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Abstract
This paper deals with the physicochemical characterization, including thermal behaviour, by differential scanning calorimetry of
mango seed almond fat (MAF), alone and in mixtures with cocoa butter (CB). Results showed that mango almond seeds contain
about 5.28–11.26% (dw) of fat. The refraction index is 1.466, the saponification index 189.0 and the iodine index 41.76. Fatty acids
found in MAF are oleic, stearic, and palmitic acids (40.81%, 39.07% and 9.29% (w/w), respectively) as well as smaller amounts of
linoleic, with arachidic, behenic, lignoceric, and linolenic acids, among others. Calorimetric analysis showed that MAF crystallizes
between 14.6 and )24.27 °C with a DHc of 56.06 J/g and melts between )17.1 and 53.8 °C, with fusion maxima at 18.54 °C and
40.0 °C for the a and b polymorphic forms. Their fusion enthalpies are 70.12 and 115.7 J/g. The MAF solids content profile is very
similar to that of CB, both in stabilized and non-stabilized samples. The mixing compatibility was analyzed using isosolids curves of
mixtures of different compositions.
Ó 2003 Elsevier Ltd. All rights reserved.
Keywords: Mango almond fat; Cocoa butter; Fat blends; Phase change; Fusion enthalpies; Isosolids diagrams
0960-8524/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2003.07.003
72 J.A. Solıs-Fuentes, M.C. Duran-de-Bazua / Bioresource Technology 92 (2004) 71–78
substitute for traditional saturated fats of animal origin parts removed (skin, pulp and seed and, from seeds, the
as lard, butter, etc. (Bertoli et al., 1995; O’Brien, 1998). almonds) and weighed. Pulp chemical analyses con-
However, new trends are starting to use less processed firmed the ripeness stage. Moisture content (Horwitzs,
fats and oils because of the findings on the role played by 1980), ash content (Horwitzs, 1980), titrable acidity (by
trans fatty acids in some human health aspects (Khosla neutralization), reducing and total sugars content (Lane
and Sundram, 1996; Solıs-Fuentes and Dur an-de-Baz ua, and Eynon method, cited by Southgate, 1991), pH value
2001). These trends open up new perspectives for the use (potentiometer measurement), and tannins content
of natural-origin vegetable fat mixtures as alternative (Folin–Denis method, cited by Horwitzs, 1980) analyses
sources of fatty products with adequate physical char- were performed. Almonds were also characterized by
acteristics, such as melting or fusion point, solid con- measuring their content of moisture, ash, fat, crude
tents, and consistency. These mixtures should also fibre, protein (Horwitzs, 1980), tannins (Folhin–Denis
possess adequate nutritional properties (Williams et al., method, cited by Horwitzs, 1980), and cyanides (alkaline
1997; Kloek et al., 2000; Toro-V azquez et al., 2000). titration).
Mango seed almonds fat (MAF) has been the subject
of several research studies because some of its char- 2.3. Crude fat extraction and further purification
acteristics show resemblance to those of CB (Nara-
shima-Char et al., 1977; Lakshminarayana et al., 1983; Once free of their external protective layer, seed al-
Dhinigra and Kapoor, 1985; MdAlı et al., 1985; MdAli monds of mature fruits were dehydrated in an oven at
and Dimick, 1994; Jimenez-Berm udez et al., 1995; Solıs- 60 °C until they reached a moisture content of about
Fuentes, 1998). However, there are no studies of thermal 10%. Once dried, they were manually crushed and
and phase behaviour of MAF from its different varieties, ground and stored in polyethylene bags at 5 °C until use.
and particularly the physicochemical properties of MAF Fat extraction from dried almond seed meal was per-
from Manila variety are scarce. The Manila mango formed in a Soxhlet apparatus utilizing hexane as sol-
(Mangifera indica, L.) variety is a widely cultivated and vent. A 6-h extraction was carried out for total removal
processed agricultural product in Mexico, due to its of fat. Solvent was removed from the resulting product
particularly delicious and delicate flavour, its lack of under vacuum using a rotavapour. Fat was kept away
fibres, and the smallness of its seed. Considering that from light and air at 5 °C until processing and analysis
Manila mango might be an interesting source of fat, the took place.
