Abstract
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.
Highlights
Cocoa butter (CB) is one of the most expensive fats in the world and current trends in the cocoa butter market suggest further rises in cocoa butter prices, shortages, strong demand in emerging countries, and profit squeezes for companies in the future
Cocoa butter alternatives are categorized as CB equivalents (CBEs), CB replacements (CBRs), and CB substitutes (CBSs)
Due to the removal of partially hydrogenated oils (PHOs) from the Generally Recognized as Safe (GRAS) list has caused a drastic reduction in CBR use in the confectionary industry
Summary
Cocoa butter (CB) is one of the most expensive fats in the world and current trends in the cocoa butter market suggest further rises in cocoa butter prices, shortages, strong demand in emerging countries, and profit squeezes for companies in the future. Partial or full replacements of CB with these exotic butters have limitations These natural CBEs lack one or two of the main structural TAGs of cocoa butter (POP, POS and SOS). Enzymatic interesterification (EIE) of fats and oils to produce specialty fats has gained considerable attention since regio-specific microbial lipases (3.1.1.3) offer certain advantages over chemical catalysts[8] These include reaction products with a TAG composition that more closely resembles cocoa butter (1,3- specific reaction instead of random), the possibility of running the reaction at lower temperatures, enzyme re-use, lower isomerization by-products, and better control of CBE production[9]. Microbial lipases from Rhizomucor, Rhizopus, and Candida such as Lipozyme TL IM from Mucor miehei and Novozyme 435 from Candida antarctica are commercially available[10]
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