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Advanced Journal of Chemistry-Section B
Natural Products and Medical Chemistry
Journal homepage: http://www.ajchem-b.com/
Original Research Article
investigation of physicochemical and fatty acid composition of oils
from ripe and unripe blighia sapida fruit
Olaniyi O. Bashir*, Oluwaniyi O. Omolara, Oloruntele O. Ibrahim, Sekoni A. Hauwa
Department of Industrial Chemistry, University of Ilorin, Ilorin, Nigeria
A R T I C L E I N F O A B S T R A C T
Article history
Submitted: 2022-02-28
Revised: 2022-03-21
Accepted: 2022-04-07
Available online: 2022-04-16
Manuscript ID: AJCB-2202-1110
DOI: 10.22034/ajcb.2022.330991.1110
Blighia
sapida
, commonly known as ackee, is an inherent tree
crop of West Africa which is prevalent in tropical and
subtropical environments. Various parts of the ackee tree are
employed in traditional medicine for treatment of several
ailments. However, limited information exists on the health
benefits and composition of the fruit oils, thus the need for
scientific knowledge of the composition, nutritional,
antioxidant, physicochemical parameters, and the other
properties of the fruit oils for its efficient
utilization/developmental purposes. Physicochemical
properties and fatty acid composition of oils from the arils and
seeds of ripe and unripe Blighia sapida (ackee) were quantified
using standard analytical techniques. The specific gravity of the
seed oils ranged between 0.85 - 0.88; saponification value of the
oil of the ripe arils (146.74 ± 0.71) was much higher than those
of the other oils under investigation, while the oil of the unripe
seed had the lowest saponification value (76.10 ± 2.32). The
ripe aril oil had the lowest acid value of 11.20 ± 4.65 mg/g, and
ripe seed oil recorded the highest acid value of 42.09 ± 0.01
mg/g. The other parameters investigated include the ester
value, iodine value, peroxide value, and the % Free Fatty Acid.
The fatty acid composition of the oil of the ripe aril are arachidic
acid (4.9%), gondoic acid (7.76%), oleic acid (31.76%), palmitic
acid (49.20%), palmitoleic acid (1.28%), and stearic acid
(5.00%); while arachidic acid (8,58%), behenic acid (36.28%),
oleic acid (8.75%), palmitic acid (36.05%), and stearic acid
(10.34%) are the fatty acids present in the unripe aril oil. This
study concludes that ackee oils may find usage as industrial
oil.The results confirmed ackee fruit to be a moderately oily
fruit that can be exploited, with proper refining, to produce
edible oil, soap, cosmetics, and the other industrial products.
K E Y W O R D S
Blighia sapida
Physicochemical Parameters
Fatty Acid
Oil
Advanced Journal of Chemistry, Section B, 202
2
,
4
(
1
),
53
-
61
Olaniyi O. Bashir
et. al. /Ad. J. Chem. B, 2022, 4(1), 53-61
54
G R A P H I C A L A B S T R A C T
1. Introduction
Blighia sapida, also known as ackee, is an
inherent tree crop of West Africa and it is also a
member of the sapindacea family predominant in
tropical and subtropical environments. The ripe
arils of the ackee fruit -yellow to cream colored,
are nutty-flavored and edible; ripe seed vary
from deep brown to shiny black, while the unripe
is greenish in color [1]. It is a moderate oil plant,
and the arils are the major component of the
Jamaican national dish, ackee and salt fish.
Although some controversies do exist on the
introduction of ackees to Jamaica, but many
authors have the belief that ackee was brought to
the country in the 18th century via a slave ship [2,
3, 4]. Since then, the fruit has become very
popular among Jamaicans and has been declared
in the Country’s National Fruit. The ripe fruit arils
are either freshly eaten, fried, dried, roasted or
made to soup sauce in some parts of West Africa
[5]. Ackee arils have been reported to have
comparable proximate composition to many
known legumes and oil seeds [1, 6, 7], however
they have little commercial or nutritional
significance in the West African sub-region.