aim of this research was: to determine the general
composition of mango, var. Manila, its almond seed 2.4. Fat purification
characteristics, including its fat (MAF) composition and
some specific properties. The MAF thermal and phase MAF of mature fruits was purified using an adapta-
behaviour were studied and its interactions in mixtures tion of the Wesson method (Mehlenbacher, 1970): crude
with cocoa butter (CB) were investigated using differ- fat was dissolved in petroleum ether in a ratio 1:5 (w/v).
ential scanning calorimetry (DSC) and drawing the re- Potassium hydroxide at 14% was added to dissolved fat
sulting isosolids diagrams. (1 ml KOH per gram of dissolved fat) with vigorous
stirring for 3 min. Then 50% ethyl alcohol was added in
a ratio of 1:2.5 (w/v) while stirring and it was left to
2. Methods stand until phase separation. The ether phase contained
the neutral fat. The soap alcohol phase was repeatedly
2.1. Sampling reextracted with ether. Ether extracts were processed in
a rotavapour to recover purified fat. Purified fat was
Mangoes from Mangifera indica, L., Manila variety kept in a freezer (5 °C) away from light until processing
were obtained from a plantation located in the coastal and/or analysis.
mango-producing zone of the State of Veracruz in
Mexico. Two stages of physiological ripeness or matu- 2.5. Physicochemical properties
rity were selected, pre-mature and mature, in order to
compare the fat contents and the physical and chemical MAF refraction index, iodine index, saponification
characteristics of both stages. index, etc. were analyzed using officially approved
techniques (Horwitzs, 1980; Hendrikse et al., 1994).
2.2. Fruits characterization
2.6. Fatty acids pattern
The size and proportions of constitutive parts as well
as the chemical composition for each stage of ripeness Fatty acids present in the MAF were analyzed using
were determined in randomly sampled fruits. Three ex- gas chromatography coupled to mass spectroscopy,
emplars for each maturation stage were taken, their adapting the Bannon et al. (1982) and Hendrikse et al.
J.A. Solıs-Fuentes, M.C. Duran-de-Bazua / Bioresource Technology 92 (2004) 71–78 73
(1994) methodology. Fat was converted into the corre- The temperature programme for the calorimeter was:
sponding methyl esters of its fatty acids. These were
dissolved in heptane, separated by packed column (a) Cooling to )60 °C and heating at 10 °C/min to 90 °C.
chromatography and passed to a mass spectrometer for Registration of the fusion profile.
identification through comparison of the spectra with (b) Heating at 90 °C for 10 min, and cooling at 10 °C/
previously injected standards. min to )60 °C. Registration of the crystallization
profile.
2.7. Fatty acids methylic esters preparation (c) Heating at 90 °C, cooling at )60 °C for 10 min, and
heating at 10 °C/min to 90 °C. Registration of the
The boron trifluoride method (AOAC, 1995) was profile and enthalpy of fusion.
used for fatty acid methyl ester preparation and ap-
proximately 1 ml of the resulting heptane layer was The enthalpies of fusion needed to melt the fat sample
transferred to a glass tube and injected into the chro- crystals, as well as the crystallization enthalpies needed
matograph. Chromatograms and mass spectra for each to solidify them, were calculated using the area below
fatty acid methyl ester were obtained. the integration curve and the thermogram baselines.
Temperature ranges of fusion and crystallization were
2.8. Gas chromatography–mass spectroscopy determined using the thermograms, through the identi-
fication in the curves of the onset and offset temperatures
Fatty acid methyl esters analysis was performed in a for the phase changes.
