 1.9 2.6 2.7 4.0 4.7 5.4 6.1 6.7 7.4 0.7

28.7 27.0 27.5 27.1 24.6 23.2 21.4 20.1 18.4 16.7 25.2

25.2 19.9 19.9 19.6 19.3 19.1 18.8 18.5 18.2 17.9 35.5

34.6 37.8 35.4 34.9 34.6 33.9 33.5 32.9 32.5 32.2 35.2

8.1 8.5 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 3.2

1 2 3 4 5 6 7 8 9 10 CBa

Fatty acid constituents (%) C8

C10

C12

C14

C16

C18

C18:1

C18:2

0.0 0.0 0.0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.0

0.0 0.0 0.0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.0

1.4 2.8 4.2 5.6 7.1 8.5 9.8 11.3 12.1 14.0 Trace

1.1 1.7 2.3 2.9 3.4 4.0 4.5 5.1 5.6 6.2 0.7

28.8 27.8 28.1 26.7 25.2 23.8 22.7 20.9 20.2 18.2 25.2

25.2 20.5 20.4 20.4 20.3 20.2 19.9 19.8 19.7 19.5 35.5

35.2 38.4 36.5 35.8 35.5 35.2 34.9 34.8 34.4 34.2 35.2

8.2 8.7 8.4 8.3 8.2 8.0 7.9 7.8 7.7 7.6 3.2

Kheiri (1982) and Pease (1985).

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

6

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx

packed bed reactor. They reported that the thermograms of their products obtained by scanning differential calorimetry were similar to that of CB, but exhibited several distinct peaks due to the presence of diglycerides and trisaturated triglycerides. They also reported that PMF could be used as a suitable raw material for interesterification with stearic acid using Lipozyme™, leading to the production of CBEs whose composition resembles closely to that of CB. Table 5 shows the composition of PMF, pure CB, and CBEs which were produced in their study. In comparison with all extraction methods, supercritical fluid extraction (SFE) is feasible in terms of quality product and has the potential to produce a higher yield and a good quality cocoa butter replacers blends. 9.2. Cocoa butter from vegetable oils Chang et al. (1990) produced cocoa butter-like fat from vegetable oils such as cottonseed and olive oils by enzymatic interesterification reaction. They produced cocoa butter fat from the reaction mixture by two filtration steps. They investigated the reaction time for the best yield of the major components such as POS of cocoa butter-like fat. The highest yield of POS was reported in reaction time at 4 h and the yield of POS reached equilibrium after 20 h. About 23 and 28% of POS and SOS were found in their studied cocoa butter-like fat. They isolated the yield of cocoa butter-like fat around 19%. Due to the higher SOS level content, the melting point of their produced cocoa butter was higher. The melting point of their products was between 29 and 49 °C. 9.3. Mango seed kernel fat Mango (Mangifera indica) is the most popular tropical fruits in the world. Mango juice and its product such as nectar drinks are the predominant fruit juice, especially in tropical and subtropical areas. In the industry, only large edible portion of mangoes are used or consumed. As a result considerable amounts of peels and seeds are discarded as industrial waste or raised as by-products. A significant large amount of these by-products particularly comes from the tropical or subtropical fruit processing industries. Due to increasing popularity and production of mangoes worldwide, disposal amounting 35 to 60% of the fruit weight represents a growing problem as the plant material is prone to microbial spoilage (Larrauri et al., 1996). Moreover, drying cost, storage, and shipment of these by- products are economically limiting factors (Schieber et al., 2001). The mango seed represents about 10–25% of the total fruit and the kernel about 45–75% of the seed and 20% of the total fruit, depending on the varieties (Arogba, 1997; Hemavathy et al., 1988). Many researchers have extracted and fractionated mango seed kernel fats using solvent extraction method (hexane, chloroform, acetone, and methanol) as mentioned in the literature (Abdalla et al., 2007; Ali et al., 1985; Lakshminarayana et al., 1983; Nzikou et al., 2010; Solís-Fuentes and Durán-de-Bazúa, 2004). According to mango varieties, the kernels contain about 5.28–15% of fats on dry a basis (Abdalla et al., 2007; Gunstone, 2011; Solís-Fuentes and Durán-de-Bazúa, 2004). The iodine value of mango seed kernel fat is 39–48 and the melting point is 34–43 °C (Gunstone, 2011).

Table 5 Triglyceride (TG) composition of PMF, CB and CBEs produced by interesterification reaction (Undurraga et al., 2001). Sample

POP

POS

SOS

Other TGs

DGs

PMF CB CBE

74.3 23.4 23.4

14.3 42.8 38.5

2.0 27.5 20.2

9.4 3.6 8.2

– 2.7 9.7

DG: diglycerides.