Various parts of the ackee tree have been
reported to be employed in traditional medicine
for the treatment of several ailments and
disorders such as fever, malaria, internal
haemorrhage, dysentery, yellow fever, diabetes,
and constipation in West Africa. The roots, bark,
leaves, pods, and seeds were identified in the
treatment of 22 diseases in Benin [5]. The
consumption of ackee roots bark extract have
also been reported to exerted significant
hypoglycaemic effect on the normoglycemic
albino rats [8]. However, the limited information
exists on the use and benefits of oil components
from ripe and unripe arils and seed. The
substantial scientific knowledge on the
constituents like proximate/nutritional,
physicochemical, and fatty acid composition of
ackee arils and seeds could ensures the
development of more efficient ways to convert
the fruit into useful products with improved
commercial value.
Olaniyi O. Bashir
et. al. /Ad. J. Chem. B, 2022, 4(1), 53-61
55
This study aims to determine the
physicochemical properties of oils extracted from
both the seeds and arils of ripe and unripe Blighia
sapida fruit, compare the oil qualities, and
determine the possible application as industrial
or pharmaceutical base.
2. Materials and Methods
2.1. Sample collection
Blighia sapida fruits were collected from different
locations in Ilorin, Kwara State in North Central
Nigeria.
2.2. Sampling Method
The ripe and unripe fruits were harvested from
the ackee plant into separate bags and were
transported to the laboratory. The ripe fruits are
red-colored fleshy and the fruits have split open
to reveal the seeds and arils. The un-opened
capsules are considered as unripe, regardless of
the red color. The fruit samples were identified in
the Herbarium of the Department of Plant
Biology, University of Ilorin.
2.3. Sample Preparation
The ripe and unripe fruits were cut opened and
each separated into the three components -pod,
aril, and seed-. The pods were discarded, while
the remaining samples (ripe and unripe arils and
seeds) were washed in clean water separately
and oven dried at a temperature not more than
40℃ until there was no further significant
reduction in the weight of the samples. The dried
samples were then pulverized separately with
mortar and pestle, sieved to obtain fine particles,
and kept in separate labeled airtight bottles for
further processing.
2.4. Extraction
The cold extraction method described by Adebiyi
et al. [9] was used. The samples were extracted
with n-hexane in clean, flat-bottomed containers
for 5 days at room temperature with occasional
shaking and stirring. The extracts were filtered
through a fresh cotton plug, and then a Whatman
filter paper and the filtrate concentrated over a
rotary evaporator. Oils of the ripe and unripe
arils and the obtained seeds were stored in
separate clean airtight containers for subsequent
analyses.
2.5. Characterization
2.5.1. Specific Gravity
Equal volume of water and oils were weighed
separately in a clean specific gravity bottle of
weight (W0). The specific gravity of the oil
samples was calculated using the formula (Eq. 1),
[10].
𝑆𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝐺𝑟𝑎𝑣𝑖𝑡𝑦 =
=
(1)
In which,
W0 = Weight of empty specific gravity bottle
W1 = Weight of water + specific gravity bottle
W2 = Weight of test sample + specific gravity
bottle
2.5.2. Acid value
The acid value of each sample was determined by
titrating oil in ethanol - diethyl ether solvent
mixture with 0.1 N sodium hydroxide using
phenolphthalein as indicator [11], until a pink
color was observed which persisted for 15
seconds. Acid value was calculated using Eq. 2.
𝐴𝑐𝑖𝑑 𝑉𝑎𝑙𝑢𝑒 = . × ×
(2)
Where,
N = Normality of NaOH used,
V = Volume (mL) of NaOH used
W = Weight (g) of sample used
Percentage free fatty acid (% FFA) (as oleic)
was determined as shown in Eq.3 by the product
of acid value and (NaOH titration) conversion
factor 0.503 [11].
