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Industrial Crops and Products 33 (2011) 3034

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Industrial Crops and Products
j our nal homepage: www. el sevi er . com/ l ocat e/ i ndcr op
Characteristics, chemical composition and utilisation of Albizia julibrissin seed oil
I. Nehdi

King Saud University, College of Science, Chemistry Department, Riyadh 1145, Saudi Arabia
a r t i c l e i n f o
Article history:
Received 29 June 2010
Received in revised form 17 August 2010
Accepted 20 August 2010
Keywords:
Albizia julibrissin
Seed oil
Physicochemical properties
Fatty acids
Triacylglycerols
DSC
a b s t r a c t
The physicochemical characteristics, fatty acid and triacylglycerol compositions, DSC prole and UV/vis
spectrum of oil extracted from Albizia julibrissin seeds were determined in this study. The oil content
and the moisture of the seeds were 10.50% and 1.56%. The free fatty acid, the peroxide value, the p-
anisidine value, the saponication value, the iodine value were 2.54%, 6.61mequiv. O
2
/kg of oil, 1.98,
190.63 (mg KOH/g) and 111.33 (g/100g of oil), respectively. The specic extinction coefcients K
232
, K
268
were 7.55 and 0.96, respectively. Linoleic acid (C
18:2
, 58.58%), palmitic acid (C
16
, 13.86%) and oleic acid
(C
18:1
, 10.47%) were the dominant fatty acids in the A. julibrissin seed oil. LLL (36.87%), OLL (21.62%), PLL
(16.69%) and PLO+SLL (8.59%) were the abundant triacylglycerol representing>83% of the seed oil (L:
linoleic, O: oleic, P: palmitic, S: stearic). The DSC melting curves reveal that: melting point =14.70

C and
melting enthalpy=54.34J/g. A. julibrissin seed oil showed some absorbance in the UV-B and UV-C ranges.
The results of the present analytical study show that A. julibrissin is a promising oilseed crop, which can
be used for making soap, hair shampoo and UV protectors. Furthermore, the high level of unsaturated
fatty acids makes it desirable in terms of nutrition.
2010 Elsevier B.V. All rights reserved.
1. Introduction
The species Albizia julibrissin, commonly named mimosa,
powder-puff tree, silk tree, are widely distributed in Asia, Africa,
Australia, and tropical and subtropical America (Zheng et al.,
2004; Kim et al., 2007). It is native to Asia from Iran to Japan
(Cheatham et al., 1996). The genus Albizia (also Albizzia) belonging
to Fabaceae/Leguminosae family (Mimosoideae subfamily), consists
of approximately 150 species (Wang et al., 2006). Most species
are deciduous woody trees and shrubs. They are easily identied
by their bipinnately compound leaves. Its wood can be used for
building and furniture-making. The young leaves are edible (Zheng
et al., 2004). A. julibrissin is an umbrella-shaped tree growing to
6m tall (Lau et al., 2007), with a broad crown of level or arching
branches. It resprouts quickly if cut or top-killed, and the A. julib-
rissin bark is dark greenish grey in colour and striped vertically as it
gets older. The leaves are bipinnate, 2045cm long and 1225cm
broad, divided into 412pairs of pinnae, each with 1030 pairs of
leaets; the leaets are oblong, 612mm long and 14mm broad.
From June to July, a head inorescence of attractive pink owers is
produced at the top of the branch (Zheng et al., 2004). The sweetly
scentedowers areagoodnectar sourcefor honeybees. A. julibrissin
fruit consists of at pods withbulgingseeds, eachpod818cmlong,
1.52.5cm wide and can be seen from June to February. Typically

Corresponding author. Tel.: +966 14697118; fax: +966 4675992.


