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Production of cocoa butter-like fat from interesterification of vegetable oils
Abstract
Cocoa butter-like fat was prepared from completely hydrogenated cottonseed and olive oils by enzymatic interesterification.
The optimum reaction time to produce the major-component of cocoa butter, 1(3)-palmitoyl-3(1)-stearoyl-2-monoolein (POS),
was 4 hr. The cocoa butter-like fat was isolated from the reaction mixture by two filtration steps. The yield of cocoa butter-like
fat was 19%, based on the weight of the original oils. Chromatographic analysis of the product by reversephase high-performance
liquid chromatography (HPLC) has shown it contains triglyceride components similar to those of cocoa butter, but that it has
slightly more diglycerides. The melting point of this product, as measured by a differential scanning calorimeter, is 39°C,
which compares well to the 36°C melting point of natural cocoa butter.
... Vegetable oils are abundant in C18:1 acid, hence are very suitable to blend with cocoa butter replacer (CBR) and it is very good for confectionery fat due to its lower melting point. Most of the CBR are obtained from natural plant fats or produced specifically by chemical or enzymatic fractionation from plant fats (Reddy and Prabhakar, 1989;Bloomer et al., 1990;Chang et al., 1990;Reddy and Prabhakar, 1990;Sridhar et al., 1991;Chong et al., 1992;Nesaretnam and Md. Ali, 1992;Mojovic et al., 1993;Lipp and Anklam, 1998a (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;Jimenez-Bermudez et al., 1995;Kaphueakngam et al., 2009;Lakshminarayana et al., 1983;Solis-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), illipe fat (Gunstone, 2011) etc. are conducted . ...
... Procedures for chemical interesterification of cheap fats and oils to produce analogs have been developed for years and are found to be practical to industries (Liu et al., 1997). Recently, preparation of CBE through 1, 3-specific lipase-catalyzed interesterification has received much attention because lipases offer certain advantages over other chemical catalysts (Chang et al., 1990). The purpose of interesterification is to incorporate selectively stearic residues into triglycerides in positions 1 and 3 until a composition resembling CB composition is obtained. ...
... CBE are also produced by the blending of CB with milk fat, lauric fats, MAF or hydrogenated cottonseed oil (Kaphueakngam et al., 2009;Solis-Fuentes and Duran-de-Bazua, 2004). Production of a cocoa butter-like fat from the interesterification of totally hydrogenated cottonseed and olive oils was studied (Chang et al., 1990). ...
Cocoa butter (CB) is the byproduct of cocoa bean processing industry and is obtained from the mature bean from the Theobroma cacao plant. It is an important ingredient in the chocolate and other confectionery industries. It's valued for its unique physicochemical properties which is given by its peculiar fatty acid composition. The major triacylglycerols (TAG) present in CB is symmetrical and contains very less amount of highly unsaturated fatty acid. The major fatty acids present in it are palmitic acid, stearic acid, oleic acid and linoleic acid, but low amounts of lauric acid and myristic acid. Increasing demand and shortage of supply for CB, poor quality of individual harvests, economic advantages and some technological benefits have induce for the development of its alternative called cocoa butter replacer (CBR). In the CBRs the TAG compositions are similar but are not identical to genuine CB. Most of them are produced by either modification of natural fat or by their blending in different proportion. However, it couldn’t satisfy the consumer and fulfill the demand of confectionery industries. This review gives a brief idea about the processing of cocoa pod, the production of cocoa butter and its composition with fats that are commonly used as its Replacers
... Vegetable oils are abundant in C18:1 acid, hence are very suitable to blend with cocoa butter replacer (CBR) and it is very good for confectionery fat due to its lower melting point. Most of the CBR are obtained from natural plant fats or produced specifically by chemical or enzymatic fractionation from plant fats (Reddy and Prabhakar, 1989;Bloomer et al., 1990;Chang et al., 1990;Reddy and Prabhakar, 1990;Sridhar et al., 1991;Chong et al., 1992;Nesaretnam and Md. Ali, 1992;Mojovic et al., 1993;Lipp and Anklam, 1998a (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;Jimenez-Bermudez et al., 1995;Kaphueakngam et al., 2009;Lakshminarayana et al., 1983;Solis-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), illipe fat (Gunstone, 2011) etc. are conducted . ...
... Procedures for chemical interesterification of cheap fats and oils to produce analogs have been developed for years and are found to be practical to industries (Liu et al., 1997). Recently, preparation of CBE through 1, 3-specific lipase-catalyzed interesterification has received much attention because lipases offer certain advantages over other chemical catalysts (Chang et al., 1990). The purpose of interesterification is to incorporate selectively stearic residues into triglycerides in positions 1 and 3 until a composition resembling CB composition is obtained. ...
... CBE are also produced by the blending of CB with milk fat, lauric fats, MAF or hydrogenated cottonseed oil (Kaphueakngam et al., 2009;Solis-Fuentes and Duran-de-Bazua, 2004). Production of a cocoa butter-like fat from the interesterification of totally hydrogenated cottonseed and olive oils was studied (Chang et al., 1990). ...
Cocoa butter (CB) is the byproduct of cocoa bean processing industry and is obtained from the mature bean from the Theobroma cacao plant. It is an important ingredient in the chocolate and other confectionery
industries. It's valued for its unique physicochemical properties which is given by its peculiar fatty acid composition. The major triacylglycerols (TAG) present in CB is symmetrical and contains very less amount of
highly unsaturated fatty acid. The major fatty acids present in it are palmitic acid, stearic acid, oleic acid and linoleic acid, but low amounts of lauric acid and myristic acid. Increasing demand and shortage of supply for CB, poor quality of individual harvests, economic advantages and some technological benefits have induce for the development of its alternative called cocoa butter replacer (CBR). In the CBRs the TAG compositions are similar but are not identical to genuine CB. Most of them are produced by either modification of natural fat or by their blending in different proportion. However, it couldn’t satisfy the consumer and fulfill the demand of confectionery industries. This review gives a brief idea about the processing of cocoa pod, the production of cocoa butter and its composition with fats that are commonly used as its Replacers.
... CBEs have chemical and physical properties compatible with those of CB and can be used to replace CB in chocolate confectionery products. Much attention has been given to the production of cocoa butter-like fats from fats and oils of lower value via interesterification with lipase [4][5][6][7][8][9], but enzymatic synthesis of cocoa butter equivalents is still of great interest in the oil and fats industry. Interesterification is an acyl-arrangement reaction. ...
... Our products (CBEs) had SMP range of 30.0 to 34.5°C, compared to commercial CB with SMP of 31.8 to 32.6°C. Abigor et al. [5], 33.8°C; Liu et al. [6], 34.3°C; Chang et al. [9], 39°C. We can also conclude that the most similar SFC profile to CB was obtained from blend E (Figure 4). ...
