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Physico-chemical, Thermal and Oxidative Properties of Wild

Chironji (Buchanania lanzan Spreng.) Kernel Oil


Sumedha N Sahu, Swapnil G Jaiswal and S N Naik*
Center for Rural Development and Technology, Indian Institute of Technology,
Hauz Khas, New Delhi

ABSTRACT in diverse ways to treat a variety of health issues1.


The present investigation aims to evaluate the Researchers have found that the addition of chironji
quality and stability of chironji seed oil by exploring biomaterial as an emulsifier with sunflower oil proved
its physicochemical properties, composition, oxidative to be a good emulsion for drug delivery2. Scientific
stability, thermal behaviour and also promote this studies such as. antioxidant, anti-inflammatory,
underutilized fruit scientifically in order to increase cytotoxic, analgesic, adaptogenic, wound healing,
market for chironji oil which will create revenue for anti-diarrhoeal activities of chironji plant (root, bark,
the tribal peoples of India. Experimental findings seed, flower and leaf) have been studied by some
of this study shows that yield of oil obtained after researchers in recent past3-8. The fruits of the plant
solvent extraction is more (56%). Fatty acid profile constitute valuable foodstuff for humans and are a
shows that oleic acid was the principal fatty acid. commonly used ingredient in the preparation of many
Chironji oil contains 41.79% saturated fatty acids Indian sweets as well as aromatic items. Chironji is
and 58.21% unsaturated fatty acids. Viscosity of also used as a dressing material in many deserts
chironji oil (28.6 centipoise) was found to be lower and sweet food items (Kheer, Halwa, Basundi etc.).
than almond oil as reported in the previous literature. Chironji plants are facing severe threat of genetic
Other physicochemical properties namely acid erosion as a result of large scale urbanization and
value, saponification value, iodine value, percent developmental activities in tribal inhabited areas9.
unsaponifiable matter were also studied. Oxidative In order to trigger research in the area of genetic
stability study and thermal behaviour of oil proves diversity and conservation efforts of chironji, 72 genetic
chironji oil is stable. Chironji oil can be used as resources of chironji and their morphometric data for
an additive or blending agent for lipid based food fruit, stone and kernel have been reported earlier10.
materials. This study indicates its multi-dimensional
The seed kernels of chironji are eaten raw or
prospects such as the nutritional characteristics and
roasted which form a substitute for almond and the
by and large its socio-economic values for the under-
kernel yields a light yellow, sweet oil with a mild,
privileged Indian tribal class people as a means of
pleasant aroma. Oil content of chironji has been
sustenance.
reported to be 35-50%1. Earlier reports on fatty acid
KEYWORDS: Buchanania lanzan, Physico-chemical composition and total lipid composition of chironji
properties, thermal stability, viscosity, fatty acid seed oil revealed that this oil has high oleic acid
composition. content (55-60%) and found to be stable component
for formulations of delayed action tablets11-12. Oil and
INTRODUCTION
fats are essential ingredients in the formulation and
Buchhnania lanzan (Chironji) is an evergreen moderate processing of foods in nutritional product. The oxidative
sized tree belonging to family Anacardiaceae, and thermal stability of fats and oils play an important
commonly found throughout the greater part of India role in determining the quality of lipid containing
in dry deciduous forests. Chronji plant is one of products. According to some researchers, thermal
the important wild plants having numerous benefifial analysis is an alternative method of measuring oil
nutrients and is an important element in Ayurvedic stability13-14. There are several reports in the medicinal
medical application. All the parts of chironji plant such and nutritional potential of this plant are available but
as fruit, roots, leaves, seeds, gum and oil are used as of now no such data is available on the oxidative
*
stability and thermal behaviour of chironji seed oil
To whom correspondence should be addressed which will incorporate positive input in the field of
E-mail: naiksn@gmail.com antioxidant study by blending them with other oils.