The major fatty acid contained in mango seed kernel fats are oleic, stearic and palmitic acids. Apart from these fatty acids, it also contains smaller amount of linoleic, arachidic, behenic, lignoceric and linolenic acids (Solís-Fuentes and Durán-de-Bazúa, 2004). The fatty acid compositions in different varieties of mango seed kernel fats are shown in Table 6. The POS (11%), SOS (40%), SOO (23%), POO (5%), SOA (4%) and OOO (5%) are the major triglycerides contained in mango seed kernel fat (Gunstone, 2011). Table 7 shows the stearin fraction of mango seed kernel fat, sal fat, shea fat, kokum butter, Illipé butter and their triglyceride compositions used in CBEs formulation. Up till now, lots of research have been conducted for the extraction and fractionation of various mango seed kernel fat as their lipid compositions as well as unique physical and chemical properties are similar to that of CB (Ali et al., 1985; Ali and Dimick, 1994; Dhinigra and Kapoor, 1985; Jiménez-Bermúdez et al., 1995; Lakshminarayana et al., 1983; Narashima-Char et al., 1977; SolísFuentes, 1998). Recently, Kaphueakngam et al. (2009) produced cocoa butter equivalent by blending mango seed almond fat (MAF) with palm oil mid-fraction (PMF). Seven blends of MAF-PMF with different ratios (100/0, 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90 and 0/100) have been studied using various techniques. Their results showed that palmitic acid, stearic acid and oleic acid were predominant fatty acid in all blends, which were similar to cocoa butter components. They reported that the major fatty acid, the melting behaviour and slip melting point of the 80/40 (wt%) blend resemble to that of cocoa butter. In another study, SolísFuentes and Durán-de-Bazúa (2004) studied the thermal behaviour of mango seed almond fat and its mixtures with cocoa butter. They reported that the fatty acid contents and the physiochemical properties of mango almond fat are similar to those of cocoa butter. They also showed that the MAF curves for solid–liquid phase change and the solid fat content MAF profiles are great similar to those of cocoa butter. The properties of MAF, thermal conduct and the presence of a and b crystalline forms in MAF made it a suitable fat like cocoa butter. The isosolid diagrams showed the compatibility between the mixture of MAF and CB fats, even better than that of mixtures of CB with milk fat, lauric fats, or hydrogenated cottonseed oil (Solís-Fuentes and Durán-de-Bazúa, 2004). 9.4. Kokum butter Kokum butter (Garcinia indica Choisy Syn Brindonia indica) belongs to the family of Guttiferae, and is found in the western peninsular coastal regions and the states of Maharashtra, Goa, Karnataka and Kerala India and parts of Eastern India in the states of West Bengal, Assam, and North Eastern Hill regions and other parts of peninsular India. It is a small evergreen tree and is also known as mangosteen, goa butter tree, kokum butter tree (Baliga et al., 2011). The mature tree yield fruits annually and takes 5 months to complete its fruiting process and by March to May the ripe fruits are ready for harvesting. The fruits are spherical and red to dark purple in colour and the edible pulp is sour. Each fruit contains 3 to 8 large seeds covered with pulp and the kernel contain around 40–44% hard and brittle fat with melting point of 38–42 °C (Gunstone, 2011). The seed accounts for nearly a quarter of the total fruit weight and it contains 23–26% oil. The oil is solid at room temperature and is known as kokum butter. Kokum butter is extracted from the seeds, has highly demanded in confectionary industries, especially in chocolate industries, due to its light grey colour, greasy texture, and is bland to taste (Nayak et al., 2010). To extract the oil is a laborious process and is carried out in the extractor. Normally, the kernels are separated carefully and then pressed in expeller to extract the oil. Traditionally, the oil is extracted by boiling the kernel in water but solvent extraction is also used. Two types of major fatty acid such as stearic (50–60%)

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

7

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx Table 6 Fatty acid compositions of mango seed kernel fat (%) from different studies. Variety

Origin

Fatty acids (%)

References

16:0

18:0

18:1

18:2

18:3

20:0

22:0

24:0

43 varieties Manila

India Mexico

3–18 9.29

24–57 39.07

34–56 40.81

1–13 6.06

– 0.64

1–4 2.48

– 0.64

– 0.49

10 varieties

Bangladesh

41.1– 43.8 41.09 46.22 46.1

6.0– 7.6 6.97 7.33 8.2

0.6– 1.0 – 2.30 1.2

1.7– 2.6 – – –

–

Thailand Congo Egypt

38.2– 40.2 46.55 37.73 38.3

–

Keaw Kibangou Zebda, Balady and Succary (mixed)

7.9– 10.0 5.39 6.43 5.8

Lakshminarayana et al. (1983) Solís-Fuentes and Durán-de-Bazúa (2004) Ali et al. (1985)

– – –

– – –

Kaphueakngam et al. (2009) Nzikou et al. (2010) Abdalla et al. (2007)

Table 7 The monounsaturated triglycerides (%) of selected fats and its fraction suitable for use in CBE (Gunstone, 2011).

a

Fat type

POP

POS

SOS

Mango kernel fractiona Kokum butter Sal fractiona Shea fractiona Illipé butter Cocoa butter

1 Trace Trace 1 7 16

16 6 10 7 24 37

59 72 60 74 45 26

Stearin (hard/higher-melting) fraction.