... Other authors have achieved different yields of CBEs. Chang et al. [9] reported a yield of CB-like fat of 19% when fully hydrogenated cottonseed oil (HCO) was interesterified with olive oil at a weight ratio of 1:1 and up to 53.0% when CBE were synthesized from palm oil and HCO in supercritical CO 2 [6]. The yield of CB-like fat of 45.6% also reported by Abigor et al. [5] when refined, bleached, deodorized palm oil (RBDPO) was interesterified with fully hydrogenated soybean oil (FHSO) at a weight ratio of 1.6:1. ...
Interesterification of fat blends containing palm oil midfraction (PMF) and fully hydrogenated soybean oil (FHSO) at various weight ratios, catalyzed by an immobilized Thermomyces lanuginosa lipase (Lipozyme TL IM), was studied for production of cocoa butter equivalents (CBEs). CBEs have chemical and physical properties compatible with those of cocoa butter (CB) and can be used to replace CB in chocolate confectionery product. The CBEs were isolated from the crude interesterification mixture by fractional crystallization in organic solvent. Triacylglycerol (TAG) composition of the starting blends, the interesterified blends and the fat products were analyzed by reversed-phase high performance liquid chromatography (RP-HPLC) in combination with refractive index (RI) detector. Enzymatic interesterification of the substrates resulted in the formation of a complex mixture of acylglycerols and free fatty acids. Concentration of several TAGs were increased, some were decreased, and several new TAGs were formed. The main TAGs of PMF (POP, POO) and TAGs of FHSO (PSS, SSS) were decreased, whereas the desired CB TAGs (POS, SOS) were increased. Our research indicated that acyl exchange occured mainly between the palmitoyl group from the PMF and the stearoyl group from the FHSO. Fractional crystallization of the fatty acid-free acylglycerols in hexane and acetone gave the fat products whose their TAG distributions were comparable to that of CB but that they also contain diacylglycerol (DAG). The substrate weight ratio of PMF to FHSO to produce a fat product containing the highest major TAGs component of CB (POS and SOS) was 1:2.
... Versatile low-calorie fat substitutes or TAGs, such as novel fatty acid esters [8,9], medium chain TAGs [10,11], Salatrim [12,13], and Caprenin [14,15], have been manufactured using chemoenzymatic and biotechnological methods [16,17]. To evaluate the caloric values of these lowcalorie lipids, several methods are available for the estimation, including balance study, disposition study, as well as growth method [17,18]. ...
... Accordingly, the objective of this study was to estimate the caloric value of the LCCB manufactured by enzymatic transesterification [16,17]. Employing CB as a caloric control, a growth method on restricted diet was conducted over 3 weeks on weanling Wistar male rats to assess the caloric value of LCCB. ...
... Other advantages are lower energy consumption and better product control, moreover solvent-free reaction has been considered as eco-friendly and economical. While chemical catalysts will randomize all of the fatty acids in triacylglycerol (TAG) mixture, 1, 3speci c lipase can incorporate fatty acids into the sn-1, 3-positions without changing the fatty acid residues in the sn-2position (Chang et al., 1990;Daniel et al., 2001;Zarringhalami et al., 2010). Vegetable oils such as mahua, kokum and mango fats, palm oil mid fraction, tea seed oil, and olive oil have been popularly used to prepare CBE by microbial lipases in batch stirred tank reactor (Wisdom et al., 1986). ...
Bakery and confectionary fats were prepared by enzymatic interesterification of sal fat with palm stearin and palm mid fraction blends in various ratios. Slip melting point, free fatty acids, fatty acid composition, solid fat content and triglyceride composition were determined. Fatty acid composition revealed that the blends were rich in palmitic (13.9-58.5%), stearic (7.7-36.7%) and oleic (25.2-39.9%) with no trans fatty acids. Blends of sal:PSt (50:50), sal:PMF (50:50 and 25:75) showed high solid fat content at 20 and 25 °C with short melting range. After interesterification, plasticity of products increased, which were comparable with commercial bakery fat. Some of the blends alone showed short melting profile like cocoa butter. Interesterification produced significant alteration in the triacylglycerol composition of the blends studied. Blends and the interesterified products prepared showed favorable characteristics with no transfats and hence could be used in the place of commercial bakery and confectionary fats.
... Previous research has been using mixture of hydrogenated cottonseed oil and olive oil (1:1) to produce CBE [6]. Slip melting point (SMP) of CBE produced from this study was 39˚C. ...
Cocoa butter (CB) is an important major constituent of chocolate and other confectionary products. Several factors such as premium price, uncertainty in supply and variability in quality, have led the search for an alternative such as cocoa butter equivalent (CBE) from available and cheap commercial oils or fats. The aim of this research was to produce CBEs which contain omega-3 and omega-6 by blending hard palm oil mid-fraction (PMF) with canola oil. The reaction was performed by using Lipozyme RM IM as the biocatalyst. It aims to retain omega-3 and omega-6 content in CBE after interesterification. The effect of lipase load (LL), time reaction (TR) and stearic acid (ST) on CBE properties were studied to produce nearly similar CBE properties to CB. The best reaction conditions for maximizing POS (palmitic-oleic-stearic), SOS (stearic-oleic-stearic), and SMP (slip melting point) value while minimizing POP (palmitic-oleic-palmitic) and the levels of diacylglycerol (DAG) formation were; LL, 7.5% (w/w); TR, 8 hours; ST, with 44% stearic acid addition. Omega-3 (5.35%) and omega-6 (1.97%) content in CBE (after interesterification) were not significantly different (p > 0.05) to omega-3 (5.71%) and omega-6 (2.16%) content in initial mixture (before interesterification). The properties of CBE which include POP, POS, SOS, DAG and SMP values were 30.33%, 17.53%, 3.26%, 6.75%, and 46.45°C, respectively under these conditions.
... Fusion of fats was tested by MTDSC analysis, which was performed to the cocoa beans before they underwent the drying process. The peaks in the intervals of 25-40 and 80-100 C in Figure 5, these correspond to the fusion of fats [38,39] and evaporation (water and volatile compounds), respectively. These processes are endothermic and demand about of 46 J g À1 and 109 J g À1 for the first and second peaks of Figure 6, respectively. ...
In this work, it was evaluated the morphological changes of the porous structure of the cocoa bean samples subjected to microwave drying. The use of microwaves (MWs) applied by ON-OFF on cocoa bean samples allowed to avoid both the burning and the roasting of the beans. During the MWs drying process, phenomena of breakage of cellular structure, coalescence and, pore plugging altered the average pore diameter, the pore volume, surface area, and Pore Size Distribution (PSD). When the results of sun-dried beans were compared with those of beans dried by MWs, it was concluded that the average pore diameter, the pore volume, the surface area and, PSD were also affected by the solar drying; however, the breakage of cellular structure did not occur
... So running this type of EIE reaction in solvent is a necessity. In 1990, Chang et al. 33 , synthesized a cocoa butter-like fat through EIE of a fully hydrogenated cottonseed oil and olive oil mixture. The maximum POS content was produced after 4 hours on and the highest yield of the reaction was 19% w/w. ...