E-mail address: inahdi@ksu.edu.sa.
510oval-shapedseeds, about 1.25inlength, are producedper pod.
Seeds and seed pods may be dispersed by wind, gravity and water.
Becauseof its graceful owers andumbrella-likecanopy, A. julib-
rissin has been widely planted along roadways or in gardens for
ornamental purposes. It is also grown in sandy areas to prevent
erosion.
The bark and owers of the A. julibrissin tree are used in China
as medicine (Lau et al., 2007). Bark extract is a sedative drug and
an anti-inammatory for treating swelling and pain of the lungs,
skin ulcers, wounds, bruises, abscesses, boils, haemorrhoids and
fractures, and has displayed cytotoxic activity (Higuchi et al., 1992;
Ikeda et al., 1997; Pharmacopoeia, 2005). Asians administered A.
julibrissin bark extract to patients to treat insomnia, diuresis, sthe-
nia, and confusion (Zhu, 1998). The owers have been commonly
used to treat anxiety, depression and insomnia (Kang et al., 2007).
The seeds are a source of oil (Wang et al., 2006) and furthermore
they are used as a food for livestock and wildlife. Similarly, the
seeds of the tree A. julibrissin have been shown to possess prote-
olytic enzymes which clotted milk readily, without developing any
bitterness in cheese after 3 months of ripening (Otani et al., 1991).
A. julibrissin is one of several energy crops being tested in
the Auburn University energy crop research program, showing an
annual forage yield of 4.5 dry tons acre
1
(10.7Mgha
1
year
1
)
from four harvests per year, and an average total biomass yield of
37.3Mgha
1
year
1
fromone harvest per year over a 4-year period
(Sladden et al., 1992).
To our knowledge, until now a physicochemical characteriza-
tion of the oil produced from the seeds of A. julibrissin has not
0926-6690/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2010.08.004
I. Nehdi / Industrial Crops and Products 33 (2011) 3034 31
been reported. This investigation was undertaken to determine the
physicochemical properties, UV/vis spectra, fatty acid, triacylglyc-
erol and thermal proles of seed oil extracted from A. julibrissin
grown in Tunisia, and to compare these results with those of the
common soybean oil which is the most imported and consumed oil
in Tunisia. This work also reports the possible uses of this new A.
julibrissin seed oil and it alternative of soybean oil.
2. Materials and methods
2.1. Seed material
Mature pods of A. julibrissin were collected in February 2007
from two trees from Sidi thabet city (Tunisia). These trees are
located in: latitude 48

24

N; longitude 13

74

E; altitude: 17m. The


seeds were directly isolated and then hand-picked to eliminate
damagedones. The selectedseeds were oven-driedat 60

Cfor 24h.
The dried seeds were milled in Basic IKA Werke Mill (MF10) then
sieved using a 1mm mesh sieve and stored at 15

C until analy-
ses. Crude soybean oil was purchased from an oil renery located
in Tunis (ETS Abdelmoula).
2.2. Lipid extraction
Oil was extracted fromseeds using hexane. The ground dried A.
julibrissin seeds (40g) were placed into a cellulose paper cone and
extracted with 400ml hexane using a soxhlet extraction apparatus
for 8h. The solvent was removed via a rotary vacuumdistillation at
4050

C ushing with nitrogen to blanket the oil during storage.


The residue was weighedandstoredat 20

Cuntil it was analyzed.


The weight of the oil extracted from 40g of the seed powder was
determined to calculate the lipid content. The result was expressed
as the lipid percentage in the dry seed powder.
2.3. Analytical methods
Analysis was carried out in triplicate. The values of differ-
ent parameters were expressed as the meanstandard deviation
( x S.D.).
2.3.1. Moisture
Moisture of the seeds was determined according to the AOAC
Ofcial Method 930.15 (AOAC, 1990).
2.3.2. Acid value and acidity (% free fatty acids)
The acid value and acidity of seed oil was determined according
to the standard (ISO 660, 1996). Acidity was calculated using oleic
acid factor.
2.3.3. Iodine value
The iodine value was determined according to the standard (ISO
3961, 1996).
2.3.4. Saponication value
The saponication value was determined according to the stan-
dard (ISO 3657, 2002).
2.3.5. Peroxide value
The peroxide value was determined according to the standard
(ISO 3960, 2001).
2.3.6. Spectroscopic indices (K
232
, K
268
), UV/vis spectra
The spectroscopic indices, K
232
and K
268
, in the UV region,
were determined according to the standard (ISO 3656, 2002) and
the oil was diluted with isooctane. Three spectra (200290nm,
290400nm, and 400800nm) of oil solutions (0.1, 1, and 10%, v/v)
in hexane were measured with a spectrophotometer (JASCOV-530,
WITEG Labortechnik., Gmbh).
2.3.7. Anisidine value
The anisidine value was determined according to the standard
(ISO 6885, 2006).
2.3.8. Thermal characteristics (DSC prole)
The thermal characteristics of seed oil were measured by
using a differential scanning calorimeter (DSC-131, SETARAM,
France). A ow of nitrogen gas (1.5ml/min) was used in
the cell cooled by helium (1.5ml/min) in a refrigerated cool-
ing system. The instrument was calibrated for temperature
and heat ow with mercury (melting point, m.p. =38.834