Table 8 Fatty acid and triacylglyceride compositions of hard butter from kokum fat and phulwara butter (Reddy and Prabhakar 1994). Phulwara butter middle fraction Fatty acid (%) Palmitic acid Stearic acid Oleic acid Linoleic acid Triacylglycerols (%) Trisaturated (GS3) Monounsaturated disaturated (GS2U) Diunsaturated monosaturated (GSU2) a

Blend 1a

was added up to 5% by the weight of the product. They also reported that the hardness of both chocolates increased with increased addition of kokum fat. Recently, extensive reviews of the chemistry and medicinal values as well as industrial uses of kokum fat are published by Baliga et al. (2011). Reddy and Prabhakar (1994) produced cocoa butter extenders with different melting profiles by blending of both middle fraction of kokum fat with phulwara butter in selected proportions (60/40, 65/35, 70/30, 75/25). In that study, the fatty acid and triacylglyceride compositions of blend 60/40 were similar to those of CB (Table 8). Their results showed that the blends with higher level of kokum fat are harder than cocoa butter and have short melting ranges. They reported that the solidification properties, fatty acid and triacylglyceride compositions and tolerance towards milk fat properties are similar to those of cocoa butter. They also reported that the melting range of their products are the same as those of CB and compatible with CB and also have tolerance towards milk fat.

CB

9.5. Sal fat 66.3 3.9 27.7 0.6

34.4 35.3 30.0 0.2

31.0 34.0 35.0 –

2.5 85.0

2.0 89.0

– 90.0

12.0

7.8

10.0

Blend 1: blend of 60% phulwara butter middle fraction with 40% kokum fat.

and oleic (36–40%) acids, and triacylglycerides that is SOS about 72% were obtained in the kokum fat (Table 7). A group of researchers reported that the addition of a small amount of SOS or SOS-rich fats in CB or chocolate increases the hardness, inhibits fat bloom and decreases the tempering time (Jewell and Bradford, 1981; Jeyarani and Reddy, 1999; Maheshwari and Reddy, 2005; Padley et al., 1972; Reddy and Prabhakar, 1994; Tonnesmann, 1977). Because of the well composition of fatty acids (stearic and oleic acid) and triglycerides, in particular SOS in the kokum fats, it is used as a suitable raw material for the production of high temperature resistant hard butter in countries with hot climate. Therefore, kokum butter could solve the tempering difficulties for chocolate manufacturers in tropical countries or in countries with a moderate climate during summer season. In dark and milk chocolate formulations, kokum fat is added in different proportions to replace CB and its effects on rheology, hardness, triglyceride compositions and heat resistance studied by Maheshwari and Reddy (2005). No significant influence have been seen in the plastic viscosity or yield stress of milk or dark chocolate when kokum fat

Sal fat (Shorea robusta) is obtained from the seed kernel of sal trees, widely grown in India, Malaysia, Borneo, Java, and Philippines. About 5% of the total forest area in India is occupied by Sal trees. The kernels constitute 72% of the weight of the sal seeds. The sal seed kernels contain 19–20% of oil which is known as Sal butter. The fatty acid compositions of Sal fat is shown in Table 9. The fatty acid profiles of Sal fat have some similarity to that of cocoa butter since oleic and stearic acids dominate. The iodine value of sal fat is 31–45 and the melting point is 30–36 °C. The POS (11%), SOS (42%), SOO (16%), SOA (13%), OOO (3%) and AOO (4%) are the major triglycerides contained in sal fat (Gunstone, 2011). Gunstone (2011) reported that fractionation of sal fat is necessary for making cocoa butter resembles triglycerides which is a valuable ingredient for CBEs. Reddy and Prabhakar (1989) produced cocoa butter extenders by blending of stearins of sal fat with phulwara butter in selected proportions. Their results showed that the solidification properties and solid fat indices of blends containing 75–85% of sal fat stearin and 15–25% of phulwara butter stearin closer to CB. Cocoa butter extenders were made by decreasing the sal fat stearin to 50–67% in the blend. They also reported that a series of cocoa butter extenders can be made by changing the sal fat and phulwara butter stearin ratios in the blends which show similar chemical and physical properties like CB. 9.6. Shea butter Shea butter belongs to the family of Sapotaceae, a common West African and sub-saharan African edible vegetable fat obtained from the shea kernel Vitellaria paradoxa (C.F. Gaertn) and also called Butyrospermum parkii L. (Bail et al., 2009; Teklehaimanot,

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

8

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx

Table 9 Fatty acids of Sal fat from different studies. Fatty acids

References

16:0

18:0

18:1

18:2

18:3

20

4.8 6.3 5.6 8.3 4.6

44.2 44.6 44.3 34.7 43.2

42.4 41.6 40.4 41.9 42.0

2.5 1.7 1.5 2.8 2.2

– – –

6.1 5.7 7.7 12.3 6.7

Table 10 Major fatty acid compositions of shea butter from different studies. Fatty acids

References

16:0

18:0

18:1

18:2

18:3

20

3.4 5.7 4.0 8.0 4.0 3.8

41.8 41.0 58.0 37.0 43.2 44.1

45.9 49.0 33.0 50.0 43.9 43.8

6.6 4.3 3.0 5.0 6.6 6.65

1.3 – – – 0.3 1.55

0.2 – 2.0 – 1.6 -

Jatto et al. (2010) Banerji et al. (1984) Hogenbrink (1984) Meara (1979) Kanematsu et al. (1978) Jacobsberg (1977)

1.3

Vedaramana et al. (2012) Bhattacharyya and Bhattacharyya (1991) Sridhar et al. (1991) Banerji et al. (1984) Chaudhuri et al. (1983)

far that could meet the exact demand of cocoa butters. To overcome the problem, further and prudential research on this topic need to be conducted finding out the precise alternatives of cocoa butter fats that could be able to fulfill the demands of cocoa butter fats. Acknowledgement The authors wish to acknowledge Universiti Sains Malaysia (USM fellowship) for the financial support. References