A cocoa butter equivalent (CBE) was synthesized enzymatically from readily available edible fats with fatty acid and triacylglycerol compositions that closely resemble the fat present in chocolate, cocoa butter. A commercially available immobilized fungal lipase, Lipozyme RM IM, was used as the reaction catalyst. Reaction parameters were a temperature of 65 °C, water activity of 0.11, a 4 h reaction time, and a substrate mass ratio of a commercial enzymatically synthesized shea stearin (SS) to palm mid-fraction (PMF) of 6:4 (w/w). Fractionation was also used after reaction completion to further approach the triacylglycerol composition of cocoa butter by removing trisaturated and unsaturated triacylglycerols. The yield of the triglyceride 1-palmitoyl-2-oleoyl, 3-stearoyl-glycerol (POS) produced was 57.7% (w/w). The amounts of 1,3-dipalmitoyl-2-oleoyl-glycerol (POP), (POS) and 1,3-stearoyl-2-oleoyl-glycerol (SOS) in the final CBE were 11.2%, 36.3%, and 34.8%, respectively. In comparison, the amounts of POP, POS and SOS in the cocoa butter used in this study were 15.2%, 38.2%, and 27.8%, respectively. No significant differences (P > 0.05) in melting point and enthalpy of fusion between CB and the CBE were observed. In comparison, a non-interesterified blend of SS and PMF (60:40 w/w) showed significantly (P < 0.05) higher melting point and lower enthalpy of fusion compared to CB. The crystal polymorphic form V of CB (β2-3L) was similar to that of CBE and SS/PMF (60:40 w/w). The solid fat content (SFC) vs. temperature profile of the CBE generally resembled that of CB, except that the CBE had significantly (P < 0.05) higher SFCs at 5, 10, 15, 20 and 25 °C compared to both CB and SS/PMF (60:40 w/w). Addition of 15% (w/w) CBE to CB did not cause any changes in physical properties (melting point, SFC and crystal polymorphic forms) of the CB. This study demonstrates the potential for synthesizing a CB-like CBE using a green, rapid, straightforward one step enzymatic conversion followed by fractionation from widely available edible fats.
... Des stratégies biotechnologiques, qu'il s'agisse d'approches enzymatiques ou fermentaires ont été également mises en évidence (Ratledge, 1987;. Concernant l'utilisation des enzymes, elles mettent en oeuvre des lipases libres ou immobilisées, qui catalysent des réactions de transestérification d'huiles par des acides gras en milieux anhydres, afin d'aboutir à la synthèse des triglycérides recherchés (transestérification de l'huile de palme par l'acide stéarique aboutissant à la synthèse des triglycérides de type POS et SOS - Chang et al., 1990;Bloomer et al., 1990). Afin de produire un équivalent de beurre de cacao, plusieurs études mettant en jeu des microorganismes oléagineux ont été, également, effectuées. ...
La réponse biochimique de la levure oléagineuse Yarrowia lipolytica LGAM S(7)1 sur différentes sources carbonés est étudiée. Le microorganisme présente une croissance cellulaire importante, accompagnée d'une accumulation élevée en lipides, lorsque la stéarine (acides gras libres saturés) sert de substrat. Le processus d'accumulation lipidique est influencé par le pH du milieu, la quantité d'azote extracellulaire, la température ainsi que la concentration initiale en stéarine. Y. lipolytica présente une importante croissance sur des mélanges stéarine/huile de colza oléique hydrolysée. L’accumulation des graisses est corrélée à la présence de stéarine dans le milieu. Des lipides cellulaires, composés majoritairement de triglycérides et présentant une composition totale proche du beurre de cacao, sont synthétisés. La souche procède à une consommation de ses réserves lipidiques, alors qu'une quantité encore importante de substrat extracellulaire n'est pas consommée. Un modèle mathématique décrivant ce phénomène, dans une première approche, est développé. La croissance cellulaire est également importante dans les milieux osidiques, composés de glycérol technique et/ou de glucose, avec des paramètres de croissance similaires pour les deux substrats. Malgré les rapports molaires C/N élevés, Y. lipolytica n'accumule pas de graisses ; par contre, une formation importante d'acide citrique est observée. Les lipides cellulaires analysés, montrent la prédominance d'acides gras insaturés. La croissance de la souche sur glycérol, a été modélisée. L’utilisation de mélanges oses/stéarine variés, présente des résultats divers mais intéressants. Le glycérol s'avère un co-substrat plus adéquat que le glucose, en permettant une accumulation lipidique plus importante. Dans tous les cas, la concentration des lipides cellulaires est moindre si on la compare à l'utilisation de la seule stéarine. Cependant, la composition des lipides présente une meilleure similitude avec le beurre de cacao.
... Attempts have been made to prepare cocoa-butter-like fats by interesterification of hydrogenated cottonseed oil and olive oil and subsequent fractionation (Chang et al., 1990). The preparation of CBS by means of lipase-catalyzed interesterification constitutes a better research field (Abigor et al., 2003) owing to the availability of lipases that catalyze the regioselective interchange of acyl groups at the sn 1 and sn 3 positions of the TAG structure. ...
... Attempts have been made to prepare cocoa-butter-like fats by interesterification of hydrogenated cottonseed oil and olive oil and subsequent fractionation (Chang et al., 1990). The preparation of CBS by means of lipase-catalyzed interesterification constitutes a better research field (Abigor et al., 2003) owing to the availability of lipases that catalyze the regioselective interchange of acyl groups at the sn 1 and sn 3 positions of the TAG structure. ...
... profile, composition and polymorphism as CB, which should be compatible with CB without exhibiting any eutectic behaviour (McGinley, 1991). Attempts have been made to prepare cocoa butter-like fats by interesterification of hydrogenated cottonseed oil and olive oil and subsequent fractionation (Chang et al., 1990). Edible beef tallow also has been solvent-fractionated from acetone to produce cocoa butter-like fractions (Luddy et al., 1973). ...
The acylglycerol structure exemplifies the major lipid building block and therefore is an interesting structure to modify. Such modification is driven by: (1) consumers who have become more concerned about the relationship between diet and wellness, and (2) new and novel functional compounds can be prepared when the original structure of a lipid is modified. This trend has led to the design of functional foods or nutraceuticals, namely, fortified, enriched, modified and enhanced foods. Advances in the biochemistry and engineering of enzymatic reactions and reactors have improved the knowledge and understanding of such reaction systems and thus, make available a generation of structured lipids. In the present work, we detail several efforts carried out to prepare novel compounds, as well as industrial applications and possible future enzymatic procedures to obtain new food products.
... Mild reaction conditions and easy process control make enzymatic interesterification preferable in producing enriched lipids [2,11]. Moreover, it offers more raw materials that can be used, especially in CBE production [2,[12][13][14][15]. ...
