Identification of cocoa butter equivalents added to cocoa butter I. An approach by fatty acid composition of the triacylglycerol sub-fractions separated by Ag+-HPLC

 Separation of the six sub-fractions of triacylglycerols (TAG) from cocoa butter, three cocoa butter equivalents (CBEs: calvetta, choclin and coberine) and their mixtures was carried out by silver ion high-performance liquid chromatography. The percentage fatty acid composition of all these sub-fractions was then measured by high-resolution gas chromatographic analysis of the methyl esters of the constitutive fatty acids. In particular, the percentage quantities of all acids in the fully saturated sub-fraction of pure fats and some of their mixtures were evaluated as a function of the percentage CBEs added to cocoa butter in order to devise multiple regression models. The aim was to obtain statistical tools for the identification and/or quantification of added CBEs. The results obtained show the effectiveness of TAG sub-fraction percentage fatty acid composition data for the purposes of research, as well as the potential use of stereospecific analysis of the same sub-fractions. In fact, the stereospecific analysis of TAG fractions from cocoa butter and CBEs already carried out has enabled observation of the different distributions of various fatty acids in the glycerol backbone of TAG from cocoa butter and the CBEs under study, and this will certainly result in the development of more powerful and discriminating statistical models. Received: 12 August 1997 / Revised version: 19 December 1997     

Identification of cocoa butter equivalents added to cocoa butter. III. Stereospecific analysis of triacylglycerol fraction and some its subfraction

In previous papers, six cocoa butter equivalent (CBE) samples were considered to carry out a study about the detection of their presence in cocoa butter (CB). In this work the % fatty acid (FA) compositions of triacylglycerol (TAG) subfractions separated by Ag⁺-High Performance Liquid Chromatography (Ag⁺-HPLC) from CB, CBE and CB/CBE mixtures were investigated. The fully saturated (SatSatSat) TAG subfractions isolated from CB, CBE and CB/CBE mixtures were the most suitable for the aim of the research. In fact, the multiple regression models obtained using the % FA composition of SatSatSat subfractions permitted to carry out effective CBE detections. In the present work the attempt to improve the statistical approach using as variables the results of the stereospecific analysis of the TAG fraction and of its main subfractions from CB, CBE and CB/CBE mixtures is described.     

Identification of cocoa butter equivalents added to cocoa butter by fatty acid composition of the triacylglycerol sub-fractions separated by Ag+-HPLC – II –

 In a previous study the fatty acid compositions of triacylglycerol sub-fractions, separated by Ag⁺-HPLC, were studied in samples of cocoa butter, cocoa butter equivalents (CBE) and some of their mixtures. In this paper similar research is described which was carried out on three other CBE (Illexao 30–61, Illexao 30–63, Illexao 30–71). The results show the particular significance of the fully saturated sub-fraction, in which notable percentage changes in C16 : 0 and C18 : 0 contents were also detectable in the two mixtures with the lowest CBE content (5% or 15%, w/w) relative to genuine cocoa butter. Multiple regression analysis was used to verify the percentages changes of fatty acid contents in the fully saturated sub-fraction as a function of the percentage of CBE added to genuine cocoa butter. Received: 19 December 1997 / Revised version: 25 June 1998     

Evaluation of high oleic-high stearic sunflower hard stearins for cocoa butter equivalent formulation

Cocoa butter equivalents (CBEs) are produced from vegetable fats by blending palm mid fraction (PMF) and tropical butters coming from shea, mango kernel or kokum fat. In this regard, high oleic-high stearic (HOHS) sunflower hard stearins from solvent fractionation can be used in CBE production since their compositions and physical properties are similar to those found in the above-mentioned tropical butters. In this work, three sunflower hard stearins (SHS) ranging from 65% to 95% of disaturated triacylglycerols and a shea stearin (used as reference) were blended with PMF to evaluate their potential use in CBEs formulation. Isosolid phase diagrams of mixtures of PMF/SHS showed eutectic formation for SHS 65 and SHS 80, but monotectic behaviour with softening effect for SHS 95. Three CBEs from SHS and shea stearin were formulated according to phase behaviour diagrams and solid fat content data at 25 °C. Isosolid phase diagrams of mixtures of these CBEs with cocoa butter showed no eutectic behaviour. Therefore, CBEs elaborated from SHS exhibited full compatibility with cocoa butter.     