2004). Shea kernel contains 40–55% oil, called shea butter (Casten and Synder, 1985; Gunstone, 2011; Olajide et al., 2000). Traditionally, shea butter is extracted using organic solvent. The iodine value of shea fat is 52–56 and the melting point is 32–45 °C (Gunstone, 2011). The major fatty acid contents of shea butter from different studies are summarized in Table 10. The POP (3%), POS (6%), SOS (42%), SOO (26%), SOL (5%), SLS (5%) and OOO (6%) are the main triglycerides contained in shea fat (Gunstone, 2011). Based on the triglyceride compositions, shea butter is used as cocoa butter substitutes in the chocolate and confectionary industry in Europe (Olajide et al., 2000). Recently, a group of researchers reported that the variety, climate and regional differences influence the quality of fatty acid compositions as well as fat properties of shea butter (Bail et al., 2009; Cardi et al., 2005; Di Vincenzo et al., 2005; Sanou et al., 2006). 9.7. Illipé butter Illipé butter (Shorea stenoptera) is also called Borneo tallow and produced from the seed kernel of the trees widely grown in Sarawak Malaysia, Java Indonesia, the Philippines and the other parts of Borneo. The ripe Illipé nuts contain about 40 to 60% valuable edible fats. The melting point of Illipé butter is 37–39 °C and iodine value is 29–38 (Firestone, 1999). The major fatty acid contained in Illipé butter are palmitic (18–21%), stearic (39–46%) and oleic (34–37%) acids. The fatty acid compositions of Illipé butter resemble that of cocoa butter. The main triglycerides of Illipé butter are POP (7%), POS (34%) and SOS (45%) which is closer to that of cocoa butter. Recently, Gunstone (2011) reported that Illipé butter can be used directly as cocoa butter equivalent without further processing. 10. Conclusions CB is a unique fat. Due to shortage of supply, high price, and technological reasons efforts have been made to find an alternative to CB. A number of natural fats have been investigated for CB alternatives that could have closer physical properties. Thus, CB alternatives are produced either by blending or modifying fats in some proportions. The individual analysis of plant triglycerides in terms of fatty acid compositions are well discussed in this review. However, no alternatives of cocoa butter fats have been found so

Abdalla, A.E.M., Darwish, S.M., Ayad, E.H.E., El-Hamahmy, R.M., 2007. Egyptian mango by-product 1. Compositional quality of mango seed kernel. Food Chemistry 103, 1134–1140. Adeyeye, E.I., Akinyeye, R.O., Ogunlade, I., Olaofe, O., Boluwade, J.O., 2010. Effect of farm and industrial processing on the amino acid profile of cocoa beans. Food Chemistry 118, 357–363. Adu-Ampomah, Y., 1996. The cocoa breeding programme in Ghana: achievements and prospects for the future. Cocoa Growers’ Bulletin 50, 17–21. Adu-Ampomah, Y., Sersah, J.A., 1987/1988. Annual Report. Cocoa Research Institute of Ghana. Ali, M.A.R., 1996. Effect of co-fractionation technique in the preparation of palm oil and sal fat based cocoa butter equivalent. International Journal of Food Science and Nutrition 47 (1), 15–22. Ali, M.A.R., Dimick, P.S., 1994. Thermal analysis of palm midfraction, cocoa butter and milk fat blends by differential scanning calorimetry. Journal of the American Oil Chemists’ Society 71 (3), 299–302. Ali, M.A., Gafur, M.A., Rahman, M.S., Ahmed, G.M., 1985. Variations in fat content and lipid class composition in ten different mango varieties. Journal of the American Oil Chemists’ Society 62 (3), 520–523. Amin, I., Jinap, S., Jamilah, B., 1997. Vicilin-class globulin and their degradation during cocoa fermentation. Food Chemistry 59, 1–5. Amin, I., Jinap, S., Jamilah, B., 1998. Proteolitic activity (aspartic endoproteinase and carboxypeptidase) of cocoa bean during fermentation. Journal of Science Food and Agriculture 76, 123–128. Amin, I., Jinap, S., Jamilah, B., Harikrisna, K., Biehl, B., 2002. Oligopeptide patterns produced from Theobroma cacao L. of various genetic origins. Journal of Science Food and Agriculture 82, 733–737. Arogba, S.S., 1997. Physical, chemical and functional properties of Nigerian mango (Mangifera indica) kernel and its processed flour. Journal of the Science of Food and Agriculture 73, 321–328. Asep, E.K., Jinap, S., Tan, T.J., Russly, A.R., Harcharan, S., Nazimah, S.A.H., 2008. The effects of particle size, fermentation and roasting of cocoa nibs on supercritical fluid extraction of cocoa butter. Journal of Food Engineering 85, 450–458. Bail, S., Krist, S., Masters, E., Unterweger, H., Buchbauer, G., 2009. Volatile compounds of shea butter samples made under different production conditions in western, central and eastern Africa. Journal of Food Composition and Analysis 22, 738–744. Baliga, M.S., Bhat, H.P., Pai, R.J., Boloor, R., Palatty, P.L., 2011. The chemistry and medicinal uses of the underutilized Indian fruit tree Garcinia indica Choisy (kokum)—a review. Food Research International 44, 1790–1799. Banerji, R., Chowdhury, A.R., Misra, G., Nigam, S.K., 1984. Butter from plants. Fette Seifen Anstrichmittel 86, 279–284. Bhattacharyya, S., Bhattacharyya, D.K., 1991. Enzymatic acidolysis of sal fat and its fractions. Oleagineux 46, 509–513. Bloomer, S., Adlercreutz, P., Mattiasson, B., 1990. Triglyceride interesterification by lipase. 1. Cocoa butter equivalents from a fraction of palm oil. Journal of the American Oil Chemist’s Society 67 (8), 519–524. Bracco, U., 1994. Effect of triglyceride structure on fat absorption. The American Journal of Clinical Nutrition 60, S1002–S1009. Calliauw, G., Foubert, I., De Grevt, W., Dijckmans, P., Kellens, M., Dewettinck, K., 2005. Production of cocoa butter substitutes via two-stage fractionation of palm kernel oil. Journal of the American Oil Chemists’ Society 82, 783–789. Cardi, C., Vaillant, A., Sanou, H., Kelly, B., Bouvet, J., 2005. Characterization of microsatellite markers in the shea tree (Vitellaria paradoxa C.F. Gaertn) in Mali. Molecular Ecology Notes 5 (3), 524–526.