The study to find cocoa butter equivalent (CBE) as an alternative to cocoa butter (CB) from available and low cost commercial oils or fats has been increased recently. Current study investigates the blending of hard palm oil mid-fraction (PMF) with canola oil to produce high nutritional CBE using immobilized lipase from Rhizomucor miehei. The experiments were designed using Response Surface Methodology (RSM) to optimize the percentage of saturated-unsaturated-saturated (StUSt) triacylglycerols (TAGs). The experiment was performed at hard PMF concentration of 50 to 90% (w/w), lipozyme load between 5% and 10% (based on the weight of substrate) with a reaction time between 2 to 14 hours. The best reaction conditions to attain this target was 89.35% (w/w) of hard PMF concentration, 2 hours of reaction time, and 5% (based on the weight of substrate) of lipozyme load, resulting CBE which contains 64.44±1.18% of StUSt. The addition of canola oil improved the nutritional value of CBE which was marked by the higher percentage of linoleic acid (omega-6, 4.53±0.06%) and linolenic acid (omega-3, 0.74±0.14%) in CBE than CB (omega-6, 2.68±0.34%). Enzymatic interesterification was not altering fatty acid content in the CBE, especially linoleic acid (omega-6) and linolenic acid (omega-3) which was characterized by no significant difference (p > 0.05) between the fatty acid profile of initial mixture (before interesterification) and CBE (after interesterification).
... It usually prepared from lower value fats and oils, so is able to reduce the selling price. Enzymatic interesterification is one of the fat or oil modification techniques which offer more raw materials that can be used to produce CBE, such as high oleic fat or oil [2,[7][8][9]. Moreover, enzymatic interesterification was preferable due to its advantages, such as mild reaction conditions, easy process control, and minimal waste disposal [8]. ...
The study to find cocoa butter equivalent (CBE) as an alternative to cocoa butter (CB) from available and low cost commercial oils or fats has been increased recently. Current studies investigates the blending of hard palm oil mid-fraction (PMF) with canola oil to produce CBE using immobilized lipase from Rhizo-mucor miehei. The experiments were designed using Response Surface Methodology (RSM) to optimize the percentage of saturated-unsaturated-saturated (StUSt) triacylglycerols (TAGs). The experiment was performed at hard PMF concentration of 50 to 90% (w/w), lipozyme load between 5% and 10% (based on the weight of substrate) with a reaction time between 2 to 14 hours. The best reaction conditions to attain this target was 89.71% (w/w) of hard PMF concentration, 2 hours of reaction time, and 5% (based on the weight of substrate) of lipozyme load, resulting CBE which contains 65.27% of StUSt.
... Previous research has been using mixture of hydrogenated cottonseed oil and olive oil (1:1) to produce CBE [7]. Slip melting point (SMP) of CBE produced from this study was 39˚C. ...
Cocoa butter (CB) is an important major constituent of chocolate and other confectionary products. Several factors such as premium price, uncertainty in supply and variability in quality, have led the search for an alternative such as cocoa butter equivalent (CBE) from available and cheap commercial oils or fats. The aim of this research was to produce CBEs which contain omega-3 and omega-6 by blending hard palm oil mid-fraction (PMF) with canola oil. The reaction was performed by using Lipozyme RM IM as the biocatalyst. It aims to retain omega-3 and omega-6 content in CBE after interesterification. The effect of lipase load (LL), time reaction (TR) and stearic acid (ST) on CBE properties were studied to produce nearly similar CBE properties to CB. The best reaction conditions for maximizing POS, SOS, and SMP value while minimizing POP and the levels of diacylglycerol (DAG) formation were; LL, 7.5% (w/w); TR, 2 hours; ST, with 44% stearic acid addition. Omega-3 (7%) and omega-6 (1.97%) content in CBE (after interesterification) were not significantly different (p > 0.05) to omega-3 (7.75%) and omega-6 (2.16%) content in initial mixture (before interesterification). The properties of CBE which include POP, POS, SOS, DAG and SMP values were 30.91%, 20.54%, 3.69%, 5.63%, and 46.25°C, respectively under these conditions.
... O tratamento do material bruto inclui: lavagem, moagem e aquecimento com um sal, ao fim do qual servirá como suporte para imobilização de enzimas. Nos suportes, as lipases podem ser facilmente removidas da mistura e reutilizadas, logo, a escolha do suporte em que a enzima será imobilizada também é importante, pois determina o acesso da enzima ao substrato, e portanto, bom grau de interesterificação(WISDOM, 1984;CHANG et al. 1990).Na prática, as características do fluxo no meio de suporte é de grande importância no projeto das colunas dos reatores, e isto é segredo comercial (TOMBS, 1997). O tempo de reação, a ser determinado em função de uma série de variáveis (temperatura, suporte, solvente, substrato, etc.) também é fundamental. ...
Apresenta breve revisão bibliográfica sobre interesterificação química e enzimática, abordando os aspectos gerais e comparando seus usos. Enfoca também a produção de substitutos da manteiga de cacau a partir de óleos vegetais e outros alimentos por interesterificação enzimática.
... tigate cocoa butter equivalents generated from milk fat blends (Md Ali and Dimick 1994), interesterified vegetable oils (Chang et al 1990) and interesterified palm oil fractions (Bloomer et al 1990). Recently, Sessa et al (1996) applied statistical and mathematical techniques to DSC melting curve data to devise an index to determine the level of saturation of transesterified jojoba wax ester blends based on heats of fusion enthalpies. ...
A series of wax ester blends was constructed by transesterifying native jojoba oil with 50–500 g kg−1 completely hydrogenated jojoba wax esters. This series, when subjected to a standardised differential scanning calorimetry (DSC) tempering method gave either 1, 2 or 3 enthalpic events which represented the diunsaturated, monounsaturated and saturated species. These species were verified by measuring the melting points of a native and completely hydrogenated jojoba wax ester and also by demonstration that DSC thermograms of a synthetic monounsaturated wax ester possessed an endotherm with a melt between the diunsaturated and completely saturated species. The heats of fusion and heats of crystallisation enthalpies of all three enthalpic events exhibited excellent correlation with the level of saturation. Chemometric indices were devised from heats of fusion and crystallisation enthalpies to estimate the level of saturation in these blends. From these indices and also from regression analyses of each species' individual events we could optimise the level of saturation needed to best mimic the melt and crystallisation properties of cocoa butter. The wax ester blend with 400 g kg−1 saturation most closely resembled the thermal properties of cocoa butter where the monounsaturated species of the jojoba blend gave identical thermograms to tempered cocoa butter.
