Preparation of Low-Diacylglycerol Cocoa Butter Equivalents by Hexane Fractionation of Palm Stearin and Shea Butter

Herein, we prepared 1,3-dipalmitoyl-2-oleoyl glycerol (POP)-rich fats with reduced levels of diacylglycerols (DAGs), adversely affecting the tempering of chocolate, via two-step hexane fractionation of palm stearin. DAG content in the as-prepared fats was lower than that in POP-rich fats obtained by previously reported conventional two-step acetone fractionation. Cocoa butter equivalents (CBEs) were fabricated by blending the as-prepared fats with 1,3-distearoyl-2-oleoyl glycerol (SOS)-rich fats obtained by hexane fractionation of degummed shea butter. POP-rich fats achieved under the best conditions for the fractionation of palm stearin had a significantly lower DAG content (1.6 w/w%) than that in the counterpart (4.6 w/w%) prepared by the previously reported method. The CBEs fabricated by blending the POP- and SOS-rich fats in a weight ratio of 40:60 contained 63.7 w/w% total symmetric monounsaturated triacylglycerols, including 22.0 w/w% POP, 8.6 w/w% palmitoyl-2-oleoyl-3-stearoyl-rac-glycerol, 33.1 w/w% SOS, and 1.3 w/w% DAGs, which was not substantially different from the DAG content in cocoa butter (1.1 w/w%). Based on the solid-fat content results, it was concluded that, when these CBEs were used for chocolate manufacture, they blended with cocoa butter at levels up to 40 w/w%, without distinctively altering the hardness and melting behavior of cocoa butter.     

Fast Melt Cocoa Butter Tablet: Effect of Waxes,Starch, and PEG 6000 on Physical Properties of the Preparation

A fast melt tablet (FMT) is well regarded as an alternative delivery system that might help resolve a patient’s non-compliance issue. The main objective of this study was to develop a cocoa butter-based FMT. Additives, namely 5–15% of PEG 6000, beeswax, paraffin wax, and corn starch, were incorporated into the cocoa butter-based FMT to study the effects of these additives with the physical characteristic of a cocoa butter FMT. An optimum-based formulation was chosen according to the desired hardness and disintegration time and the taste masking property achieved with the model drug—dapoxetine. The analysis demonstrated that incorporating beeswax (15%) and paraffin wax (15%) could prolong the disintegration time by at least two-fold. On the contrary, the presence of corn starch was found to cause an increase in the hardness and reduction of the disintegration time. The disintegration mechanism might be presumed due to the synergistic effect of starch swelling and cocoa butter melting. The hardness value and in vitro disintegration time of the optimum formulation were recorded at 2.93 ± 0.22 kg and 151.67 ± 6.98 s. In terms of dissolution, 80% of dapoxetine was released within 30 min and the dissolution profile was comparable to the innovator product. The formulation was palatable and stable for at least 1 year. The exposure of the FMT formulation at 30 °C for 12 months was reported to be stable. Along with the sound palatability profile and high drug load capacity, the current formulation possesses the desired characteristics to be scaled up and marketed.     

The Use Of Hplc To Separate Triglycerides In Confectionery Fats Using Ultra Violet Detection

Abstract

The triglycerides of confectionery fats have been separated by reverse phase HPLC using mixtures of either acetonitrile and tetrahydrofuran or acetonitrile and methyl tertiary butyl ether using UV detection at 237 nanometres. The method has been applied to samples of cocoa butter, cocoa butter equivalents, milk fat and other vegetable fats. The fat from a milk chocolate has been separated by the above system.     