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx Casten, J., Synder, H.E., 1985. Understanding Pressure Extraction of Vegetable Oils. Volunteers in Technical Assistance (VITA), no. 40. Virginia, USA, pp. 1–15. Chaiseri, S., Dimick, P.S., 1989. Lipid and hardness characteristics of cocoa butters from different geographic regions. Journal of the American Oil Chemist’s Society 66, 1771–1776. Chang, M.-K., Abraham, G., John, V.T., 1990. Production of cocoa butter-like fat from interesterification of vegetable oils. Journal of the American Oil Chemist’s Society 67 (11), 832–834. Chaudhuri, G., Chakrabarty, M.M., Battacharyya, D., 1983. Modification of some tree borne seed fats for the preparation of high priced confectionery fats. Fette Seifen Anstrichmittel 85, 224–227. D’Alonzo, R.P., Kozarek, W.J., Wade, R.L., 1982. Glyceride composition of processed fats and oils as determined by glass capillary gas chromatography. Journal of the American Oil Chemists’ Society 59, 292–295. Davis, T.R., Dimick, N., 1989. Lipid composition of high melting seed crystals formed during cocoa butter solidification. Journal of the American Oil Chemists’ Society 66, 1494–1498. de Magalhães, J.T., Sodré, G.A., Viscogliosi, H., Grenier-Loustalot, M.-F., 2011. Occurrence of Ochratoxin A in Brazilian cocoa beans. Food Control 22, 744–748. Dhinigra, S., Kapoor, A., 1985. Nutritive value of mango seed kernel. Journal of the Science of Food and Agriculture 36, 752–756. Di Vincenzo, D., Maranz, S., Serraiocco, A., Vito, R., Wiesman, Z., Bianchi, G., 2005. Regional variation in shea butter lipid and triterpene composition in four African countries. Journal of Agricultural and Food Chemistry 53 (19), 7473– 7479. Erickson, J.A., Weissberger, W., Keeney, P.G., 1983. Tocopherols in the unsaponifiable fraction of cocoa lipids. Journal of Food Science 38, 1158–1162. Food and Agriculture Organization (FAO), 1977. FAO corporate document repository. FAO Economic and Social Development Series. . Food and Agriculture Organization (FAO), 2012. Committee on Commodity Problems. The Future of the World Cocoa Economy: Boom or Bust? 69th Session, 28–30 May 2012, Rome, Italy. . Firestone, D., 1999. Physical and Chemical Characteristics of Oils, Fats, and Waxes. AOCS, Champaign, IL. Gunstone, F.D., 2011. Vegetable Oils in Food Technology Composition, Properties and Uses, second ed. Willy-Blackwell, CRC Press, pp. 291–343. Hashimoto, S., Nezu, T., Arakawa, H., Ito, T., Maruzeni, S., 2001. Preparation of sharpmelting hard palm midfraction and its use as hard butter in chocolate. Journal of the American Oil Chemists’ Society 78 (5), 455–460. Hassan, M., Philippe, J.B., Alain, P., Gerard, G., 1995. Production of cocoa butter quivalents from prickly-pear juice fermentation by an unsaturated fatty acid auxotroph of Cryptococcus curvatus grown in batch culture. Process Biochemistry 30 (7), 629–634. Hassan, M.N., Rahman, N.A.N., Anuar, B.O., Ibrahim, M.H., Omar, A.K.M., 2000. Simple f fractionation through the supercritical carbon dioxide extraction of palm kernel oil. Separation and Purification Technology 19, 113–120. Hemavathy, J., Prabhakar, J.V., Sen, D.P., 1988. Drying and storage behaviour of mango (Mangifera indica) and composition of kernel fat. Asian Food Journal 4, 59–63. Herrero, M., Cifuentes, A., Ibanez, E., 2006. Sub and supercritical fluid extraction of functional ingredients from different natural sources: plants, food-by-products, algae and microalgae: a review. Food Chemistry 98, 136–148. Herrero, M., Mendiola, J.A., Cifuentes, A., Ibáñez, E., 2010. Supercritical fluid extraction: Recent advances and applications-a review. Journal of Chromatography A 1217, 2495–2511. Hogenbrink, G., 1984. Compatibility of specialty fats with cocoa butter. In: 38th Pensylvania Manufacturing Confectioner’s Association Production Conference, pp. 116–120. Hoskin, J.C., Dimick, P.S., 1984. Role of non-enzymatic browning during the processing of chocolate flavor: a review. Processing and Biochemistry 19, 92– 103. Hoskin, J.C., Dimick, P.S., 1994. Chemistry of flavour development in chocolate. In: Beckett, S.T. (Ed.), Industrial Chocolate Manufacture and Use, second ed. Van Nostrand Reinhold, New York, pp. 102–115. Hultin, H.O., 1994. Oxidation of lipids in seafoods. In: Shahidi, F., Botta, J.R. (Eds.), Seafoods: Chemistry, Processing Technology and Quality. Chapman & Hall, London, pp. 49–74. International Cocoa and Commodities Organisation, 2000. ICCO Celebration of Cocoa 2000. K.P. Partners in Publishing, London. International Cocoa and Commodities Organisation (ICCO). Quarterly Bulletin of Cocoa Statistics, vol. xxxvi, no. 4, Cocoa year 2009/2010. Jacobsberg, B., 1977. Causes de l’adification du beurre du karite au tours de la preparation et du stockage des amandes. Oleagineux 32, 529–533. Jatto, W.O., Yuanfa, L., Shan, L., Wang, X., Aworh, O., 2010. Liquid-Gas chromatographic analysis of fatty acid content of south-western nigerian shea butter (Vitelleria paradoxum). Electronic Journal of Environmental, Agricultural and Food Chemistry 9 (2), 358–363. Jewell, G.G., Bradford, L., 1981. Considerations in chocolate formulation. Manufacturing Confectionary 61 (1), 26–30. Jeyarani, T., Reddy, Y.S., 1999. Heat resistant cocoa butter extenders from mahua (Madhuca latifolia) and kokum (Garcinia indica) fats. Journal of the American Oil Chemists’ Society 76, 1431–1436.