The advantages of solid fat content determination in cocoa butter and cocoa butter equivalents by the Karlshamns method

This paper describes the preparation of samples and the evaluation techniques applied to determine the Solid Fat Content (SFC) by means of pulsed nuclear magnetic resonance (NMR) in confectionery fats characterized by distinct polymorphism (cocoa butter, cocoa butter equivalents and their mixtures). Due to the deviation of SFC values in certain softer cocoa butter equivalents at the temperature of 20 °C, an internal method devised at Karlshamns Oils & Fats AB is applied as well. When compared to the official IUPAC 2.150 (b) method, Karlshamns' method involves a lower temperature and a prolonged period of time at the stage of the final SFC stabilization in the pre-treatment of fat samples. The calculation of SFC in the analysed samples for the purposes of this paper was carried out by employing both methods (the indirect method and a serial procedure). The results are presented graphically. Differences were reflected in the SFC of the fats and their mixtures that were under observation depending on the method and temperatures applied. The obtained results indicated a considerable advantage of employing the Karlshamns method since the results yielded by this method are more lucid. Moreover, the behaviour of fats in the production process can be more easily predicted on the basis of these results.     

Composition and thermal analysis of ternary mixtures of avocado fat:palm stearin:cocoa butter (Avo:PS:CB)

Avocado fat is a semi-solid substance with potential functional lipid characteristics. A study was carried out to evaluate the effect of addition of palm stearin and cocoa butter on the solidification behavior of avocado fat to formulate a mixture to become similar to lard. A total of three mixtures were prepared: avocado fat:palm stearin:cocoa butter (88:7:5), avocado fat:palm stearin:cocoa butter (86:7:7), avocado fat:palm stearin:cocoa butter (84:7:9; w/w), and identified by the mass ratio of avocado fat to palm stearin and cocoa butter. The fat mixtures were compared with lard in terms of the fatty acid and triacylglycerol compositions using gas chromatography and high-performance liquid chromatography, thermal properties using differential scanning calorimetry and solid fat content using p-nuclear magnetic resonance. Although there were considerable differences between lard and the fat mixtures with regard to fatty acid and triacylglycerol compositions, some similarities were seen with regard to thermal properties and solid fat content profile. Of all the fat mixtures, avocado fat:palm stearin:cocoa butter (84:7:9) displayed closer similarity to lard with respect to thermal transitions at –3.59°C and its solid fat content profile showed the least difference to that of lard throughout the temperature range measured.     

Physical properties of tempered mixtures of cocoa butter,CBR and CBS fats

Physical characteristics of precrystallised binary mixtures of cocoa butter (CB) and 5, 10, 15, 20, 25 and 30% (w/w) cocoa butter replacer (CBR) or cocoa butter substitute (CBS) were determined. The lipid composition was obtained by chromatography and the solid fat content (SFC) by nuclear magnetic resonance. Tempering was carried out using a lab‐scale agitated jacket vessel reactor. Bars made with tempered samples were submitted to X‐ray diffraction and rupture tests. Snap values of crystallised mixtures decrease with an increase in the amount of alternative fat. X‐ray diffraction patterns confirmed the predominant formation of the beta polymorph habit for CB and beta prime form for CBR and CBS. Mixtures of CB and CBR exhibit chemical compatibility. The knowledge of the snap values and of the variation of SFC with temperature proved to suffice to adequately anticipate the influence of the addition of alternative fats on chocolates physical attributes.     

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

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.     