C,
H=11.469J/g), tin (m.p. =231.928

C, H=60.22J/g), indium
(melting point, m.p. =156.598

C, H=28.5J/g) and lead (melting


point, m.p. =327.45

C, H=24.72J/g). The oil samples (45mg)


were weighed in open solid fat index (SFI) aluminum pans (No.
S08/HBB37408, SETARAM) with an empty pan used as a refer-
ence. The sample and reference pans were then placed inside the
calorimeter and kept at 70

C for 2min. The temperature was


increased from70 to 70

C at a rate of 5

C/min. The samples were


then kept at 70

C for 1min, and then decreased again, at the same


rate, down to 70

C. The scans were performed at 5

C/min.
2.3.9. Fatty acid composition
The fatty acid methyl ester (FAME) composition was deter-
mined by converting the oil to fatty acid methyl esters by adding
1ml of n-hexane to 40mg of oil followed by 200l of sodium
methoxide (2M). The mixture is heated in the bath at 50

C for few
seconds followed by adding 200l HCl (2N). The top layer (1l)
was injected into a GC (Agilent 6890N, California, USA) equipped
with a ame ionization detector (FID) and a polar capillary col-
umn(HP-Innowax polyethylene glycol, 0.25mminternal diameter,
30m length and 0.25m lm in thickness) to obtain individual
peaks of fatty acid methyl esters. The detector temperature was
275

C and the column temperature was 150

C held for 1min


and increased at the rate of 15

C/min to 200

C and the rate of


2

C/min to 250

C and held for 4min. The run time was 45min.


The fatty acid methyl esters peaks were identied comparing their
retention times with individual standard FAME (approximately
99% pure purchased from Supelco, USA) of lauric (C
12:0
), myris-
tic (C
14:0
), palmitic (C
16:0
), palmitoleic (C
16:1
), stearic (C
18:0
), oleic
(C
18:1
), linoleic (C
18:2
), linolenic (C
18:3
), arachidic (C
20:0
), eicosenoic
(C
20:1
), behenic (C
22:0
), lignoceric (C
24:0
) acids and analysed with
the Agilent Technologies Chemstation A09.01 Software. The rela-
tive percentage of the fatty acid was calculated on the basis of the
peak area of a fatty acid species to the total peak area of all the fatty
acids in the oil sample. Fatty acid methyl esters peak identication
was conrmed by GCMS (NIST 2002 database) operating under
similar conditions as used for the GCFID.
2.3.10. Triacylglycerol composition
The triacylglycerols (TAGs) prole was obtained by a reverse
phase high performance liquid chromatography (HPLC) (Agilent
1100, CA, USA) equippedwitha G1354 quaternary pump, a G1313A
standardauto sampler, anda G1362Arefractive index detector. The
chromatogram was carried out using Agilent Technology Chem-
station software. The TAGs were separated using a commercially
packed Hypersil ODS column (125mm4mm) with a particle size
of 3m and were eluted from the column with a mixture of ace-
tonitrile/acetone (65/35) at a ow rate of 0.5ml/min; the TAG was
detected with a refractive index detector. Ten microliters of 0.05g
oil dilutedin1ml (chloroform/acetone 50/50, v/v) was injectedinto
the HPLC. The total run time was 45min. Due to the limitation of
commercially available TAGs standard; the identied TAGs of A.
32 I. Nehdi / Industrial Crops and Products 33 (2011) 3034
Table 1
Comparison of physico-chemical properties of A. julibrissin seed oil with those of
soybean oil.
Parameter Albizia julibrissin Soybean
Acid value 5.080.11 1.720.08
Free fatty acid (as oleic %) 2.540.11 0.860.08
Peroxide value (mequiv. O
2
/kg) 6.610.18 1.520.05
Saponication value (mg KOH/g) 190.630.73 179.450.68
Iodine number (g/100g oil) 111.331.32 122.560.98
E
232
7.550.05 2.780.03
E
270
0.960.03 0.730.02
p-Anisidine value 1.980.11 2.480.13
Refractive index (20