... tearoyl-2-oleoyl glycerol, SOS)가 23-30%, oleic acid가 sn-2 위치이며 palmitic acid가 sn-1,3 위치에 결합되어 있는 대칭구조(1,3-dipalmitoyl-2-oleoyl glycerol, POP)가 14-17%로 알려져 있다. 카카오 재배지역에 따라 차이를 보이기 도 하는 이와 같은 TAG 조성은 유지가 상온에서는 딱딱함 과 부러지기 쉬운 성질을 가지며 사람의 입안에서는 완전히 녹아버리는 예민한 융점을 가지게 하는 주요한 원인이다 (1,2 Structured lipid was obtained from the reaction condition; molar ratio of substrates (canola oil : palmitic ethyl ester : stearic ethyl ester)=1:3:9, enzyme amount=6% Lipozyme TLIM, and reaction time=40 min. ...
Synthesis conditions of cocoa butter equivalents were optimized using the response surface method (RSM) by interesterification of canola oil (Ca), palmitic ethyl ester (PEE), and stearic ethyl ester (StEE). The reaction was catalyzed by immobilized lipase (Lipozyme TLIM) from Thermomyces lanuginosa to produce structured lipids containing a composition of triacylglycerols similar to cocoa butter. Reaction conditions were optimized using D-optimal design with the three reaction factors of the substrate molar ratio of canola oil to palmitic ethyl ester and stearic ethyl ester (Ca : PEE : StEE=1:1:3, 1:1.66:5, 1:2:6, 1:2.33:7, 1:3:9, ), enzyme ratio (2~6%, ), and reaction time (30~270 min, ). The optimal conditions that minimized acyl-migration while maximizing 1-palmitoyl-2-oleoyl-3-stearoyl glycerol (POS), 1,3-distearoyl-2-oleoyl glycerol (SOS), and 1,3-dipalmitoyl-2-oleoyl glycerol (POP) were predicted, resulting in Ca : PEE : StEE=1:3:9, 6% of enzyme ratio, and 40 min of reaction time. The reaction product of structured lipids was synthesized again under the same conditions, showing 10.43 area% of acyl-migration, 25.31 area% of POS/PSO, 19.79 area% of SOS, and 11.22 area% of POP.
... Procedures of chemical interesterification for analogs have been developed for years from cheap fats and oils and are found to be practical to industries [7]. Recently, preparation of CBE through 1, 3-specific lipase-catalyzed interesterification has received much attention because lipases offer certain advantages over other chemical catalysts [8]. While chemical catalysts will randomize all of the fatty acids in a triacylglycerol mixture, 1, 3-specific lipase can incorporate fatty acids into the sn-1, 3-positions without changing the fatty acid residues in the sn-2-position [9]. ...
Supercritical carbon dioxide (SC-CO2) has been studied as a medium for esterification of camel hump fat and tristearin in producing cocoa butter analog using Immobilized Thermomyces lanuginosus lipase (Lipozyme TL IM) as a biocatalyst. Process conditions (pressure, temperature, tristearin/camel hump fat ratio, water content, and incubation time) were optimized by conducting experiments at five different levels using the response surface method (RSM). A second-order polynomial response surface equation was developed indicating the effect of variables on cocoa butter analog yield. Contour maps generated using the response surface equation showed that all the experimental variables significantly affected the yield. The pressure, 10MPa; temperature, 40°C; SSS/CHF ratio, 1:1; water content, 10% (w/w); and incubation time, 3h were found to be the optimum conditions to achieve the maximum yield of cocoa butter analog.
... 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. 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. ...
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.
... Human milk fat substitutes have also been produced using lipases derived from C. antaractica, Alcaligenes sp. and Rhizopus oryzae from palm stearin and tripalmitin via acidolysis with palmitic and oleic acids [9, 10]. Liquid vegetable oils are cheap starting materials which can be modified using lipases to produce products with desired TAG profiles111213. High oleic sunflower lines produce sunflower oil containing high levels of oleic acid (~80%) and triolein (OOO) (>70%). The High Oleic Sunflower Oil (HOSO) does not contain enough solids for many applications but can be structurally modified by enzymatic acidolysis to increase the disaturated (Sat-O-Sat) TAG level. ...
The acidolysis of high oleic sunflower oil (containing >70% triolein) with 11 different stearic–palmitic acid mixtures at an oil:acid ratio of 1:1.3 (w/w) has been performed using a 1,3 regiospecific lipase (Rhizopus oryzae), to produce specialised fats with a high disaturated triacylglycerol (TAG) content (∼40%). The final conversions corresponded well to predictions from a probability model. The variation of TAG composition with time was also measured to study the reaction kinetics. Initially, a reaction scheme was formulated allowing all possible acidolysis reactions of TAGs with stearic, palmitic and oleic fatty acids at the 1 and 3 TAG positions. It was found that a first order scheme produced good fits to data and that reactions involving stearic and palmitic reactions in equivalent positions produced very similar fitted rate constants. When these rate constants were constrained to be equal, acceptable fits were also obtained. As the acidolysis reactions occur via the formation of diacylglycerols (DAGs) by hydrolysis (7.1–10.9%), a further scheme was tested whereby all possible reactions involving DAGs were included (with equal rate constants for equivalent reactions with palmitic and stearic acid to limit the number of fit parameters). This produced only a small increase in goodness of fit. Assuming a single value of rate constant for all reactions produced poor fits.
Cocoa butter is the main ingredient for chocolate and chocolate related confectionery products. Because of the high price, high demand and limited supply, cocoa butter alternatives are becoming important. Different vegetable fats are used for cocoa butter alternative preparation by using blending, fractionation, hydrogenation and interesterification techniques. Depending on their compatibility with cocoa butter, cocoa butter alternatives have been classified into three categories namely cocoa butter equivalent, cocoa butter replacer and cocoa butter substitute. Fatty acid and triacylglycerol profile are important chemical properties that can impact on various physical properties such as melting and crystallization behavior. Depending on temperatures and storage duration, different fat polymorphic forms are formed. Cocoa butter alternatives have been recommended for various usages like chocolate, confectionery filling, coatings and other confectionery products based on their unique physical and chemical properties.KeywordsCocoa butter alternativeCocoa butter equivalentCocoa butter replacerCocoa butter substituteChocolate and confectioneryFat bloom
In this work, it was evaluated the morphological changes of the porous structure of the
cocoa bean samples subjected to microwave drying. The use of microwaves (MWs) applied by ON-OFF on cocoa bean samples allowed to avoid both the burning and the roasting of the beans. During the MWs drying process, phenomena of breakage of cellular structure, coalescence and, pore plugging altered the average pore diameter, the pore volume, surface area, and Pore Size Distribution (PSD). When the results of sun-dried beans were compared with those of beans dried by MWs, it was concluded that the average pore diameter, the pore volume, the surface area and, PSD were also affected by the solar drying; however, the breakage of cellular structure did not occur.