Thus,
%𝐹𝑟𝑒𝑒 𝐹𝑎𝑡𝑡𝑦 𝐴𝑐𝑖𝑑 = 0.503 × 𝐴𝑐𝑖𝑑 𝑣𝑎𝑙𝑢𝑒 (3)
2.5.3. Ester value
Phenolphthalein indicator was added to 95%
ethanol containing the oil sample, and titrated
against 0.1M ethanolic potassium hydroxide
(KOH) until a pink color was observed. The
mixture was then refluxed for about 1 hour after
which distilled water and phenolphthalein
Olaniyi O. Bashir
et. al. /Ad. J. Chem. B, 2022, 4(1), 53-61
56
indicator were added and the mixture finally
titrated to neutrality indicated by change in color
using 0.5M hydrochloric acid (HCl) [11]. The
ester value was then calculated using the
expression (Eq. 4);
𝐸𝑠𝑡𝑒𝑟 𝑉𝑎𝑙𝑢𝑒 [𝐸] = . ×
(4)
In which,
V is the difference in volume of HCl consumed
by the blank compared to sample titrations
after reflux.
W is the weight of the sample.
2.5.4. Saponification value
2 grams of each oil sample in alcoholic KOH were
heated and refluxed for about an hour, allowed to
cool and then washed using hot neutral ethyl
alcohol. Phenolphthalein indicator was added
before titrating with standard HCl solution. The
saponification value was calculated using the
expression (Eq. 5);
𝑆𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑐𝑎𝑡𝑖𝑜𝑛 𝑉𝑎𝑙𝑢𝑒 = . ×()
(5)
Where,
B= volume in mL of standard HCl required for
the blank.
S= volume in mL of standard HCl required for
the sample.
N= normality of standard solution.
W= weight in gram of the taken oil.
2.5.5. Peroxide value
The method specified by Adeniyi, et al. [12] was
employed. 2 g of oil sample was dissolved in
chloroform, followed by addition of acetic acid,
and freshly prepared saturated potassium iodide
solution. The mixture was stirred, and kept away
from light for about 5 minutes, shaken vigorously
with water, and few drops of starch solution were
added. The liberated iodine was titrated against
0.01 N sodium thiosulfate solution. The
procedure was repeated on the other samples
and blank test was also conducted. The peroxide
value is thus expressed as the milliequivalent of
active oxygen per kg of the sample (Eq. 6).
𝑃𝑒𝑟𝑜𝑥𝑖𝑑𝑒 𝑉𝑎𝑙𝑢𝑒 = (
)× ×
(6)
Where
V0 = volume of the sodium thiosulfate solution
used for blank,
V1 = volume of the thiosulfate solution used for
sample determination,
T = normality of used sodium thiosulfate
solution, and
M = the mass of the test sample in gram.
2.5.6. Iodine Value
The method specified by Yusuf, et al. [12] was
used; 23 mL Wij’s solution was dissolved in
carbon-tetrachloride containing the dissolved oil
sample and allowed to stand for 2 hours in the
dark at 25 °C. 20 mL of 10% KI solution was then
added to the mixture before titrating with 0.2 N
Na2S2O3 using starch solution as the indicator. A
blank determination was also carried out and the
iodine value calculated. Thus (Eq. 7):
𝐼𝑜𝑑𝑖𝑛𝑒 𝑉𝑎𝑙𝑢𝑒 = . ×(
)
(7)
Where,
N = Normality of thiosulfate solution,
V1 = Volume (mL) of used thiosulfate solution in
test sample
V2 = Volume (mL) of used thiosulfate solution in
blank,
W = Weight of sample
2.5.7. Fatty Acid Composition of Ripe and
Unripe Ackee arils and Seeds Oils
20 g of each oil sample was trans-esterified in
methanol for about 3 hours under reflux using
concentrated sulfuric acid as the catalyst [13].
The product was then analyzed with gas
chromatography.
2.6. Data Processing
The results are expressed as mean ± standard
deviation of triplicate trials. SPSS version 16.0
was used for the statistical analysis. One way
analysis of variance (ANOVA) and Duncan’s
multiple range tests were carried out and also
statistical significance of differences were
accepted at the 5% limit (P ≤ 0.05).