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Previous study proved that high oleic acid content of Fatty acid profile by GC and GC-MS: Fatty acid methyl
chironji oil shows high stability by keeping their shelf esters (FAME) of chironji oil were prepared according
life longer12. to the method described by Hammond17. FAME was
analysed using Nucon-5765 (Nucon Engineers, Delhi,
This study of this plant and plant products have
India) gas chromatograph with flame ionization detector
reported presence of substantial elements with potent
(FID). Experimental parameters were maintained as per
pharmacological and nutritional importance. Though the
the reported conditions18. GC-MS analysis of chironji oil
medicinal and nutritional prospective of chironji seed
esters was done in Shimadzu QP-2010 plus with TD
oil have been well studied, the oxidative and thermal
stability of seed oil and its potential use as antioxidant 20, Kyoto, Japan (Advanced Instrumentation Research
rich source and blending agent with other edible oils Facility Laboratory, J.N.U Delhi, India). The operational
are yet to be studied. In the present investigations, we conditions for GC-MS analysis were: Column Rtx®-5Ms
aimed to evaluate the quality and stability of chironji (30m x 0.25 mm x 0.1μm of film thickness); Carrier
seed oil by exploring its physicochemical properties, gas – helium (1 ml/min) and an injection volume of
composition, oxidative stability and thermal behaviour 2μl (split ratio of 10.0); Injector temperature 250oC;
which will be helpful for further studies in the direction Oven temperature was programme from 140oC (5
of food and pharmaceutical purpose. min hold time) with an increase of 4oC/min to 280oC
(15 min hold time); Ion source temperature 220oC,
MATERIAL AND METHODS Interface temperature 260oC.
Materials
Thermal stability test: The TGA was done using
Plant material and extraction: Chironji fruits were
TA-Q600 (USA) instrument to identify the thermal
collected from the tribal district of western Odisha
degradation patterns of oil. Samples of 15 to 20 mg
(Bargarh), a south eastern part of India and soaked
were heated from room temperature to 800oС with a
overnight in water to remove pulp and foreign materials.
ramping speed of 10oС/min under inert atmosphere.
After removal of outer covering of the nut, they are kept
The DSC analysis was done by a TA- Q600 (USA)
in oven to remove further moisture. Kernels from the
instrument. Samples of 8 to 10 mg were equilibrated
dried nuts were separated by stone hammering. About
and then heated at a ramping rate of 10oС /min to
50 g of kernel was crushed and subjected to solvent
400oС and cooling rate of 20oС /min was applied and
extraction by using hexane as a solvent. Solvent was
then heated again at the same ramping rate 10oС /
removed in rotary evaporator and concentrated oil
min to 400oС19.
sample was weighed to calculate final yield.
Oxidative stability test: Oxidative stability test was
Methods
carried out in the Rancimat 743 instrument to know
Proximate analysis: Elemental analysis of chironji kernel the induction period (IP) of chironji oil. Experimental
powder (5 mg) was carried out using the Elemental conditions like temperature (110-130oC) and air flow
Vario ELIII (Germany) in order to quantify carbon, rate (20 L/h) was set according to the conditions
hydrogen and nitrogen percentage. Protein content of suggested by Jaiswal20. Amount of oil sample taken
the chironji kernel was determined by the multiplication in each reaction vessel to carry out experiment was
of percent nitrogen with universal conversion factor 3g. All the experiments were carried out in triplicates
6.2515. Anthrone method was used to determine and IP was reported in hours (hr).
the carbohydrate content. Other physicochemical
properties such as ash content, moisture content, Statistical analysis: Experimental data of proximate
iodine value, acid value, saponification value, percent analysis and rancimat test was subjected to statistical
unsaponifiable matter, percent free fatty acids were analysis using SPSS 16 (statistical software package).
determined using standard procedure16. Values of the experiments are expressed as mean±
standard deviation.
Viscosity: Modular compact rheometer series MCR52
(Anton Paar, USA) was used in order to know the RESULTS AND DISCUSSION
time dependant viscosity of the extracted oil. Rheoplus Proximate analysis: Previous reports suggest that
inbuilt software was used to control the experimental chironji oil may be used as a substitute for almond oil
parameters. Cup and cone type system was used for for food and pharmaceutical applications. It has been
the measurement by keeping temperature constant found that the oil yield of the seed kernel was 56%
(25±1oC). The frequency used was 10–4-100 Hz and (28 g) using hexane as a solvent. The physicochemical
time of analysis used was 120 seconds for each properties such as acid value, free fatty acid, iodine
experiment. Viscosity of the samples is reported in value, saponification value, percent unsaponifiable
centipoise (cP). matter and viscosity of oil are reported in Table 1.

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Results of higher saponification value (205.79±2.60) of saturated fatty acids (41.79%) and unsaturated fatty
and lower percent unsaponifiable matter (1.4±0.30) acids (58.21%). Results of fatty acid composition and
indicate that chironji seed oil is normal triglycerides and presence of triglycerides are comparable with some
can be used for food, pharmaceutical and cosmetic earlier study11, 12.
applications after proper safety evaluation. Iodine
value of oil was found to be low (59.10±1.43) which
keeps oil in non-drying group. Some compositional
parameters of chironji kernel, oil and de-oiled cake
are mentioned in Table 2. Results of compositional
characteristics are comparable with previous results
reported in literature1, 21.