Lipases (triacylglycerol acylhydrolases EC: 3.1.1.3) are universal enzymes, present in all the living creatures, i.e. plants, animals, fungi and bacteria. Their basic function is to catalyze the hydrolysis of lipid into free fatty acid and glycerol at the interface of aqueous and organic solvent, which broadens its applications in various industries. Lipases catalyze a wide range of industrially important reactions: transesterifications, esterifications, interesterifications, etc. and also shows enantio-selectivity due to which they are considered as indispensable tools in food, pharmaceuticals, biofuel, diagnostics, chiral chemistry, drug, detergent, oleochemicals, cosmetics, leather, biosensor industry, etc. The present chapter deals with the production of lipases and their various applications in the food industry such as dairy, bakery, egg processing, oil and fat, flavouring and aroma, meat and fish processing, etc. Various advanced technologies such as metagenomics, directed evolution, genetic engineering, protein engineering, etc. have been discussed to add desired trades in enzymes and to achieve high yield. Light has also been thrown on the key players in global lipase industry and commercially available lipases in the ending notes.
Incorporations of nature fatty acids which were palmitic acid and stearic acid into the end positions of soybean oils were done using sn-1,3 specific immobilised lipase from Rhizomucor miehei at different ratios in order to produce symmetrical triglycerides without changing the fatty acids at sn-2 position. The optimum ratio for the process was 25:75 w/w. There were 19.2% increase of SFA for P25 and 16% increase for S25 at the sn-1,3 positions. The research findings indicated that the structured lipids produced from enzymatic interesterification possessed a higher oxidative stability than soybean oil. The newly formed structured lipids (SUS type) could be good sources for various applications in food industry.
Bioorganic catalysis is emerging as a powerful tool to complement traditional catalytic reactions in organic synthesis. A wide range of reactions can be catalyzed using biocatalysts, and this article attempts to introduce the reader to the variety of reactions that have been demonstrated. Although these reactions are possible in the laboratory, the challenge is to make them economically feasible on an industrial scale. Each biotransformation process has some unique obstacles to overcome before it is translated from the laboratory to commercial scale, and some of these problems are discussed. Biocatalytic properties are amenable to dramatic modification using genetic and solvent engineering, setting them apart from traditional catalysts. Many biocatalytic processes are being run on a commercial scale and one such reaction utilizing a transaminase is presented as a case study.
Cocoa butter (CB) is an essential ingredient in chocolate as it forms the continuous phase of chocolate. It is responsible for the gloss, texture, and typical melting behavior of chocolate. Although cocoa butter is the ideal ingredient, the varying supply and increasing price depending on fluctuating cocoa bean prices forced manufacturers to seek alternatives. Cocoa butter can be replaced by other vegetable fats, collected under the name Cocoa Butter Alternatives (CBAs). The CBAs are divided into three main categories according to their functionality and similarity to cocoa butter: the Cocoa Butter Equivalents (CBEs), the Cocoa Butter Replacers (CBRs), and the Cocoa Butter Substitutes (CBSs). A CBE should allow processing of chocolate products in an identical manner to that of cocoa butter-based products. The specific fatty acid profile and their distribution on the glycerol backbone in natural oils and fats affect their functional properties like crystallization and melting behavior. Therefore, the use of only one technique is not sufficient and several techniques need to be combined together to produce a cocoa butter alternative fat. Interesterification is an important modification technique resulting in the redistribution of the fatty acids along the glycerol backbone, which results in a change of the physicochemical properties of the fat.
The acylglycerol structure exemplifies the major lipid building block and therefore is an interesting structure to modify. Such modification is driven by: (1) consumers who have become more concerned about the relationship between diet and wellness, and (2) new and novel functional compounds can be prepared when the original structure of a lipid is modified. This trend has led to the design of functional foods or nutraceuticals, namely, fortified, enriched, modified and enhanced foods. Advances in the biochemistry and engineering of enzymatic reactions and reactors have improved the knowledge and understanding of such reaction systems and thus, make available a generation of structured lipids. In the present work, we detail several efforts carried out to prepare novel compounds, as well as industrial applications and possible future enzymatic procedures to obtain new food products.
IntroductionEnantiomerically Pure Pharmaceutical IntermediatesAmino AcidsOther ApplicationsReferences
The traditional fat ingredients for chocolate are cocoa butter (CB) and milk fat (MF). If we add sugar confectionery to this, then we can also include certain vegetable oils, especially coconut oil (CN) used in toffees and fillings. Nowadays, there is a much wider range of fats available, designed mainly to replace the expensive cocoa butter and milk fat, but also coconut oil. As far as fats intended to replace cocoa butter are concerned, these are generally termed ‘cocoa butter alternatives’ (CBAs). These may be designated by their application but the more systematic approach adopted in this chapter is to designate them according to their chemical composition, which is the fundamental basis of their properties. As in Europe the legislation in Australia and New Zealand has been in the process of change.
1-Palmitoyl-2-oleoyl-3-oleoyl glycerol (POO) and 1-palmitoyl-2-oleoyl-3-palmitoyl glycerol (POP) were enriched from palm stearin using an acetone fractionation process. Response surface methodology was employed to optimize the purity of POO (Y1, %) and POP (Y2, %) along with POO+POP content (Y3, g) based on independent variables such as fractionation temperature (X1, 25, 30, and the ratio of palm stearin to acetone (X2, 1:3, 1:6 and 1:9, w/v). Fractionation conditions were optimized to maximize Y1, Y2, and Y3, in which fractionation temperature was 29.3 oC with a 1:5.7 acetone ratio. With such parameters, 60.9% of POP and 23.8% of POO purity were expected with a 75% yield (3.0 g) of POO and POP.
The main goal of the present research is to restructure olive oil triacylglycerol (TAG) using enzymatic acidolysis reaction to produce structured lipids that is close to cocoa butter in terms of TAG structure and melting characteristics. Lipase-catalyzed acidolysis of refined olive oil with a mixture of palmitic-stearic acids at different substrate ratios was performed in an agitated batch reactor maintained at constant temperature and agitation speed. The reaction attained steady-state conversion in about 5 h with an overall conversion of 92.6 % for the olive oil major triacylglycerol 1-palmitoy-2,3-dioleoyl glycerol (POO). The five major TAGs of the structured lipids produced with substrate mass ratio of 1:3 (olive oil/palmitic-stearic fatty acid mixture) were close to that of the cocoa butter with melting temperature between 32.6 and 37.7 °C. The proposed kinetics model used fits the experimental data very well.