Analysis of triacylglycerol isomers in Malaysian cocoa butter using HPLC–mass spectrometry

Chocolate is acclaimed for its unique and highly desirable flavor and its unusual melting characteristics (a narrow melting point range centered a few degrees below body temperature ∼32 to ∼35 °C). The triacylglycerol (TAG) composition of cocoa butter is responsible for this important melting behavior. The exact composition of the primary TAG in a Malaysian cocoa butter sample was elucidated by ESI/tandem mass spectroscopy. The cocoa butter sample consisted primarily of the TAG, POP, POS and SOS with smaller amounts of PLP, POO, PLS, and SOO, where P, O, S, and L indicated palmitic, oleic, stearic and linoleic acid, respectively. The use of tandem mass spectroscopy or MS/MS was critical for the identification of coeluted TAG, such as POO and PLS. The fragmentation pattern provided by diacylglycerol sodium adduct ions, enabled the identification of co-eluted TAG by the loss of a fatty acid fragment and the corresponding diacylglycerol sodium adduct ion.     

Evaluation model for cocoa butter equivalents based on fatty acid compositions and triacylglycerol patterns

Food Science and Biotechnology - An effective evaluation model was established to digitize the quality of cocoa butter equivalents (CBEs) based on determinations of total and sn-2 fatty acid...     

Quality of Malaysian cocoa butter during storage

Malaysian pure prime pressed and deodorised cocoa butters were obtained from local cocoa grinders and analysed for quality deterioration. Approximately 5 kg of each sample was packed in corrugated paper boxes lined with low‐density polyethylene plastic material of thickness 73.2 µm. The water vapour transmission rate and gas transmission rate (for oxygen) of the plastic material were 3.21 g m^?2 day^?1 (37.8 °C, 90 ± 2% RH) and 71.57 cm³ m^?2 day^?1 (23.0 °C, 0% RH) respectively. The butters were stored at 15 ± 4 °C and 70 ± 4% RH for up to 24 months. Samples were taken every 2 months and analysed for free fatty acid content, saponification value, iodine value, refractive index and peroxide value. The findings indicated that the free fatty acid content, iodine value and peroxide value of both types of cocoa butter increased with storage duration. The other parameters showed no significant changes. However, the free fatty acid content and peroxide value after 24 months of storage were still below the limits specified in Malaysia. Therefore we conclude that both types of Malaysian cocoa butter are still in good condition after 24 months of storage, with minimal quality deterioration. Copyright © 2004 Society of Chemical Industry     

Enzymatic synthesis of cocoa butter analog through interesterification of lard and tristearin in supercritical carbon dioxide by lipase

Substrate oil composition, reaction time, acyl donor, temperature, and pressure affected the triacylglycerol (TG) content of cocoa butter analog during the interesterification reaction catalyzed by lipase in a supercritical carbon dioxide (SC-CO₂) system. Among oil sources used to interact with tristearin, the content of 1(3)-palmitoyl-3(1)-stearoyl-2-monoolein (POS) (P, palmitate; O, oleate; S, stearate) and 1-palmitoyl-2, 3-dioleoylglycerol (POO) in analog was most similar to the corresponding TG content of cocoa butter when analog was prepared with lard. The optimized interesterification reaction using lard and tristearin (at a mole ratio of 1.4) as substrates to produce cocoa butter analog in a SC-CO₂ system was at 17 MPa, 50 °C, pH 9, for 3 h with an immobilized lipase, Lipozyme IM-20, from Mucor miehei. The lyophilized enzyme facilitated the production of cocoa butter analog in anhydrous substrates (a_w 0.33). The yield and melting point of the purified cocoa butter analog by a silica column was 63% and 34.5 °C, respectively, when the analog was produced under optimal conditions.     