TABLE 1
Physicochemical Properties of Chironji Oil

Properties Chironji Oil


Acid value (mg KOH/g) 18.53±0.47
Free fatty acids (mg KOH/g) 9.31±0.24
Fig.1 : GC Profile of Chironji Oil
Iodine value (gI2/100g) 59.10±1.43
Saponification value (mg KOH/g) 205.79±2.60 TABLE 3
Unsaponifiable matter (% w/w) 1.4±0.30 Fatty Acid Composition of Chironji Oil

Viscosity (cP) 28.6±0.24 Fatty acid Lipid number Amount (%)


All values are the means of triplicate determination ± Myristic acid C14:0 2.90
standard deviation. Palmitic acid C16:0 31.42

TABLE 2 Stearic acid C18:0 7.47


Compositional Parameters of Chironji Seed Oleic acid C18:1 53.71

Parameter Sample part Mean ± SD (%) Linoleic acid C18:2 4.50

Carbon (C) Kernel 61.91±1.21 The compounds identified from chironji oil
Hydrogen (H) Kernel 9.66±0.73 analysed by GC-MS are shown in Table 4. The
identification of the compounds were performed by
Nitrogen (N) Kernel 4.51±0.59
matching their fragmentation pattern in mass spectra
Carbohydrate Kernel 10.87±0.61 with NIST-11and Wiley-8 library. The principal chemical
Protein Kernel 28.19±1.09 compounds found were 9-Octadecanoic acid (37.28);
Hexadecanoic acid (21.61); 1- Tetradecanol (14.58); 9-
Ash De-oiled cake 5.63±0.96
Hexadecanoic acid (2.16); 1-Dodecanol (1.96), Methyl-
Moisture Kernel 2.86±0.91 eicosanoate (1.88); Oleic acid eicosyl ester (1.81);
De-oiled cake w9.66±0.31 2-Methoxy decanoic acid (1.47) etc. Fragmentation
pattern of some important chemical compounds of the
Oil 0.87±0.07 oil were shown in Fig.2 (a),(b),(c),(d),(e). It was found
All values are the means of triplicate determination ± that the plant seed oil is rich in fatty acids content.
standard deviation. This investigation showed that the octadecanoic acid
and hexadecanoic acid (21.47) were the major fatty
Fatty acid profile by GC and GC-MS analysis: Fatty acids. This variation of chemical composition in the
acid composition of oil analysed by GC is displayed fatty acids oil could be due to different geographic
in Fig.1 and values are reported in Table 3. Oleic and climatic environmental conditions of the plants22.
acid (53.71%) is the principal fatty acid followed by Earlier studies suggest that the content and chemical
palmitic acid (31.42%),stearic acid (7.47%), Linoleic composition of oil in oilseeds are hampering by
acid (4.50%), myristic acid (2.90%). Fatty acid the geographical location and climatic conditions,
composition of oil contains approximately 40:60 ratios particularly temperature and rainfall23-25.

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TABLE 4
GC-MS Profiling of Chironji Oil
Compounds identified R. Time (min) % Area
Tridecane 3.59 0.89
1-Dodecanol 6.87 1.96
1-Tetradecanol 12.37 14.58
9-Hexadecanoic acid, methyl ester 17.91 2.16
Hexadecanoic acid, methyl ester 19.0 21.61
9-Octadecanoic acid, methyl ester 23.51 37.28
Octadecanoic acid, methyl ester 23.77 5.96
Methyl 9-cis,11-trans-octadecadienoate 24.69 0.65
2-Methoxy decanoic acid 26.20 1.47
Cis-11-Eicosenoic acid, methyl ester 27.00 0.66
Eicosanoate <methyl-> 27.57 1.88
Heptadecanedioic acid, 9-oxo-, dimethyl ester 29.04 0.25
Phthalic acid, bis(2-ethylhexyl) ester (6CI,8CI) 31.90 0.38
Tetracosanoate <methyl-> 35.20 0.66
Docosanoate <methyl-> 38.62 0.84
Thiositosterol disulphide 41.51 0.24
Hexadecanoic acid, tetradecyl ester 42.73 0.99
Oleic acid, eicosyl ester 47.15 1.81
Tetracosyl pentafluoropropionate 47.64 0.25