9

Jiménez-Bermúdez, M., Silva-Hernández, E.R., Solís-Fuentes, J.A., Durán-de-Bazúa, M.C. (1995). La grasa de semilla de mango comoposible sustituto de la manteca de cacao. In: I Congreso Iberoamericano de Ingenier_ıa de los Alimentos, November 4–7. Campinas, S.P. Brazil. Jinap, S., 1994. Organic acids in cocoa beans—a review. ASEAN Food Journal 9, 3–12. Jonfia-Essien, W.A., West, G., Alderson, P.G., Tucker, G., 2008. Phenolic content and antioxidant capacity of hybrid variety cocoa beans. Food Chemistry 108, 1155– 1159. Kanematsu, H., Maruyama, T., Niiya, I., Imamura, M., Matsumoto, T., 1978. Studies on the hard butter II. On the general properties of vegetable cocoa butter substitutes. Journal of the Japanese Oil Chemists’ Society 21, 519–520. Kaphueakngam, P., Flood, A., Sonwai, S., 2009. Production of cocoa butter equivalent from mango seed almond fat and palm oil mid-fraction. Asian Journal of Food and Agro-Industry 2 (04), 441–447. Keen, C.L., Holt, R.R., Oteiza, P.I., Fraga, C.G., Schmitz, H.H., 2005. Cocoa antioxidants and cardiovascular health. American Journal of Clinical Nutrition 81, 298S– 303S. Kheiri, M.S.A., 1982. Formulation, Evaluation and Marketing of Cocoa Butter Replacer’s Fat. Palm Oil Research Institute of Malaysia (PORIM), Kuala Lumpur. Kris-Etherton, P.M., Keen, C.L., 2002. Evidence that the antioxidant flavonoids in tea and cocoa are beneficial for cardiovascular health. Current Opinion in Lipidology 13, 41–49. Lakshminarayana, G., Chandrasekhara-Rao, T., Ramalingaswamy, P.A., 1983. Varietal variations in content characteristics and composition of mango seed and fat. Journal of the American Oil Chemists’ Society 60 (1), 88–89. Larrauri, J.A., Ruperez, P., Borroto, B., Saura-Calixto, F., 1996. Mango peels as a new tropical fibre: preparation and characterization. Lebensmittel-Wissenschaft und – Technologie 29, 729–733. Lee, K.W., Kim, Y.J., Lee, H.J., Lee, C.Y., 2003. Cocoa has more phenolic phytochemicals and a higher antioxidant capacity than teas and red wine. Journal of Agricultural and Food Chemistry 51, 7292–7295. Lehrian, D.W., Keeney, P.G., 1980. Changes in lipid component of seed during growth and ripening of cocoa fruit. Journal of the American Oil Chemists’ Society 57, 61–65. Li, S., Hartland, S., 1992. Influence of co-solvents on solubility and selectivity in extraction of xanthines and cocoa butter from cocoa beans with supercritical CO2. The Journal of Supercritical Fluids 5, 7–12. Li, S., Hartland, S., 1996. A new industrial process for extracting cocoa butter and xanthines with supercritical carbon dioxide. Journal of the American Oil Chemists’ Society 73 (4), 423–429. Lipp, M., Anklam, E., 1998. Review of cocoa butter and alternative fats for use in Chocolate. Part A. Compositional data. Food Chemistry 62, 73–97. Lipp, M., Simoneau, C., Ulberth, F., Anklam, E., Crews, C., Brereton, P., de