Hewlett Packard gas chromatograph model 5890 series
II, coupled to a mass spectrometer with an electronic 2.11. Contents of solid fat
ionization detector. The system had an AT Silar capil-
lary column 30 m long, 0.32 mm internal diameter and The amounts of solids in the fats as a function of
0.25 lm film thickness. Compound identification was the temperature were calculated using DSC experiments,
carried out using a data base complemented with in- the Lambelet and Raemy (1983), methodology and the
ternal standards of fatty acids methyl esters. Helium was computational package Origin (Microcal, 1999). Since
the carrier gas with a flow of 0.4 mL/min and a pressure solid fat contents (SFC) depend on temperature these
at 50 °C of 38 kPa. Injector temperature was 250 °C and values may be presented as a function of temperature.
starting oven temperature was 100 °C. The temperature Partial areas of the thermograms were calculated and
programme was 2 min at 100 °C increased by 4 °C/min correlated with solids percentages considering that at
to 180 °C which was maintained for a final time of 5 )60 °C, samples are 100% solids.
min. The mass analyzer range was 10:450 m/z.
2.12. Thermal behaviour of mixtures MAF–CB
2.9. Cocoa butter
A matrix was created with mixtures of MAF and CB
Commercially available pure CB was characterized in in different proportions. Each sample was prepared with
the same way as MAF (iodine index and fatty acids its duplicate and fusion profiles were studied using DSC,
analysis). following the methodology and equipment described
above. Samples were tested before and after stabilization
2.10. Thermal profile (samples that were stored for 15 days at 5 °C). Solid fat
contents were calculated as described above and the
Samples of purified MAF, and purified CB, were fed diagrams of isosolids were produced using the same
to a differential scan calorimeter (Dupont Inst. DSC Origin (Microcal, 1999) programme and the Statistica
910) equipped with a thermal analysis data station programme (StatSoft, 2000).
(Thermal Analysis 2100). The purging gas used was
nitrogen at a flow of 20 mL/min. The instrument was
calibrated with indium (melting point, 156.6 °C; DHf , 3. Results and discussion
28.45 J/g). Samples between 5 and 15 mg were weighed
in a thermobalance (TA), in aluminium SFI capsules The physiological development of the mangoes used
with a precision of ±0.1 mg, which were then hermet- for MAF extraction was characterized using chemical
ically sealed. An empty sealed capsule was used as analysis of the pulps. The average compositions
reference. In order to find the thermal history of the (mean ± standard deviation of triplicate analyses) for
samples, many MAF and CB samples were previously unripe mango fruits pulps were: moisture content,
tempered by heating at 90 °C for 5 min and then cooled 74.57 ± 0.26%; pH values of 3.40 ± 0.23; ash con-
at 24 °C for 24 h. These samples were then stored for tent, 1.11 ± 0.22; total sugar content, 24.50 ± 1.05%;
15 days at 5 °C. titrable acidity, 7.55 ± 0.25; tannins, 0.089 ± 0.008%; and
74 J.A. Solıs-Fuentes, M.C. Duran-de-Bazua / Bioresource Technology 92 (2004) 71–78
Table 1
Heat Flow
1 3 5
Chemical composition of Mexican mango var. Manila almonds
> >Exo
2
Characteristics (%) Unripe fruits Mature fruits Heating
a
Average ±r Average r
Moisture contents 32.98 ± 1.63 19.80 ± 1.17
Ashes contents 1.45 ± 0.012 2.08 ± 0.036
Fat contents 5.28 ± 1.13 9.36 ± 1.87
Crude fibre 1.24 ± 0.06 7.58 ± 0.32 4
Proteins 1.80 ± 0.02 4.62 ± 0.13 -80 -60 -40 -20 0 20 40 60 80 100
Tannins 0.04 ± 0.004 1.60 ± 0.034
Cyanides 0.01 ± 0.0007 0.006 ± 0.001
Temperature, °C
FNEb 90.14 ± 0.86 69.25 ± 6.18
Fig. 1. Differential scanning calorimetry crystallization and fusion
a
Mean ± standard deviation of triplicate analyses. curves for stabilized MAF. Refer to Table 3 for (1, 2, 3, 4 and 5)
b
Free nitrogen extract. transition temperatures.