C) 1.4710.002 1.4770.002
State at ambient temperature Liquid Liquid
Colour Yellow Dark yellow
Phosphorus, mg/kg 35.430.93 173.671.63
julibrissin seed oil were concluded by comparing the retention time
of standardTAGs peak andthe retentiontime of other oils (ax seed
oil, olive oil, corn oil and sunower oil) chromatographs obtained
under similar analytical conditions.
3. Results and discussion
3.1. The physicochemical properties of seed oil
Seeds of A. julibrissin contained 10.50% of oil (dry weight basis)
and 1.56% of moisture. This seed oil content is comparable with
those of other seed oils such as Phoenix canariensis (10.36%) (Nehdi
et al., in press), Spanish broom (10.50%) (Cerchiara et al., 2010),
raspberry (10.70%) (Oomah et al., 2000) and prickly pear (10.90%)
(Ennouri et al., 2005).
Table 1 reports the comparison of physicochemicals properties
of A. julibrissin seed oil with those of soybean oil. The free fatty acid
content of A. julibrissin seed oil (2.54%) is higher than of soybean
oil (0.86%) indicating that some hydrolytic reactions occur during
the extraction (Ku and Mun, 2008). The oxidative state of oils is
determined using the peroxide value, anisidine value and specic
extinctions K
232
and K
268
. The peroxide value of A. julibrissin seed
oil (6.61mequiv. O
2
/kg of oil) is higher than that of soybean oil
(1.52mequiv. O
2
/kg of oil) indicating the presence of some quantity
of hydroperoxide in A. julibrissin seed oil. This oil can be stored for
a long time without deterioration, since oils become rancid when
the peroxide value ranges from 20 to 40mequiv. O
2
/kg of oil. The
phosphorus content of A. julibrissin seed oil is 35.43ppm, lower
than that of soybean oil (173.67ppm), showing that the quantity
of phospholipids in A. julibrissin seed oil is low. The specic extinc-
tion coefcient at 232nm(K
232
) is related to the degree of primary
oxidation of the oil and thus directly correlated to the amount of
hydroperoxide (Maskan and Bagci, 2003; Ku and Mun, 2008). K
232
is also an indicator of polyunsaturated FA conjugation, whereas
K
268
and K
270
are related to the secondary oxidation products (-
unsaturated ketone, -diketone) (Karleskind, 1992). The relatively
highvalue of K
232
(7.55) of A. julibrissinseedoil conrms that this oil
is muchoxidizedthansoybeanoil. The lowvalue of K
268
(0.96) indi-
cates that A. julibrissin seed oil contains a lowquantity of secondary
oxidation products. The low anisidine values show that the both
oils contain a weak amount of -unsaturated aldehyde compounds
(Karleskind, 1992).
The saponicationvalue of A. julibrissinseedoil (190.63) is lower
than that of soybean (179.45) but similar to that of other oils such
as linseed oil (190.86), sunower oil (188.98) and olive oil (191.93)
(Cerchiara et al., 2010). As reported by Akbar et al. (2009), high
saponication value indicates that oils are normal triglycerides and
very useful in production of liquid soap and shampoo industries.
Therefore, the value obtained for A. julibrissin seed oil in this study
Table 2
Comparison of fatty acid compositions (%) of A. julibrissin seed oil with those of
soybean oil.
Fatty acid A. julibrissin Soybean
Saturated
C
8:0
0.110.03 nd
C
10:0
0.140.04 nd
C
12:0
0.100.02 0.110.03
C
14:0
0.090.01 0.120.03
C
15:0
0.130.01 nd
C
16:0
13.860.19 15.650.03
C
17:0
nd 0.140.03
C
18:0
4.260.07 4.980.23
C
20:0
2.180.04 0.550.07
C
22:0
0.530.03 0.340.04
C24:0
2.620.02 nd
C
25:0
0.210.01 nd
C
26:0
1.260.02 nd
Monoinsaturated
C
14:1
nd 0.090.01
C
15:1
0.110.02 nd
C
16:1
0.440.02 0.120.03
C
17:1
0.120.04 0.090.02
C
18:1
10.470.42 20.980.23
C
20:1
0.300.06 0.320.06
C
22:1
nd 0.380.08
C
24:1
nd 0.130.03
Polyinsaturated
C
18:2
58.580.71 50.170.83
C
18:3
3.350.09 8.180.53
C
20:2
0.290.05 0.390.09
C
20:4
1.570.06 0.120.04
SAFA 25.13 21.89
MUFA 11.34 22.11
PUFA 63.79 58.86
U/S 2.96 3.69
SAFA: saturated fatty acids; MUFA: monounsaturated fatty acids; PUFA: polyunsat-