Enzymatic modification of natural triacylglycerols and the properties of the obtained products S u m m a r y Structured triacylglycerols (sTAG) are chemical compounds with a precisely defined chemical and stereochemical structure whose natural nutritional and physico-chemical properties have been modified. Modified TAG can be synthe-sized with the application of genetic engineering, physical, chemical and enzy-matic methods. Due to the demand for the precisely determined structure of the resulting sTAG, their synthesis with the use of lipases is preferred. Prepared pure fatty acids or their esters, as well as synthetic monoacid triacylglycerols are necessary for sTAG synthesis. The use of such unnatural sub-strates requires additional processes and is cost consuming. Additionally, it can lead to loss of valuable components present in natural oils and contribute to a decrease in the oxidative stability of the resulting products. The application of naturally occurring fats or oils can considerably simplify sTAG synthesis and re-duce the costs of the processes. Recently, much attention has been paid to an assessment of nutritional properties of structured triacylglycerols or acylglycerols. The aim of this article is to present the methods of sTAG synthesis, includ-ing examples of the use of naturally occurring triacylglycerols as substrates.
Human milk has characteristics of great importance for the newborn. Its composition shows all nutrients in quantity and quality needed, in addition to providing protection against infections and allergies and stimulating the immune system. Therefore, the composition of fatty acids and their distribution in the triacylglycerols are targets of studies on infant formula, and the triacylglycerols of human milk fat should serve as a model for the lipid components. This review aims to report studies of technology in lipids in order to produce structured lipids as substitutes of human milk fat.
An extracellular lipase gene ln1 from thermophilic fungus Thermomyces lanuginosus HSAUP0380006 was cloned through RT-PCR and RACE amplification. Its coding sequence predicted a 292 residues protein with a 17 amino acids signal peptide. The deduced amino acids showed 78.4% similarity to another lipase lgy from T. lanuginosus while shared low similarity with other fungi lipases. Higher frequencies hydrophobic amino acids related to lipase thermal stability, such as Ala, Val, Leu and Gly were observed in this lipase (named LN). The sequence, -Gly-His-Ser-Leu-Gly-, known as a lipase-specific consensus sequence of mould, was also found in LN. High level expression for recombinant lipase was achieved in Pichia pastoris GS115 under the control of strong AOX1 promoter. It was purified to homogeneity through only one step DEAE-Sepharose anion exchange chromatography and got activity of 1328U/ml. The molecular mass of one single band of this lipase was estimated to be 33kDa by SDS-PAGE. The enzyme was stable at 60°C and kept 65% enzyme activity after 30min incubation at 70°C. It kept half-activity after incubated for 40min at 80°C. The optimum pH for enzyme activity was 9.0 and the lipase was stable from pH 8.0 to 12.0. Lipase activity was enhanced by Ca2+ and inhibited by Fe2+, Zn2+, K+, and Ag+. The cell-free enzyme hydrolyzed and synthesized esters efficiently, and the synthetic efficiency even reached 81.5%. The physicochemical and catalytic properties of the lipase are extensively investigated for its potential industrial applications.
Milk fat was interesterified with oleic acid by catalysis of an immobilized lipase in a microaqueous two-phase system. A commercial lipase from Rhizopus oryzae and a controlled pore glass carrier were selected for preparation of an immobilized lipase. The prepared immobilized lipase showed a Michaelis constant of 77 mM and a maximum velocity of 40 U/g of carrier on the hydrolysis of triolein. Conditions for interesterification catalyzed by the immobilized lipase were optimized by the reaction between trimyristin and oleic acid under various conditions. The interesterification of milk fat with oleic acid was performed in isooctane with .3% (vol/vol) water content. The fatty acid composition and thermal characteristics of the triglycerides of the interesterified milk fat were investigated. The interesterified milk fat had about 50% more oleic acid and a significantly lower palmitic acid content than those of the original milk fat. The crystallization and melting curves obtained by differential scanning calorimetry analysis showed that the transition temperature of the major milk fat peaks decreased by 7.6 and 5.4°C, respectively. The results suggest that the prepared immobilized lipase can induce rather specific interesterification between oleic acid and palmitic acid in the milk fat triglycerides, which produces a lower melting milk fat, without losses of the short-chain fatty acid composition.
The behavior of conjugated fatty acid triglycerides and diglycerides on reverse-phase chromatography was studied. Trieleostearin
is a geometric isomer of trilinolenin. The conjugated double bond arrangement in trieleostearin enhances its hydrophobic interaction
with the stationary phase and causes it to be eluted later than trilinolenin. In separation of “critical pairs” of tri- and
diglycerides, diglycerides elute later than triglycerides due to the longer fatty acid constituent. Position isomers of 1,2-
and 1,3-diglycerides can be separated by reverse-phase high-performance liquid chromatography.
A continuous flow apparatus is set up to study the enzymatic interesterification of palm oil by stearic acid in supercritical carbon dioxide. Domestic edible palm oil is mixed with stearic acid and loaded to a saturation tank in which the oil is extracted by supercritical carbon dioxide. The current of the extraction solution bubbled from the saturation tank is delivered to an enzyme-packed column. In this study, five triglycerides (POP, POS, POO, OOO, and SOO) and two free fatty acids (stearic acid and palmic acid) are selected as indicators to monitor the interesterification. The results show that the Mucor miehei dominantly catalyzes the interesterifications of POP+S«POS and POO+S«SOO when the stearic acid content in the extraction solution is abundant. A very limited amount of SOS is also irregularly found in the product samples. POS and SOO are rarely produced when the loaded stearic acid is completely elutriated, and the weight fraction of POO is significantly increased by the depletion of POP. It is presumed that the palmitoyl group in the 1,3 position is substituted much more readily, and that the stearic acid is a reactive acyl donor for the interesterification in supercritical carbon dioxide when catalyzed by Mucor miehei. That large amounts of palmic acid are found in the transesterified oil confirms this presumption.
Lipids in biological matter are mostly triacylglycerols (TAG). Lipolytic enzymes, primarily lipases, are indispensable for bioconversion of such lipids from one organism to another and within the organisms. In addition to their biological significance, lipases are very important in the field of food technology, nutritional and pharmaceutical sciences, chemical and detergent industries, and clinical medicine because of their ability to catalyze various reactions involving a wide range of substrates. Conventionally, lipases have been viewed as the biocatalysts for the hydrolysis of TAG (fats and oils) to free fatty acids, monoacylglycerols (MAG), diacylglycerols (DAG), and glycerol. The main advantages of lipase catalysis are selectivity, stereo-specificity, and mild reaction conditions. Despite these advantages and the fact that enzymatic splitting of fats for fatty acid production was described as early as in 1902, the lipase-catalyzed process has not replaced the commercial physicochemical process for the continuous splitting of TAG utilizing super-heated steam. The limited exploitation of lipase technology may be attributed to high enzyme cost, large reaction volume, requirement for emulsification of substrate, and risk of microbial contamination. Many of these limitations originate from the fact that lipases are employed mainly in water-rich reaction media where the solubility of the substrate TAG is very small. To circumvent this problem and to realize the full potential of lipase, researchers have explored newer approaches by manipulating the conditions under which the lipases act. Many of these novel approaches for lipase catalysis have been the outcome of the discovery that enzymes can be active in water-poor, non-polar media (Hanhan, 1952; Misiorowski and Wells, 1974; Zaks and Klibanov, 1984). Also, the finding that lipases can act in organic solvents has led lo an expansion of their applicability in a wide variety of chemical reactions. Lipase catalysis in some of the well established reaction media has previously been reviewed (Brockerhoff and Jensen, 1974; Brockman, 1984; Lilly et al., 1987; Hailing, 1990; Inada el al, 1990; Malcata et al., 1990). The present review is intended to present a compilation and comparison of novel reaction systems used for lipase catalysis. This review describes briefly the general characteristics of lipase reactions, applications of lipase in various fields, and conventional lipase technology. The lipase-mediated biochemical reactions, particularly the hydrolysis of TAG in novel reaction media is discussed in greater detail.