Greyt, W., Schwack, W., Wiedmaier, C., 2001. Composition of genuine cocoa butter and cocoabutter equivalents. Journal of Food Composition and Analysis 14, 399– 408. Maheshwari, B., Reddy, S.Y., 2005. Application of kokum (Garcinia indica) fat as cocoa butter improver in chocolate. Journal of the Science of Food and Agriculture 85, 135–140. Malaysian Cocoa Board (MCB), 2011. Department of Statistic Malaysia. . McHugh, M.A., Krukonis, V.J., 1994. Supercritical Fluid Extraction: Principles and Practice, second ed. Butterworth-Heinemann, Boston, pp. 293–310. Meara, M. L., 1979. Confectionery fats. In: Proceedings of the International Congress on Oilseeds and Oils, New Dehli, India. Moreton, R.S., 1988. Single cell oil. In: Moreton, R.S. (Ed.), Physiology of Lipid Accumulating Yeast. Longman Scientific and Technical, London, pp. 1–32. Nair, P.K.P., 2010. 5-Cocoa (Theobroma cacao L.). The Agronomy and Economy of Important Tree Crops of the Developing World. Elsevier, London, pp. 131–180. Narashima-Char, B.L., Reddy, B.R., Thirumala-Rao, S.D., 1977. Processing mango stones for fat. Journal of the American Oil Chemists’ Society 54, 494–495. Nayak, C.A., Rastogi, N.K., Raghavarao, K.S.M.S., 2010. Bioactive constituents present in Garcinia indica Choisy and its potential food applications – a review. International Journal of Food Properties 13, 441–453. Norulaini, N.A.N., Zaidul, I.S.M., Anuar, O., Omar, A.K.M., 2004. Supercritical enhancement for separation of lauric acid and oleic acid in palm kernel oil (PKO). Separation and Purification Technology 39, 133–138. Norulaini, N.A.N., Setianto, W.B., Zaidul, I.S.M., Nawi, A.H., Azizi, C.Y.M., Mohd Omar, A.K., 2009. Effects of supercritical carbon dioxide extraction parameters on virgin coconut oil yield and medium-chain triglyceride content. Food Chemistry 116, 193–197. Nzikou, J.M., Kimbonguila, A., Matos, L., Loumouamou, B., Pambou-Tobi, N.P.G., Ndangui, C.B., Abena, A.A., Silou, T., Scher, J., Desobry, S., 2010. Extraction and characteristics of seed kernel oil from mango (Mangifera indica). Research Journal of Environmental and Earth Sciences 2 (1), 31–35. Olajide, J.O., Ade-Omowaye, B.I.O., Otunola, E.T., 2000. Some physical properties of shea kernel. Journal of Agricultural Engineering Research 76, 419–421. Omar, A.K.M., Rahman, N.A.N., Hassan, M.N., 1998. Process for a simultaneous extraction and fractionation of palm kernel oil using supercritical carbon dioxide as a solvent. Malaysian patent no. P19805730. Padley, F.B., Paulussen, C.N., Soeters, C.J., Tresser, D., 1972. The improvement of chocolate using the mono-unsaturated triglycerides SOS and POS. Revue Internationale de la Chocolaterie 27 (9). Pantzaris, T.P., Ahmad, M.J., 2001. Properties and utilization of palm kernel oil. Palm Oil Developments 35 (11–15), 19–23.