Polymorphous transitions in cocoa butter</o:p>

Summary Large experimental evidence was collected on polymorphous transitions of triacyl glycerols (TAG) in cocoa butter by means of DSC investigations. The cooling treatment (in conditions close to those of the industrial practice) and the annealing temperature significantly affect the overall crystal fraction and the distribution of the various polymorphs. These data allowed a quantitative, although purely phenomenological, kinetic parameterization of polymorphous transitions of cocoa butter. The evaluation of the relevant kinetic constants and their dependence on the temperature allowed prediction of the yield in every polymorph after a given thermal history. Similar evidences were attained for cocoa liquor and dark chocolate where TAG are sided by other ingredients. These results can be the basis for an industrial exploitation.</o:p>     

Structure elucidation of triglycerides by chromatographic techniques. Part 2: RP HPLC of triglycerides and brominated triglycerides

The structure determination of triglycerides by RP HPLC is discussed, and the importance of temperature and mobile phase composition demonstrated. The formation of brominated triglycerides followed by RP HPLC analysis allows rapid determination of cocoa butter equivalents (CBE ) in cocoa butter and chocolate products.     

Crystallization behavior of blends of cocoa butter and milk fat or melk fat fractions

Mixtures of milk fat or milk fat fractions, produced by melt crystallization, and cocoa butter were studied using isothermal calorimetry. Crystallization of cocoa butter (at 15, 20 and 25C) was observed, and induction time for nucleation, peak time and amount of heat produced were recorded. Melting profiles and X-ray spectra were also obtained, yielding information about extent of crystallization and type of polymorph obtained. Induction time for nucleation generally increased with increasing temperature. Peak time increased at 15C, but decreased at 20C. Amount of crystallized fat decreased with increasing level of milk fat.This work was supported by the National Dairy Promotion and Research Board and the Wisconsin Milk Marketing Board. Special thanks are extended to Jennifer Wood for valuable participation in this research and to Dr. George Zografi and his research group for their assistance with the DSC studies.     

Lipase-Catalyzed Acidolysis of Palm Mid Fraction Oil with Palmitic and Stearic Fatty Acid Mixture for Production of Cocoa Butter Equivalent

Cocoa butter equivalent (CBE) was prepared by enzymatic acidolysis reaction of substrate consisting of refined palm mid fraction 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 composition of the five major triacylglycerols (TAGs) of the structured lipids was identified and quantified using cocoa butter certified reference material IRMM-801. The reaction resulted in production of cocoa butter equivalent with the TAGs' composition (1,3-dipalmitoyl-2-oleoyl-glycerol 30.7 %, 1-palmitoyl-2-oleoyl-3-stearoyl-rac-glycerol 40.1%, 1-palmitoy-2,3- dioleoyl glycerol 9.0 %, 1,3-distearoyl-2-oleoyl-glycerol 14.5 %, and 1-stearoyl-2,3-dioleoyl glycerol 5.7 %) and with onset melting temperature of 31.6 °C and peak temperature of 40.4 °C which are close to those of cocoa butter. The proposed kinetics model for the acidolysis reaction presented the experimental data very well. The results of this research showed that palm mid fraction oil TAGs could be restructured to produce value added product such as CBE.     

Lipase-Catalyzed Synthesis of Cocoa Butter Equivalent from Palm Olein and Saturated Fatty Acid Distillate from Palm Oil Physical Refinery

Cocoa butter equivalent was prepared by enzymatic acidolysis reaction of substrate consisting of refined palm olein oil and palmitic?Cstearic 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.     

The Effect of Fat Content and Fatty Acids Composition on Color and Textural Properties of Butter

The textural properties of butter are influenced by its fat content and implicitly by the fatty acids composition. The impact of butter’s chemical composition variation was studied in accordance with texture and color properties. From 37 fatty acids examined, only 18 were quantified in the analyzed butter fat samples, and approximately 69.120% were saturated, 25.482% were monounsaturated, and 5.301% were polyunsaturated. The butter samples’ viscosity ranged between 0.24 and 2.12 N, while the adhesiveness ranged between 0.286 to 18.19 N·mm. The principal component analysis (PCA) separated the butter samples based on texture parameters, fatty acids concentration, and fat content, which were in contrast with water content. Of the measured color parameters, the yellowness b* color parameter is a relevant indicator that differentiated the analyzed sample into seven statistical groups; the ANOVA statistics highlighted this difference at a level of p < 0.001.     