J.A. Solıs-Fuentes, M.C. Duran-de-Bazua / Bioresource Technology 92 (2004) 71–78 75
Cooling
3 1
MAF
4 1 6
23 CB
Heat Flow
Heat Flow
1 5
<<Endo
>>Exo
4
1 3 5
2 2 5
Heating
4 4
Fig. 2. Differential scanning calorimetry crystallization and fusion Fig. 3. Differential scanning calorimetry fusion curves for MAF and
curves for stabilized CB. Refer to Table 3 for (1, 2, 3, 4 and 5) tran- CB without stabilization. Refer Table 3 for (1, 2, 3, 4, 5, and 6)
sition temperatures. transition temperatures.
ends at )24.27 °C, with a crystallization maximum at for both fats without stabilization and subjected to im-
10.41 °C. A slight ‘‘shoulder’’ is observed at )9.90 °C, mediate heating after solidification with rapid cooling.
that might be assumed to be the solidification of the low Table 3 presents the more representative transition
fusion point fraction, constituted by triacylglycerides temperatures in the thermograms, allowing comparison
with unsaturated fatty acids. The value for DHc for this of the CB with the MAF data.
solidification process was 56.06 J/g. According to Hagemann (1988), vegetable origin
Fig. 2 shows the profile of fusion for the CB, stabi- lipids (fatty acids, acylglycerides, and fats and oils)
lized under the same conditions as MAF, and the CB present polymorphism, and in general, and with more
crystallization profile after being completely melted and frequency, solidify in three different crystalline forms: a,
maintained at 90 °C for 10 min. In this case, the ob- b0 , and b, with correspondingly higher fusion tempera-
served fusion and crystallization profiles are also rela- tures. Polymorph a (lowest fusion point) is generally
tively simple and show a great resemblance with those present after rapid cooling processes from melted fat.
for MAF. Form b0 , with a higher melting or fusion point than the
The CB also presented the two maxima for fusion. previous one, is generated through solidification of fat
The first one corresponds to the low fusion point frac- under certain conditions of temperature or due to
tion, with a maximum temperature of 11.64 °C and the transition from form a. Polymorph b, the most stable
second one corresponds to the higher fusion tempera- crystalline form, is produced from the other two forms
ture triacylglycerides with a maximum point at 36.51 °C. by incubating at slightly higher fusion temperatures
The DHf for the CB analyzed was 128.17 J/g. With re- than for the a form. Polymorphism for CB has been
spect to crystallization, it starts at 12.71 °C with a widely studied (Lutton, 1957; Schlichter-Aronhime and
maximum at 6.38 °C, and a DHc of 56.98 J/g. Garti, 1988; Loisel et al., 1998) and there is still con-
Similarities in the thermal behaviour of MAF and CB troversy with respect to the number and types of
are also evident in Fig. 3 that shows the fusion profiles forms in which it crystallizes. One of the most accepted
Table 3
Transition point temperatures and crystallization and fusion enthalpies for MAF and CB
Sample DH (J/g) Transition temperature (°C)
1 2 3 4 5 6
Crystallization
MAF 56.06 14.64 10.41 )9.90 )24.27
CB 56.98 12.71 6.38 )15.22 )26.17
Fusion
Stabilized MAF 115.72 )17.16 5.32 26.18 40.01 53.84 n.d.
Non-stabilized MAF 70.12 )15.94 )2.31 2.01 10.62 18.54 42.23
Stabilized CB 128.17 )11.02 11.64 22.80 36.51 52.47 n.d.
Non-stabilized CB 80.02 )3.50 8.08 19.70 23.11 40.18 n.d.
n.d.: Not determined.
76 J.A. Solıs-Fuentes, M.C. Duran-de-Bazua / Bioresource Technology 92 (2004) 71–78
30
100 Non-stabilized CB
26
SFC = 5
80
Solid Fat Content
10
Temperature °C
Stabilized CB 22
20
60 18 30
Stabilized MAF 14 50
40 60
10 70
Non-stabilized MAF
20
6 80
0 2
0.0 0.2 0.4 0.6 0.8 1.0
-20 -10 0 10 20 30 40 50 60 70 MAF (Weight Fraction)
Temperature, °C
Fig. 5. Isoline diagram of solid fat content (SFC) for mixtures of
Fig. 4. Solid fat content for stabilized and non-stabilized MAF and MAF and CB in non-stabilized samples.
CB.
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