3. Results and Discussion
Olaniyi O. Bashir
et. al. /Ad. J. Chem. B, 2022, 4(1), 53-61
57
3.1. Physicochemical Parameters of Ripe
and Unripe Blighia sapida Fruit Arils and Seed
Oils
Acid value is the amount of potassium hydroxide
required to neutralize the acidity of one gram of
oil sample, and it is a measure of the free fatty
acids in the oil [14]. Acid value can be used to
check the level of oxidative deterioration of oil by
enzymatic or chemical oxidation. The lower the
acid value of oil, the fewer the free fatty acids it
contains, and so the better the oil quality. An
increase in the number of free fatty acids present
is an indication of hydrolysis of triglycerides [15].
The acid values obtained for the oils in this study
as indicated in Table 1, are higher than those
earlier reported for almond seed oil (1.68 mg
KOH/g) [16], Plukenetia conophora (11.5 mg
KOH/g) [17], watermelon seed oil (7.09 mg
KOH/g) [18], and bean seed oil (2.77 mg KOH/g
and 2.74 mg KOH/g [19]. They are however lower
than those obtained by Onuekwusi et al. for both
ripe and unripe ackee seed oil (39.49 and 66.09
mg KOH/g). This implies that the ripe and unripe
arils in this study have low acid values, and seed
oils have higher acid values than the aril oils, but
lower than those earlier reported by Onuekwusi
et al . In addition, the acid value of ripe aril oil was
observed to be lower than that of unripe aril oil,
while that of ripe seed oil is much higher than the
oil from the unripe seed. In other words, acid
value of the aril oil decreases as the fruit ripens,
whereas the acid value of the seed oil increases
with ripening. This suggests that on ripening, the
acid contents of the arils translocate to the seed
part of the fruit, which is responsible for the
observed low acid value in ripe aril oil compared
to its unripe form, and the significantly high acid
value of the ripe seed oil compared to the unripe
oil. Consequently, the seed oils with the highest
acid values may be more prone to oxidative
rancidity than the aril oils.
Percentage (%) of free fatty acid is the percentage
of fatty acids in the free form rather than as fatty
acid methyl esters or triglycerides. The free fatty
acid determined above followed the same trend
as the acid value with the ripe arils having the
least value (5.61), and ripe seed having the
highest (21.12) free (unbound) fatty acids. The
lower the acidic content of an oil, the lower the
free fatty acids it contains thereby making it less
exposed to rancidity. Therefore, the ripe aril oil is
least prone to rancidity, followed by the unripe
seed oil, while the ripe seed oil is more
susceptible.
The peroxide value of an oil or fat is a measure of
the extent to which rancidity reactions can occur
or has occurred during storage. That is the
deterioration level of the oil. The double bonds
(degree of unsaturation) of fats and oils play a
significant role in its autoxidation, and peroxide
value estimation is the best test for oxidative
rancidity determination. Highly unsaturated oils
are known to absorb more oxygen and develop
higher peroxide values, and oils with higher
peroxide values are prone to rancidity (off-
flavors and off-odors) [14, 20]. The WHO/FAO
stipulated a permitted maximum peroxide level
of not more than 10 M equivalent of peroxide
oxygen/Kg of oil [14]. The peroxide value of
samples investigated are less than 10 mmol
O2/kg, ranging from 9.01 – 9.34 (mmol O2/kg)
indicating that the oils have low susceptibility to
oxidative rancidity/spoilage at room
temperature and are therefore suitable for
storage. Saponification value represents the
number of milligrams KOH required to saponify 1
g of fat/oil. It is a measure of the average
molecular weight (or chain length) of all the fatty
acids present. If more moles of KOH are required
to saponify N grams of fat/oil, it means the oil
contains more fatty acid (carboxyl) groups and
therefore shorter chain lengths, and lower
average molecular weight of the fatty acids in the
oil. Ripe ackee arils and seed oils have higher
saponification values of 146.74 and 143.68,
respectively than the corresponding unripe aril
and seed oils with values of 137.39, and 76.10,
respectively. The saponification values in this
Olaniyi O. Bashir
et. al. /Ad. J. Chem. B, 2022, 4(1), 53-61
58
study indicates that they have moderate number
of carboxyl functional groups per unit mass of the
fat corresponding to several short chain fatty
acids compared to long chain fatty acids with
relatively lower number of carboxyl groups. The
result indicates that the oils have relatively short
or medium chain lengths, and will therefore
produce more molecules of soap per gram than
oils with lower saponification values. The result
also suggested that as the plant ripen, the long
chain fatty acids breakdown to shorter chain fatty
acids.