Quantification of Porous Properties of Shear Crystallized Lipids

The aim of this study was to investigate the impact that shear and composition have on the structural properties associated with the porous phases of lipids. To accomplish this aim, we developed eight main crystallized samples using cocoa butter (CB) or trilaurin (TL) in the presence or absence of monostearate (M) (5% w/w). The samples were sheared at 500 s⁻¹ using random (RS) or laminar (LS) shear at a cooling rate of 2 °C/min. Using the maximal ball (MB) algorithm, several empirical void measurements such as connectivity (z), pore and throat volume weighted radii (R₄₃), and void fraction (v) were quantified using 3D X-ray microcomputed tomography images. Most void features were identified as micropores (R ≥ 10 μm) possibly originating from the crystallization process and post-process crystal growth. Likewise, depending on the applied treatments, mechanisms impacting void formation were found to produce noticeable variation in v (0.019 to 0.139) and to determine whether void morphology was spherical, irregular, and/or highly connected.     

Investigation of the complex thermal behavior of fats

The thermal behavior of three ural fats (displaying very different composition), cocoa butter (CB)², lard, and a stearin obtained from anhydrous milk-fat (AMF) fractionation, were studied by both DSC and X-ray diffraction as a function of temperature (XRDT). To perform temperature explorations between –30C and +80C, at rates identical to those used for DSC and ranging from 0.1 K min^–1 to 10 K min^–1, a new set of X-ray sample-holders, temperature-controlled by Peltier effect, has been developed. It is shown that the three more stable polymorphic forms of CB were easily characterized by either X-ray diffraction or DSC, and existence of two -3L forms was confirmed. On the contrary, the more complex polymorphism of lard and AMF required combined examination by DSC and XRDT and the brightness of the synchrotron source for studies at the highest heating rates. Quantitative analysis of the long spacings of XRDT recordings is invaluable for interpretation of thermal events. For instance, it was found that the simultaneous formation of two polymorphic forms, of apparent long spacing of 34 and 42 å, at the onset of lard crystallization might explain the difficulty of its fractionation.Special thanks to Courtney P. Mudd (NIH, Bethesda) for his pertinent advice on the mounting and use of thermoelectric devices. The study of lard crystallization was initiated by Valerie Portalier and suggested by Jean-Luc Vendeuvre of CTSCCV (Maisons-Alfort). For the AMF part of this study, stearin was fractionated by ADRIA Normandie, while characterization of its thermal properties was performed as part of a research program funded by ARILAIT Recherches and the French Ministry of Research and Technology.     

Induced G phase through intermolecular hydrogen bonding: X. Crystallization kinetics study on two structural isomers

A comparative systematic crystallization kinetics study has been carried out on two distinct novel liquid crystalline isomers, DBA:R:DBA and DBA:H:DBA (where DBA = p-n-decyloxybenzoic acid, R = resorcinol and H = hydroquinone) using differential scanning calorimetry. The kinetics experiment is performed from the crystal G phase (kinetophase), which is a common induced phase in both compounds. The molecular mechanism and dimensionality of crystal growth are studied from the Avrami exponent n while the characteristic crystallization time (t ^*) at each crystallization temperature is deduced from the individual plots of log t vs. Δ H.     

Cocoa Shell as a Step Forward to Functional Chocolates—Bioactive Components in Chocolates with Different Composition

Chocolate is considered as both caloric and functional food. Its nutritional properties may be improved by addition of fiber; however, this may reduce polyphenols content. The aim of this research was to determine the influence of cocoa shell addition (as a source of fiber) and its combination with different ingredients (cocoa butter equivalents (CBE), emulsifiers, dairy ingredients) on polyphenols of dark and milk chocolates. Total polyphenol (TPC) and total flavonoid (TFC) contents were determined spectrophotometrically, identification and quantification of individual compounds by high pressure liquid chromatography and antioxidant capacity by ferric reducing antioxidant power (FRAP) assay. Results showed that even though addition of cocoa shell to chocolate results in reduced contents of TPC, TFC, and individual compounds, it is not significant compared to ones reported by other authors for commercial chocolates. Other ingredients influence determined values for all investigated parameters; however, additional research is needed to reveal exact mechanisms and implications.     