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024

10

M.H.A. Jahurul et al. / Journal of Food Engineering xxx (2012) xxx–xxx

Pease, J.J., 1985. Confectionery fats from palm oil and lauric oil. Journal of the American Oil Chemist’s Society 62 (2), 426–430. Puziah, H., Jinap, S., Sharifah, K., Asbi, A., 1998. Changes in free amino acids, peptideN, sugar and pyrazine concentration during cocoa fermentation. Journal of the Science of Food and Agriculture 78, 535–542. Reddy, S.Y., Prabhakar, J.V., 1989. Confectionery fats from sal (Shorea robusta) fat and phulwara (Madhuca butyracea) butter. Food Chemistry 34 (2), 131–139. Reddy, S.Y., Prabhakar, J.V., 1994. Cocoa butter extenders from Kokum (Garcinia indica) and Phulwara (Madhuca butyracea) butter. Journal of the American Oil Chemists’ Society 7, 217–219. Rossi, M., 1996. Supercritical fluid extraction of cocoa and cocoa products. In: King, J.W., List, G.R. (Eds.), Supercritical Fluid Technology in Oil and Lipid Chemistry. AOCS Press, Champaign, Illinois, pp. 220–229. Sahena, F., Zaidul, I.S.M., Jinap, S., Karim, A.A., Abbas, K.A., Norulaini, N.A.N., Omar, A.K.M., 2009. Application of supercritical CO2 in lipid extraction – a review. Journal of Food Engineering 95, 240–253. Samsudin, S., Rahim, M.A.A., 1996. Use of palm mid-fraction in white chocolate formulation. Journal of the Science of Food and Agriculture 71, 483–490. Sanchez-Rabaneda, F., Jauregui, O., Casals, I., Andres-Lacueva, C., Izquierdo-Pulido, M., Lamuela-Raventos, R.M., 2003. Liquid chromatographic/electrospray ionization tandem mass spectrometric study of the phenolic composition of cocoa Theobroma cacao. Journal of Mass Spectrometry 38, 35–42. Sanou, H., Picard, N., Lovett, P.N., Dembélé, M., Korbo, A., Diarisso, D., Bouvet, J.-M., 2006. Phenotypic variation of agromorphological traits of the Shea Tree, Vitellaria paradoxa C.F. Gaertn., in Mali. Genetic Resources and Crop Evolution 53, 145–161. Schieber, A., Stintzing, F.C., Carle, R., 2001. By-products of plant food processing as a source of functional compounds—recent developments. Trends in Food Science & Technology 12, 401–413. Solís-Fuentes, J.A., 1998. El aprovechamiento de residuos sólidos ylíquidos de la agroindustria alimentaria, cinco ejemplos. M.S. Thesis. Facultad de Química, UNAM. México, D.F. Solís-Fuentes, J.A., Durán-de-Bazúa, M.C., 2004. Mango seed uses: thermal behaviour of mango seed almond fat and its mixtures with cocoa butter. Bioresource Technology 92, 71–78. Spangenberg, J.E., Dionisi, F., 2001. Characterization of cocoa butter and cocoa butter equivalents by bulk and molecular carbon isotope analyses: implications for vegetable fat quantification in chocolate. Journal of Agricultural and Food Chemistry 49, 4271–4277. Sridhar, R., Lakshiminarayana, G., Kaimal, T.N.B., 1991. Modification of selected Indian vegetable fats into cocoa butter substitutes by lipase-catalyzed esters interchange. Journal of the American Oil Chemists’ Society, 68, 726730.

Staby, A., Mollerup, J., 1993. Separation of constituents of fish oil using supercritical fluids: a review of experimental solubility, extraction, and chromatographic data. Fluid Phase Equilibria 91, 349–386. Staphylakis, K., Gegiou, D., 1985. Sterols in cocoa butter. Fette Set&m Anstrichmittel 87, 150–155. Steinberg, F.M., Bearden, M.M., Keen, C.L., 2003. Cocoa and chocolate flavonoids: implications for cardiovascular health—a review. Journal of the American Dietetic Association 103, 215–223. Teklehaimanot, Z., 2004. Exploiting the potential of indigenous agroforestry trees: Parkia biglobosa and Vitellaria paradoxa in sub-Saharan Africa. Agroforestry Systems 61, 207–220. Tonnesmann, B.O.M., 1977. The Manufacturing Confectioner 57 (5), 35. Undurraga, D., Markovits, A., Erazo, S., 2001. Cocoa butter equivalent through enzymic interesterification of palm oil mid-fraction. Process Biochemistry 36, 933–939. Vedaramana, N., Puhanb, S., Nagarajanc, G., Ramabrahmama, B.V., Velappana, K.C., 2012. Methyl ester of Sal oil (Shorea robusta) as a substitute to diesel fuel—a study on its preparation, performance and emissions in direct injection diesel engine. Industrial Crops and Products 36, 282–288. Wollgast, J., Anklam, E., 2000. Review on polyphenols in Theobroma cacao: changes in composition during the manufacture of chocolate and methodology for identification and quantification. Food Research International 33, 423–447. Yanamoto et al. (1995). Methods of producing white cocoa nibs and food using white cocoa nibs. United States Patent. Patent Number: 5395635. Zaidul, I.S.M., Norulaini, N.A.N., Mohd Omar, A.K., Smith Jr., R.L.(, 2006. Supercritical carbon dioxide (SC-CO2) extraction and fractionation of palm kernel oil from palm kernel as cocoa butter replacers blend. Journal of Food Engineering 73 (2006), 210–216. Zaidul, I.S.M., Norulaini, N.A.N., Omar, A.K.M., Sato, Y., Smith Jr., R.L., 2007a. Separation of palm kernel oil from palm kernel with supercritical carbon dioxide using pressure swing technique. Journal of Food Engineering 81, 419– 428. Zaidul, I.S.M., Norulaini, N.A.N., Omar, A.K.M., Smith Jr., R.L., 2007b. Supercritical carbon dioxide (SC-CO2) extraction of palm kernel oil from palm kernel. Journal of Food Engineering 79, 1007–1014. Zaidul, I.S.M., Norulaini, N.A.N., Omar, A.K.M., Smith Jr., R.L., 2007c. Blending of supercritical carbon dioxide (SC-CO2) extracted palm kernel oil fractions and palm oil to obtain cocoa butter replacers. Journal of Food Engineering 78, 1397– 1409. Zumbe, A., 1998. Polyphenols in cocoa: are there health benefits? British National Formulary. Nutrition Bulletin 23, 94–102.

Please cite this article in press as: Jahurul, M.H.A., et al. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, and characteristics. Journal of Food Engineering (2012), http://dx.doi.org/10.1016/j.jfoodeng.2012.09.024