Refined olive oil and partially hydrogenated palm oil (PHPO) blends of varying proportions were subjected to both chemical and enzymatic interesterifications. The rearranged fats were investigated for their melting points, solid fat contents at selected temperatures, fatty acid compositions and trans isomer contents, as well as evaluations, by an expert sensory panel, of their spreadibility and appearance characteristics. The analytical results were compared with those of commercial Turkish margarines. The 30:70 olive oil-PHPO blend after enzymatic interesterification was found to have properties very similar to those of Turkish package margarines, with the additional advantage of possessing higher amounts of monounsaturated fatty acids.
Cocoa butter equivalent was prepared by enzymatic acidolysis reaction of substrate consisting of refined palm olein oil and palmitic-stearic fatty acid mixture. The reactions were performed in a batch reactor at a temperature of 60 °C in an orbital shaker operated at 160 RPM. Different mass ratios of substrates were explored and the compositions of the five major triacylglycerol (TAG) of the structured lipids were identified and quantified using cocoa butter-certified reference material IRMM-801. The reaction resulted in production of cococa butter equivent with TAG compostion (POP 26.6 %, POS 42.1, POO 7.5, SOS 18.0 %, and SOO 5.8 %) and melting temperature between 34.7 and 39.6 °C which is close to that of the cocoa butter. The result of this research demonstrated the potential use of saturated fatty acid distillate (palmitic and stearic fatty acids) obtained from palm oil physical refining process into a value-added product.
Several cocoa butter-like fats, which had been prepared by fractional crystallization of the reaction product obtained on interesterifying highly-hydrogenated cottonseed oil and a triolein product or olive oil, were characterized and compared with cocoa butter.
The fats, as obtained by fractional crystallization from acetone solutions, contained varying amounts of glycerides melting above 37°C., an undesirable feature which caused the fats to thicken too much when used in chocolate type compositions under the same conditions employed with cocoa butter. The higher-melting glycerides could be removed by filtration, or their proportions could be decreased by changing the fractionation temperatures. The fats melted mostly over the same temperature range associated with cocoa butter, and the best of the fats resembled cocoa butter closely over the temperature range 0° to 30°C.
The cocoa butter-like fats resembled cocoa butter in hardness at all test temperatures.
The fats were reasonably compatible with cocoa butter, that is, in mixtures of the two, one did not cause extensive premelting of the other.
According to their cooling curves, the cocoa butter-like fats did not supercool as cocoa butter does. The former contain not only the 2-oleodisaturated glycerides of cocoa butter but also positional isomers of these glycerides. When the fats were molded under the same conditions employed with cocoa butter, linear shrinkage was only about one-third that of cocoa butter.
Lipase from Rhizopus delemar was immobilized by entrapment with photo-crosslinkable resin prepolymers or urethane prepolymers or by binding to various types of porous silica beads. The immobilized lipase preparations thus obtained were examined for their activity in converting olive oil to an interesterified fat (cacao butter-like fat), whose oleic acid moieties at 1- and 3-positions were replaced with stearic acid moieties, in the reaction solvent n-hexane. Although all of the immobilized preparations exhibited some activity, lipase adsorbed on Celite and then entrapped with a hydrophobic photo-crosslinkable resin prepolymer showed the highest activity, about 75% of that of lipase simply adsorbed onto Celite. Entrapment markedly enhanced the operational stability of lipase.
Extracellular microbial lipases can be used as catalysts for the interesterification of oils and fats. Use of specific lipases
gives products which are unobtainable by chemical interesterification methods. Some of these products have properties of value
to the oils and fats industry. The catalysts for enzymatic interesterification are prepared by coating inorganic support materials
with the lipases. For batch interesterification reactions, the catalyst particles are activated by addition of a small amount
of water and then stirred with a reactant mixture dissolved in petroleum ether. At the end of the reaction period, the catalyst
particles are removed by filtration, and the interesterified triglycerides isolated by conventional fat fractionation techniques.
The catalyst can be used in subsequent batch reactions. As an alternative to the batch reaction system, continuous enzymatic
interesterification processes can be operated by pumping water containg feedstock through a packed bed of activated catalyst.
Two triglycerides, 1-oleodisterain and 2-palmito-oleostearin, which are components of some confectionery fats, were synthesized and their melting behavior and dilatometric properties were determined. Expansivities and melting dilations of the various polymorphic forms were measured.
1-Oleodisterain was found to have two melting points, 30.3 and 42.1°C., while 2-palmito-oleostearin was found to have melting points at 24, 37, and 40.5°C. The rate of transformation of the thermodynamically unstable polymorphs at temperatures below their melting points were much more rapid than those for the corresponding 2-oleo isomers previously reported.
Mixtures of 2-oleopalmitostearin with 2-palmito-oleostearin and 1-oleodistearin with 2-oleodistearin were examined dilatometrically. In each of these mixtures the components apparently do not temper at the same rate to similar polymorphic forms and thus there is some degree of incompatibility even though in each of these mixtures the components are positional isomers. The properties of the intermediate melting mixtures are dependent on the method of tempering.
Technical considerations indicate that cocoa butter-like mixtures can be prepared readily by the esterification of mixtures of oleic, palmitic, and stearic acids, or the interesterification of their glycerides, followed by the fractional crystallization of the reaction products.
Using the indicated procedures, three cocoa butter-like fractions were prepared. One consisted essentially of oleopalmitostearins, another consisted essentially of oleodistearins, while the third consisted mostly of oleodipalmitins.
On the basis of softening point curves, the oleopalmitostearin product was most compatible with cocoa butter, the oleodistearin product was the next most compatible, while the oleodipalmitin product was least compatible. When mixed with cocoa butter, all three of the products produced consistencyvs. temperature curves whose shapes closely resembled that of cocoa butter. All of the mixtures softened over a short temperature interval though the actual temperature at which softening occurred varied. The several products are believed to be satisfactory cocoa butter replacements.
Another cocoa butter-like fat was prepared by the interesterification of 70 parts of completely hydrogenated cottonseed oil and 30 parts of olive oil and genated cottonseed oil and 30 parts of olive oil and the subsequent fractionation of the reaction product.
Intercept, Newcastle-upon-Tyne
- A R Macrae
- R C Hammond