Evaluation of the relaxation modules from the response to a constant rate of strain followed by a constant strain

The stress response σ(t) to a constant rate of strain $ \dot \varepsilon $ ε during the period 0 < t ≤ t^* and to the constant strain ε^* $ ( = \dot \varepsilon t*) $ thereafter is considered in terms of the Boltzmann superposition principle. When t ≤ t^*, the data directly give the constant-rate modulus F (t) ≡ σ(t)/ε(t), which can be converted straightforwardly into the relaxation modulus E(t). Results from illustrative calculations show that a reduction in the relaxation rate effects a decrease in [σ(t^*)/ε^*]/E(t^*) and also in the time at which [σ(t)/ε^*]/E(t) becomes essentially unity. To evaluate E(t) at t > t^*, F(t) is first obtained from σ(t) and F(t ? t^*) by using a derived equation similar to that presented by Meissner. Thereafter, F(t) is transformed into E(t). For illustration, E(t) for a rubbery solid is evaluated over some 2.5 decades of time from its response to a strain rate of 0.25 min^?1 for 0.40 min and thereafter to the attained strain of 0.10 for 5.4 min.     

Cocoa By-Products: Characterization of Bioactive Compounds and Beneficial Health Effects

The annual production of cocoa is approximately 4.7 million tons of cocoa beans, of which only 10% corresponds to the cocoa bean and the remaining value corresponds to a high number of residues, cocoa bean shell, pulp and husk. These by-products are a source of nutrients and compounds of notable interest in the food industry as possible ingredients, or even additives. The assessment of such by-products is relevant to the circular economy at both environmental and economic levels. Investigations carried out with these by-products have shown that cocoa husk can be used for the production of useful chemicals such as ketones, carboxylic acids, aldehydes, furans, heterocyclic aromatics, alkylbenzenes, phenols and benzenediols, as well as being efficient for the removal of lead from acidic solutions, without decay in the process due to the other metals in this matrix. The fibre present in the cocoa bean shell has a considerable capacity to adsorb a large amount of oil and cholesterol, thus reducing its bioavailability during the digestion process, as well as preventing lipid oxidation in meats, with better results compared to synthetic antioxidants (butylated hydroxytoluene and β-tocopherol). Finally, cocoa pulp can be used to generate a sweet and sour juice with a natural flavour. Thus, this review aimed to compile information on these by-products, focusing mainly on their chemical and nutritional composition, simultaneously, the various uses proposed in the literature based on a bibliographic review of articles, books and theses published between 2000 and 2021, using databases such as Scopus, Web of Science, ScieLO, PubMed and ResearchGate.     

Variations of Rate Coefficients and Termination Mechanism During the After‐Effects of a Light‐ Induced Polymerization of a Dimethacrylate Monomer

This work was aimed at studying variations in the termination mechanism occurring during the after‐effects of a light‐induced polymerization of a dimethacrylate monomer after the irradiation had been discontinued. The experimental method was based on differential scanning calorimetry. The initiation was stopped at various moments of the reaction corresponding to different degrees of double‐bond conversion (starting conversions). Three termination models: monomolecular, bimolecular, and mixed were used to calculate the ratio of the bimolecular termination and propagation rate coefficients k_t^b/k_p and/or the monomolecular termination rate coefficient k_t^m. The models were determined over short time intervals (conversion increments) of the dark reaction giving different values of rate coefficients for each time interval (interval approximation method). Two‐stage statistical analysis was used to find the model that best reproduced the experimental data obtained for each conversion increment. This enabled variations in the termination mechanism during the after‐effects to be followed. It was found that the termination mechanism changed with the time of the dark reaction from the bimolecular reaction to the mixed reaction when the light was cut off at low and medium double‐bond conversions. At higher starting conversions a monomolecular termination mechanism dominated from the beginning of the dark reaction. The mixed termination model was the only model to describe correctly the variations of rate coefficients in the dark, i. e., the increase in k_t^m and the decreasein the k_t^b/k_p ratio.     