Time dependant viscosity analysis: Viscosity of chironji to monounsaturated fatty acid and saturated fatty
oil was measured by rheometer at room temperature acids29-31.
(25 oC) correspondence with time (120 seconds) in Differential Scanning Calorimetry: Differential scanning
order to evaluate changes in viscosity. Twenty data calorimetry (DSC) was used to determine the
points were measured at the interval of 6 seconds as occurrence of exothermal or endothermal changes
shown in Fig.3. Viscosity of chironji oil at first data with increase in temperature.
point was noted at 28.6 cP and last data point at 1.8
cP with decreasing viscosity by one. The viscosity of Fig.4 (b) shows a DSC profile for the sample of
other oils namely almond (81.92 cP), olive (86.62 cP) chironji oil, the peak above the baseline representing an
exothermic event. The peak of exotherm was 323oС,
and walnut (59 cP) is more than chironji oil26. Augusto27
indicating that the curing and thickening behaviour of
reported time dependant steady state decay of shear
this oil will occur at this temperature. One exothermic
stress for tomato juice which is similar to decaying
peak is exhibited by the sample corresponding to its
trend of stress for chironji oil with increasing time.
glass transition. The temperatures of phase transition
were observed to be very high and may provide extra
Thermogravimetric Analysis: The result of the
structural stability. Earlier studies19 are consistent with
thermogravimetric analysis (TGA) on the chironji oil
the current result.
is reported in Fig. 4(a). TGA was used to determine
the weight loss of the oil on heating. Transitions Oxidative stability: Oxidative stability of Chironji oil
involving mass changes are noticed by TGA as a was determined by Rancimat 743 model to study
function of temperature and time. In this study the the effect of varying temperature on the stability
curve shows that the oil did not decompose before of oil. Results from this study showed that as the
249oC. The start time for decomposition of Chironji temperature increases from 110-130oC by keeping
oil was a little lower than that of other vegetable oils constant air flow rate, stability of oil decreases to its
such as olive oil (287.99oC), sunflower oil (304.00oC) half as shown in Fig.5. From the continuous three
and corn oil (305.95oC)28. Earlier reports suggest that observation of each experiment of varying temperature
polyunsaturated fatty acids are less stable compared at 110, 120 and 130oC, induction period of oil was

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Fig.2 : Mass Spectrum of different compound
a.9-Octadecenoic acid, methyl ester, b.1-
Tetradecanol, c.9-Hexadecenoic acid, methyl
ester, d.Hexadecenoic acid, methyl ester,
e.Oleic acid, eicosyl ester.

Fig.4 : Thermal Curve for Chironji Oil a. TGA analysis,


b. DSC Analysis

Fig.3 : Time Dependant Viscosity of Chironji Oil Fig.5 : Oxidative Stability of Chironji Oil

found to be 19.71±1.23, 7.83±0.98 and 3.29±1.11. chironji oil. This increase in stability of chironji oil is
Results confirmed that chironji oil is stable than pea due to the presence of more oleic acid in fatty acid
nut (6.05±0.46 at 110oC) and linseed oil (1.50±0.04 composition and lower percentage of linoleic acid
at 110oC) as reported earlier20. On the other hand (4.50) content where in almond oil, linoleic acid is
the stability of almond oil at 120oC with 20 L/h air slightly more (20-23%) which makes oil more prone
flow rate showed 4.1 hour IP32 which is lower than towards oxidation33.

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CONCLUSION 7. Chitra V, D P Prasad, P K Kumar, N A Rao, Int.
The present study evaluates the quality J. Chem. Tech. Res., 1, 1026 (2009).
and stability of chironji seed oil by exploring its 8. Kodati D, S K Pareta, A K Patnaik
physicochemical properties, composition, oxidative Pharmacologyonline, 3, 720 (2010)
stability, and thermal behaviour. The oil obtained from
chironji nuts has remarkable nutritional properties. The 9. Singh S, K V Peter (ed) in Underutilized
study shows that this oil is an excellent source of and underexploited crops, vol 2, New-Delhi
omega-9 oleic acid in particular and palmitic acid. The Publishing Agency, New-Delhi, pp 295 (2007).
results may be used for the basis of their utilities in 10. Malik S K, R Chaudhury, N S Panwar, O P
several research areas such as food, pharmaceuticals, Dhariwal, R Choudhary, S Kumar, Genet Resour.
cosmetics etc. The oxidative stability and thermal Crop Evol. 59, 615 (2012)
behaviour indicate that this oil could be the stable
11. Sengupta A, S K Roychoudhary, J. Sci. Food
component and substitute for confectionary materials
Agric., 28, 463 (1977).
and can also be used as an additive or blending
agent to stabilize other lipid based materials which 12. Hemavathy J, J V Prabhakar, J. Food Comp.
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detailed investigations are warranted to explore the
13. Hassel R L, J. Amer. Oil Chem Soc., 53, 179
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(1976)
other edible oils to increase their potential utility. The
findings shown in this study may help in improving 14. Coni E, E Podesta, T Catone, Thermochim
its socio- economic values for the unprivileged Indian Acta., 418, 11 (2004).
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Blackie Academic and Professional New York
ACKNOWLEDGEMENT (1996).
The authors sincerely acknowledge Ministry
16. IS 548-1, Methods of sampling and test for oils
of Food Processing Industries (MOFPI), India for
and fats, Part I: Methods of sampling, physical
providing financial assistance. The First author also
and chemical tests. (1964).
thankful to Dr Iswara Baitharu, Mr Rabindra Padhan
and Mr Satya Mahapatra for valuable scientific 17. Hammond E W, in Chromatography for the
suggestion and language editing and also for identifying analysis of lipids CRC Press, Boca Raton, London
and authenticating the plant material. (UK), 81 (1993)
18. Madankar C S, S Pradhan, S N Naik, Ind Crop
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