urated fatty acid.
shows that it has high potency for use in the production of liquid
soap and shampoos.
The relatively low iodine value (111.33) in A. julibrissin seed oil
compared to soybean oil (122.56) is indicative of the presence of
a lower unsaturated bonds number. A. julibrissin seed oil can be
grouped as a semi-drying oils. Among physical properties, refrac-
tive index of oils is studied: A. julibrissin seed oil shows the lowest
value of refractive index (1.471), indicating that its degree of unsat-
uration is lower than that of soybean oil (Fatouh et al., 2005). The
fatty acid composition (Table 1) conrms this result.
Table 3
Comparison of triacylglycerol compositions (%) of A. julibrissin seed oil with those
of soybean oil.
Triacylglycerol ECN A. julibrissin Soybean
LnLnLn 36 1.35 0.50
LLnLn 38 1.35 1.33
LLLn 40 2.48 6.84
OLnLn 40 0.54 0.25
LLL 42 36.87 20.67
LLnP 42 0.63 3.58
OLL 44 21.62 15.88
PLL 44 16.69 15.27
OOLn+POLn 44 0.45 1.97
OOL 46 3.25 10.20
PLO+SLL 46 8.59 11.12
PPL 46 1.31 1.84
OOO+SLO 48 0.45 2.37
POO+PLS 48 2.48 5.21
POP 48 1.58 1.51
SOO 50 0.11 0.74
POS 50 0.45 0.63
La: lauric; M: myristic; P: palmitic; S: stearic; O: oleic; L: linoleic; G: gondoic; ECN:
equivalent carbon number.
I. Nehdi / Industrial Crops and Products 33 (2011) 3034 33
Fig. 1. DSC proles of Albizia julibrissim seed oil and soybean oil.
3.2. Fatty acid and triacylglycerols (TAGs) composition
The fatty acid composition is presented in Table 2. Linoleic, oleic
and palmitic acids are the most abundant unsaturated and satu-
rated fatty acids of A. julibrissin seed and soybean oil. Linoleic acid
(C
18:2
, 58.58%), palmitic acid (C
16
, 13.86%) and oleic acid (C
18:1
,
10.47%) together compose about 84% of the total fatty acids of
A. julibrissin seed oil. Linolenic acid content of soybean (8.18%) is
higher than that of A. julibrissin seed oil (3.35%).
A. julibrissin seed oil was characterised by a polyunsatu-
rated/saturated (P/S) ratio of 2.96, inferior to that of soybean oil
(3.69). The values of these ratios are in correlation with those of
refractive index. A high ratio of P/S is regarded favourable for the
reduction of serumcholesterol and atherosclerosis and prevention
of heart diseases (Oomah et al., 2002).
The total unsaturated fatty acid of A. julibrissin seed oil is 75.11%.
The unsaturated fatty acids can inuence the physical proper-
ties of the membrane such as uidity and permeability (Nasri et
al., 2005). Oleic acid is very important in nervous cell construc-
tion. It has fundamental role in cardiovascular diseases prevention
(Nasri et al., 2005). A. julibrissin seed oil and soybean oil are rich in
polyunsaturated fatty acid (58.86% and 63.79%). Linoleic fatty acid
is indispensable for the healthy growth of human skin (Bruckert,
2001). The fatty acid composition of A. julibrissin seed oil makes
it desirable in terms of nutrition and it may be used as edible oil.
However, the safety of this oil must be tested before use for human
nutrition.
The distribution of triacylglycerols (TAGs), with equivalent
carbon number (ECN) is given in Table 3. LLL, OLL and PLL triacyl-
glycerols are the most triacylglycerols of A. julibrissin seed oil and
soybean oil. It reects a close relationship between the fatty acids
and triacylglycerol content of the oils. TAGs with ECN44, TAGs ECN
42 and TAGs ECN 46 were dominant for the both oils.
3.3. Thermal prole
DSCprovides informationonthe excess specic heat over a wide
range of temperatures (Gloria and Aguilera, 1998). Any endother-
mic or exothermic event is registered as a peak in the chart, and its
area is proportional to the enthalpy gained or lost, respectively. A.
julibrissinseedoil andsoybeanoil showedthe same melting prole.
The thermograms of the oils seem to correspond to one triglyc-
eride (Fig. 1). A. julibrissin seed oil exhibited a single peak having
the following characteristics: melting temperature (14.70