Effect of adding shea butter stearin and emulsifiers on the physical properties of cocoa butter

The aim of this study was to assess the feasibility of shea butter stearin (SBS) as cocoa butter equivalent (CBE). In this work, the optimal ratio of SBS and cocoa butter (CB) was evaluated by the solid fat content and deviation solid fat content. Emulsifiers added to SBS and CB blends were first screened based on β polymorph level, and mixture regression experiment was designed to obtain the optimized compound emulsifiers ratio, finally the characterization of shea butter chocolate was evaluated by sensory evaluation and texture profile analysis (TPA). The best compatibility was obtained when the mixture ratio of SBS and CB was 20:80, where ΔSFC within a range of 1.5 was shown. The appropriate compound emulsifiers were soy lecithin: polyglycerol polyricinoleate: Tween 60 = 1:1:1. Both sensory evaluation and TPA test showed SBS and CB blends could improve the taste and texture of chocolate with proper emulsifiers addition.     

Investigation of changes in formulation and processing parameters on the physical properties of cocoa butter emulsions

The aim of this work was to understand the physical characteristics of cocoa butter water in oil emulsions made using a process typically used for margarine production (a scraped surface heat exchanger and pin stirrer). Processing parameters were manipulated, and the effect of aqueous phase volume, polyglycerol polyricinoleate (PGPR) concentration, and the addition of a hydrocolloid to the aqueous phase were investigated. This process allowed small droplets to be formed (3–5 μm). Tempering could also be mimicked, with the temperature of the units affecting the polymorphic form of cocoa butter produced. Sintered crystalline shells were observed at the oil/water droplet interface, acting as Pickering particles. This work highlights the potential for the use of cocoa butter emulsions to give fat reduction in chocolate, using a one step process to achieve emulsification and to mimic tempering.     

Influence of cocoa butter refining on the quality of milk chocolate

A refining step is often crucial for the removal of undesired components in fats and oils. More flexible refining technologies are required due to a global decline in cocoa butter quality and to meet industry’s demand for cocoa butters with improved properties. The aim was to investigate the impact of the cocoa butter refining process on milk chocolate quality. Therefore a crude cocoa butter was subjected to a steam refining at different temperatures and this with or without a silica pretreatment. The major effect of the silica pretreatment was the complete removal of phosphorus (thus phospholipids), iron and alkaline components. During the steam refining step mainly Free Fatty Acids (FFA) were removed at increased temperatures (T ? 200 °C). The refining of the cocoa butter influenced the rheological properties of the chocolate. An increased packed column temperature, coinciding with the removal of FFA, resulted in a lower yield stress and a higher viscosity. Reduction of FFA positively influenced the crystallization kinetics and the formation of the crystal network, resulting in differences on a macroscopic scale.     

Production of stearate-rich butters by solvent fractionation of high stearic–high oleic sunflower oil

Cocoa butter equivalents (CBEs) are fats with a similar composition and melting profile as cocoa butter (CB), which are usually prepared by blending mid-palm fractions and stearate-rich tropical butters. In this regard, high stearic–high oleic sunflower oil contains disaturated triacylglycerols typically present in CBEs, albeit at a lower concentration than that required to produce a solid fat. Here we have assessed a means to fractionate this oil in order to produce solid fractions that can be used as stearic acid-rich butters appropriate for CBE formulations. Solvent fractionation of high stearic–high oleic sunflower oil was optimised in function of the oil/solvent ratio and temperature. Sunflower stearins with similar melting profiles as cocoa butter were obtained from oils of either 17% or 20% stearic acid in a single step. Different stearin products can be obtained by controlling the oil/solvent ratio and the temperature of fractionation. The use of these fractions as CBE components or confectionery fats is discussed in function of their melting profiles.     