Kinetic study of high-conversion copolymerization of butyl acrylate with methyl methacrylate in solution

Butyl acrylate (BA) and methyl methacrylate (MMA) have been copolymerized in a 3 mol/L benzene solution using 2,2′-azobis(isobutyronitrile) (AIBN) as initiator over a wide composition and conversion range. The overall copolymerization parameter k_p/k_t^1/2 and the composition of the copolymer formed have been measured as a function of conversion. Theoretical values of the coupled parameter k_p/k_t^1/2 calculated from the implicit penultimate unit model and those of cumulative copolymer composition, determined from the Mayo—Lewis terminal model, have been correlated with those experimentally obtained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1961–1965, 1997     

Cutaneous Photoprotective Activity of a Short‐term Ingestion of High‐Flavanol Cocoa: A Nutritional Intervention Study

In vivo and in vitro studies have shown that prolonged oral administration of flavanol‐rich cocoas extracts have photoprotective effects. The aim of the present study was to assess the photoprotective activity of short‐time administration of a new variety of naturally selected cocoa extract rich in bioactive compounds. We selected a cocoa powder particularly rich in polyphenols, flavanols, caffeine, theobromine and theophylline. We then investigated, in 10 healthy subjects, the photoprotective effects of one week of daily oral administration of two doses of such powder. Phototesting with solar simulated radiation was performed at baseline and after cocoa supplementation. Visual assessment of the minimal erythema dose and spectrophotometric measurement of the “a” parameter were done after 24 h from the irradiation. Oral daily supplementation of 1 g of high‐flavanol cocoa was not effective but a one‐week administration of 4–6 g of cocoa induced a statistically significant increase in the visual erythema threshold and a significant reduction in the “a” parameter. We demonstrated that a new variety of naturally selected cocoa extract, even when administered for a short time, retains a dose‐dependent photoprotective effect. These results are also indicative of the fact that topical sunscreens could be supplemented by a specific diet.     

Simultaneous Determination of Theobromine and Caffeine in Cocoa by Partial Least-Squares Multivariate Spectrophotometric Calibration

Abstract

The use of partial least - squares multivariate spectrophotometric calibration for the simultaneous determination of theobromine and caffeine in cocoa is presented. The results show that these components in a molar ratio of about 6 : 1 in cocoa have been determined simultaneously with standard deviations of about 0.05 and 0.02 for theobromine and caffeine, respectively.     

Melting Properties of Butter Fat and The Consistency of Butter. Effect of modification of cream ripening and fatty acid composition

The cold unspreadable consistency of butter after taking it out of the refrigerator is a rightful objection on behalf of consumers. The possibilities to improve the cold spreadability of butter are: the enrichment with low melting point triglycerides and the application of a good cream-ripening method. In our investigations milk fat fractions of different low melting points and plant oils of low melting points obtained by cold pressing and extraction have been used to change the original fatty acid composition of milk fat. The cream-ripening, the traditional method and the heat-step ripening method, which seemed to be the most effective to our earlier research, have been applied. The consistency of butter was examined by penetration measurements and its thermal characteristics by differential scanning calorimetric (DSC) method. The cold unspreadable consistency of butter can only be improved by the combination of the heat-step cream ripening and enrichment with low melting point triglycerides to get stable consistency at room temperature. The milk fat fraction of melting point below 5°C made the spreadability better but the spreadable consistency of margarine still cannot be attained. Plant oils with melting point below 0°C improved the cold spreadability of butter to a significantly higher degree than the former did. In the case of the same melting point the plant oil obtained by a cold method (pressing) was more effective. There is a close relationship between the consistency of butter and its product characteristics. From DSC curves the cold spreadability and room temperature stability of butter can be directly concluded. This revised version was published online in July 2006 with corrections to the Cover Date.