C) and
melting enthalpy (54.34J/g) while the characteristics of the peak
of soybean oil are: melting temperature (17.82

C) and melting
enthalpy (63.44J/g). The difference between the melting tempera-
ture is due to the fact that soybean oil is more unsaturated than A.
julibrissin seed oil.
3.4. UV/vis spectra
The strong absorbance (2.613.19) in the 418470nm range
(Fig. 2) indicates the presence of an important amount of
Fig. 2. Ultra violet/vis spectra of Albizia julibrissin seed oil and soybean oil
(gure derived from scans (=200290nm) of oil diluted 1:1000; from scans
(=290400nm) of oil diluted 1:100 and fromscans (=400800nm) of oil diluted
1:10, all in hexane.
34 I. Nehdi / Industrial Crops and Products 33 (2011) 3034
carotenoids which is responsible for the dark yellow colour of
the soybean oil. A. julibrissin seed oil shows a weak absorbance
(0.450.57) in this range which is in agreement with its yel-
low colour. A. julibrissin seed oil shows strong absorbance in the
UV-B (290320nm) and UV-A (320400nm) range. In the UV-C
(100290nm) soybean oil shows more absorbance than A. julib-
rissin seed oil. Thus, A. julibrissin seed oil can shield against UV-B
and UV-A radiations responsible for most cellular damage, and it
may be used in formulation of UV protectors.
4. Conclusion
This preliminary study shows that the A. julibrissin is a promis-
ing seedoil crop. The characterizationof A. julibrissin seedoil shows
that it could be successfully used for making soap, hair sham-
poo and in formulation of UV protectors in cosmetic. Furthermore,
the high level of polyunsaturated fatty acids makes it desirable in
terms of nutrition, and might be an acceptable substitute for highly
polyunsaturated oils such soybean oil in diets.
This newA. julibrissin crop can potentially create newrural jobs
when used for industrial products.
Acknowledgments
The author thanks Prof. Hedi Zarrouk, the previous Director
of National Institute of Research and Physico-Chemical analysis
(INRAP), Sidi Thabet, Tunisia for his invaluable collaboration in the
development of this work. The author gratefully acknowledges Ms.
Samia Omri for practical assistance. I wish to thank my colleague
Prof. Mutassim Ibrahim Khalil for his assistance in the English of
this manuscript.
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