Effect of sugar, cocoa particles and lecithin on cocoa butter crystallisation in seeded and non-seeded chocolate model systems

The effect of major chocolate ingredients (sugar, cocoa particles and lecithin), in combination with the two pre-crystallization techniques, seeding and non-seeding, was investigated with respect to the kinetics of cocoa butter crystallisation and the resulting microstructure. Confocal laser scanning microscopy (CLSM) was used to monitor microstructural evolution under dynamic thermal conditions. DSC measurements and image analysis were also applied in order to quantify the impacts of processing and formulation on microstructure. All ingredients and pre-crystallisation techniques considered proved to have a large impact on fat crystallisation kinetics and the resulting microstructure. Seeded samples tended to form multiple nucleation sites, inducing rapid growth of a crystal network. The non-seeded samples showed an altering structure, with some domains developing large spherical crystals while in other domains a more heterogeneous microstructure resulted. Lecithin showed a remarkable impact on crystallisation kinetics in both the seeded and non-seeded samples. For the seeded samples, the effect was most noteworthy in samples containing cocoa butter and sugar, where lecithin significantly reduced the induction time. In the absence of seeds, lecithin itself acted as the nucleation site for fat crystallisation.     

制备类可可脂原料用油的研究进展

近年来,巧克力市场逐年壮大,可可脂的需求也随之不断增加。而可可脂产量有限,加之成本较高,可可脂替代品成为学者和商家研究的热点。其中,类可可脂以其特有的优势,成为可可脂替代品中独具特色的一种。对制备类可可脂的原料用油进行了归纳总结,分别从类可可脂的制备方法、原料油脂组成及其相关研究方面对原料油脂进行了概述,从而加深对类可可脂的了解。     

Fatty acid tryptamides as shell indicators for cocoa products and as quality parameters for cocoa butter

The methods used to date to determine the shell content in cocoa products are very time-consuming, protracted and not specific enough, meaning that with the development of a new high-performance liquid chromatography (HPLC) method using fluorescence detection, a considerably more specific process is now available. Fatty acid tryptamides can be drawn on as indicator substances for detecting the shell content in cocoa products. The relevant substance species are docosanoyl-2-(3-indolyl)ethylamide (behenic acid tryptamide, BAT) and tetracosanoyl-2-(3-indolyl)ethylamide (lignoceric acid tryptamide, LAT). To allow conclusions on the average levels of fatty acid tryptamides (FAT) in cocoa products to be drawn, 433 cocoa samples were analysed. The natural tryptamide concentrations in cocoa shells and cocoa nibs or cocoa liquors varied significantly. The average ratio of cocoa shells to cocoa nibs/cocoa liquors is 16:1. As a result of these differences in concentration, the shell content can be determined with a high degree of accuracy via the fatty acid tryptamides in cocoa. This method also allows conclusions to be drawn on the quality of cocoa butter. The tryptamide concentrations in pressed cocoa butter and in expeller butter respectively vary greatly, so that it is possible through the FAT levels determined to gain an insight into the method of production of cocoa butter.     

Effect of cocoa butter structure on oil migration

Oil migration from a high oil content filling into adjacent chocolate causes changes in product quality. The objective of this study was to quantify the oil migration from a cream filling system into cocoa butter, which provided a model for the behavior of chocolate-enrobed confectionery products with a soft, creamy center. Magnetic resonance imaging (MRI) was used to monitor spatial and temporal changes of liquid lipid content. A multislice spin echo pulse sequence was used to acquire images with a 7.8 ms echo time and a 200 ms repetition time using a 1.03 T Aspect Imaging MRI spectrometer. Samples were prepared as a 2-layer model system of cocoa butter and model cream filling. Three methods were used to prepare the cocoa butter: static, seeded, and sheared. Samples were stored at 25 °C for a time frame of 56 d. The rate of oil migration was quantified by a kinetic expression based on the linear dependence of oil uptake by cocoa butter and the square root of the time. Samples showed distinctly different rates of oil migration, as evidenced by quantitative differences in the kinetic rate constant. Practical Application: This work will be helpful to elucidate the influence of crystallization process and structural properties such as crystal nanostructure and crystal habit on the migration of oil through a crystalline fat matrix.