Ester Value is the number of milligrams of
potassium hydroxide required to neutralize the
fatty acid esters in a gram of fat, wax or oil, etc.
This is equal to the difference in saponification
value and acid value. The unripe seed oil has the
least ester value (62.10), with the ripe aril oil
having the highest value (135.54) of the samples
under investigation.Iodine value is a measure of
the degree of unsaturation in a fat or oil sample.
It also contributes to the stability of oils to
oxidation [21]. The iodine number is an
indication of the degree of unsaturation (double
bonds) of the fatty acids; these unsaturations
(double bonds) reacts with iodine. Ripe arils oil
has relatively high iodine value of 90.01 ± 0.08.
This implies that it has a much higher degree of
unsaturation compared with the others and this
is in line with the result of GC-MS which
illustrates it to majorly contain compounds like
oleic acid and gondoic acid. This value was
considerably lower in the unripe arils with a
value of 22.81 ± 0.02. According to Essien et al.
[22], oils with iodine value in the range of 115-
150 have higher affinity for oxygen when
exposed to atmospheric oxygen and partially
hardens and can be classified as semi-drying oil.
A non-drying oil is an oil which does not harden
when exposed to air and has an iodine number
less than 115 [23], while a drying oil with iodine
number greater than 150 hardens (through
polymerization) completely. Thus, the oils in this
study (values ranging from 90.01 -7.68 mg I2/g)
belongs to the category of non-drying oils and
may not be suitable as alkyd resins for paint
formulation or used as varnishes. Seed oils have
much lower iodine value compared to the aril oils
of this study, thereby indicating a much lower
degree of unsaturation in the seed oils. However,
the oils may be useful as finishes for certain
appliances when combined with amino resins,
and the oils can also act as plasticizers.
The Specific gravity of a liquid or substance is
symbolic of its comparative miscibility with
water, wax, and the other oils [11]. The results of
the specific gravity of Blighia sapida oil samples
show values between 0.85 – 0.88 kg/dm3 for all
samples which indicates that they are denser
than water, and also that extent of maturation has
no significant effect on the specific gravity/
density of the ackee fruit oil samples.
Table 1. Physicochemical properties of ripe and unripe Ackee arils and seeds oils
Parameters Aril Oil Seed Oil
Ripe Unripe Ripe Unripe
Acid Value (mg KOH/g) 11.20 ± 0.02a 22.42 ± 0.02c 42.09 ± 0.01d 14.00 ± 0.04b
%Free Fatty Acid (mg KOH/g)
5.61 ± 0.02
a
11.30 ± 0.02
c
21.12 ± 0.03
d
7.04 ± 0.03
b
Saponification Value (mgKOH/g) 146.74 ± 0.71c 137.39 ± 1.67b 143.68 ± 3.22c 79.10 ± 2.32a
Iodine Value (mg I
2
/g) 90.01 ± 0.08c 22.81 ± 0.02b 7.61 ± 0.01a 7.68 ± 0.07a
Ester Value (mg KOH/g)
135.54 ± 0.69
d
114.96 ± 1.67
c
101.59 ± 3.55
b
62.10 ± 2.36
a
Peroxide Value (mmol O2/kg) 9.22 ± 0.02c 9.11 ±0.01b 9.01 ± 0.05a 9.34 ± 0.04d
Specific Gravity (kg/dm
3
)
0.88 ± 0.01
b
0.85 ± 0.01
a
0.87 ± 0.0
b
0.88
± 0.01
b
Results are mean ± SD of triplicate determinations. Values in the same row having the same superscripts are not
significantly different at p ≤ 0.05.
Olaniyi O. Bashir
et. al. /Ad. J. Chem. B, 2022, 4(1), 53-61
59
3.2. Fatty acid composition of ripe and
unripe ackee aril oils.
Fatty acid composition of oils from ripe and
unripe Blighia sapida fruit aril is presented in
Table 2. Palmitic acid (C16:0), a saturated fatty
acid, is the main constituent of the ripe aril oil
(49.20%), higher than the 36.05% of the same
fatty acid in the unripe arils oil. Ripe arils oil has
the second major fatty acid (31.76%) as oleic
acid, a monounsaturated omega-9 fatty acid, and
the unripe arils oil contains 36.28% Behenic acid,
a saturated fatty acid [24] which is absent in the
ripe aril oil.
Table 2. Fatty acid composition of Ripe and Unripe Blighia sapida Concentration (%)
Fatty Acid
Ripe Aril Oil
Unripe Aril Oil
Arachidic acid (C20:0)
4.91
8.58
Behenic acid (C22:0)
-
36.28
Gondoic acid (C20:1) 7.76 -
Oleic acid (C18:1) 31.76 8.75
Palmitic acid (C16:0) 49.20 36.05
Palmitoleic a
cid (C16:1)
1.28
-
Stearic acid (C18:0)
5.00
10.34
Total unsaturated fatty acids
59.11
8.75
Total saturated fatty acids 40.89 91.25
Oleic acid is a common monounsaturated fat in
human diet and has been associated with
decreased low-density lipoprotein (LDL)
cholesterol [25]. It may be partly responsible for
the hypotensive (blood pressure reducing)
nature of the ripe arils of ackee [26]. Behenic acid
is a saturated fatty acid which is poorly absorbed
and has a low bioavailability compared to oleic
acid. It is a cholesterol-raising saturated fatty acid
and has a considerably high concentration of
36.28% in the unripe aril oil, but it is totally
absent in the ripe arils oil.
Palmitic acid is the major fatty acid in the aril oil.
It is a saturated fatty acid which makes up about
20–30% of the total fatty acids in the human
body. Although it is presumed to have some
detrimental health effects because it is saturated,
nevertheless it has several positive and
important physiological activities. An optimal
intake of palmitic acid in a certain ratio with
unsaturated fatty acids, especially
polyunsaturated fatty acids (PUFAs) of both n-6
and n-3 families, and absence of other factors
such as positive energy balance, the excessive
intake of carbohydrates (in particular mono and
disaccharides), and a sedentary lifestyle is crucial
in order to maintain membrane phospholipids
balance [27].
The other fatty acids present in the ripe and
unripe aril oils include arachidic acid (4.91% and
8.58%), gondoic acid and palmitoleic acid which
are unsaturated fatty acids present only in the
ripe aril oil at relatively small quantities of 7.76%
and 1.28%, respectively. Stearic acid, a saturated
fatty acid is present in both the ripe and unripe
aril oils at values of 5.00% and 10.34%,
respectively.
4. Conclusion
The results of this study have indicated that the
oil from the arils of B. Sapida have low
susceptibility to oxidative rancidity/spoilage at
room temperature, thereby could be stored
without deteriorating for a long period and is also
suitable for consumption. The high saponification
value also suggests suitability for self-
emulsification process. Findings also revealed
that the ripe and unripe aril oils contain a right
balance of saturated and unsaturated fatty acids
Olaniyi O. Bashir
et. al. /Ad. J. Chem. B, 2022, 4(1), 53-61
60
which are essential for energy, the correct
development of young organisms, maintenance
of good health by humans, hormone production,
and cellular membranes and for organ padding.
The work also concludes that ackee aril oils could
be exploited with proper refining to produce
edible oil as well as for soap production and the
other industrial products. Exploring for the
presence of bioactive components can also make
it as having desired usage in pharmaceutical
industries.
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HOW TO CITE THIS ARTICLE
Olaniyi O. Bashir, Oluwaniyi O. Omolara, Oloruntele O. Ibrahim, Sekoni A. Hauwa, Investigation of physicochemical
and fatty acid composition of oils from ripe and unripe Blighia sapida fruit, Ad. J. Chem. B, 4 (2022) 53-61.
DOI: 10.22034/ajcb.2022.330991.1110
URL: http://www.ajchem-b.com/article_148288.html
