Jamaican ackee (Blighia sapida) oil A comparative look at the lipid

JAMAICAN ACKEE (BLIGHIA SAPIDA)
Investigating the economic potential of Jamaican ackee
Andrea Goldson Barnaby
Department of Chemistry, The University of the West Indies
Overview
Introduction
Overview
Materials & Methods
Results
Discussion
Conclusion
Introduction
The ackee (Blighia sapida Koenig) is a tropical fruit belonging to the Sapindaceae family.
The fruit while originally from West Africa can be found widely distributed throughout the island of
Jamaica.
In Jamaica the fruit is a part of the national dish ackee and cod fish and is also processed as ackee in
brine.
Extensive research has been performed on hypoglycin A (Bowen-Forbes & Minott 2012; Dundee &
Minott, 2012), a toxic component found in the unripe fruit (Fig. 1).
Only fully mature open fruits should be eaten.
Processing
The fruit is processed in brine and canned for export to the USA, Canada and the UK
Earns in excess of $13.5 M annually (STATIN 2010)
Are there alternative methods of processing the ackee?
Cryogenic Freezing of Jamaican Ackees (Blighia sapida)
Investigation of the impact of cryogenic freezing on the nutritional and
sensory attributes of ackee (Blighia sapida)
Ereca Peart1, Subramaniam Sathivel2, Andrea Goldson Barnaby1 and Ian Thompson1
1Department of Chemistry, University of the West Indies, Jamaica
2Department of Food Science and Department of Biological & Agricultural
Engineering, Louisiana State University, USA
Cryogenic freezing
Ackees (blanched and unblanched) were subject to cryogenic freezing (-10 °C, -20 °C and -30 °C)
using liquid nitrogen.
 Ascorbic acid content was determined utilizing high performance liquid chromatography
(HPLC) and lipid degradation monitored using the thiobarbituric acid assay.
 Moisture loss and fruit colour before and after freezing were also assessed.
Higher retention of ascorbic acid and lower levels of lipid degradation were observed in
unblanched samples frozen at -30 °C.
Results for colour also showed better L values at -30 °C.
Statistical analysis indicated no statistically significant impact on the investigated attributes by
cryogenic freezing.
Cryogenic freezing may be considered as an alternative method for processing ackees.
Original samples
Not blanched at -30°C
Lipid profile
Limited information regarding the fatty acid profile of the fruit with conflicting results being
reported in the literature
Oleic acid (Emanuel et al. 2013) and linoleic acid (Odutuga et al. 1992) have been reported as
the predominant fatty acid in the arilli of the fruit
Oleic acid (Esuoso & Odetokun, 1995) was reported as the major fatty acid in seeds from
Nigeria, while seeds from Benin and Ivory Coast identified gondoic acid as the predominant fatty
acid present
Health implications
Knowledge of the fatty acid profile of the fruit is important as this has implications with regards
to health and the stability of the oil
The fruit was previously linked to prostate cancer in Jamaican men due to the reported high
levels of linoleic acid present in the fruit (Ritch et al. 2007)
This research will serve to widen the database of available literature regarding the lipid profile
of the fruit grown from different geographical regions and provide well needed information to
consumers who are presently concerned about the possible link of ackee consumption and
prostate cancer
Materials and Methods
Sample preparation
Mature ackee fruits (stages 5 and 7) of the cheese and butter variety were harvested over two
time periods
Fruits were separated into their individual components, and dried to constant weight (55 oC for
6 days, Gallenkamp Laboratory Oven OV-330, England)
These were milled utilizing a Perten Instrument, Lab Mill 3600 (30 sec at 25 oC)
Seed
Aril
Raphe
Lipid extraction
Soxhlet extraction
Oil was extracted from the dried, milled portions of the fruit with
petroleum ether (bp 80-100 oC, reflux, 2h) in a Soxhlet apparatus and
concentrated in vacuo.
Fatty Acid Methyl Esters
Soxhlet extracted ackee oil (0.003g) was trans-methylated with methanol/acetyl chloride
solution (Masood et al. 2005)
Fatty acid methyl esters (FAMEs) were determined by Gas Chromatography-Mass Spectrometry
(GC-MS).
Constituents were identified with the National Institute of Standards and Technology (NIST)
library of mass spectra and subsets (match quality > 80%).
Iodine value determination
The iodine value was predicted based on the fatty acid methyl ester (FAME) profile of the fruit
1H NMR and 13C NMR Spectroscopy
1H NMR and 13C NMR characterization was performed on a Bruker AC instrument 200 MHz at
200 MHz. Samples (approx. 20 mg) were run in deuterated chloroform (CDCl3) at 25 °C with
tetramethylsilane (TMS) as the internal standard.
1H NMR was used to determine the relative percentage levels of saturated (S), monounsaturated (MUFA) and polyunsaturated fatty acids (PUFA) present in the fruit
Results & Discussion
% Crude Fat
Average
Arilli
49.79 ± 3.73
Seed
5.62 ± 1.03
Raphe
1.72 ± 0.32
Pod
0.55 ± 0.38
Fatty acid profile of the ackee fruit
aFAME
Arilli (%)
Pod (%)
Raphe (%)
Seed (%)
(C18:1)
57.15 ± 8.75
41.68 ± 2.29
55.07 ± 3.44
13.65 ± 4.05
Palmitic (C16:0)
24.91 ± 8.08
29.46 ± 3.53
23.36 ± 1.36
4.50 ± 3.86
Stearic
(C18:0)
11.24 ± 4.07
8.71 ± 0.02
13.54 ± 4.83
3.84 ± 1.86
Gondoic (C20:1)
1.79 ± 1.32
9.15 ± 1.93
2.39 ± 0.69
48.36 ± 9.09
Arachidic (C20:0)
1.10 ± 0.45
3.6 ± 0.85
1.47 ± 0.31
28.72 ± 5.33
Linoleic (C18:2)
1.03 ± 0.23
5.65 ± 2.42
7.86 ± 2.83
*0.54
cND
ND
ND
1.25 ± 0.27
Oleic
Behenic
Predicted Iodine Value
Ackee
Predicted Iodine Value
Arilli
61
Seed
63
Pod
59
Raphe
69
Characteristic 1H NMR spectrum of ackee oil
extracts
Proton assignments
Proton
CH3
CH2
CH2-CH2-COO
CH2-COO
C=C-CH2C=C
CH2O(α)
Functionality
Terminal methyl
Methylene
Acyl chains
All acyl chains
Bis allylic carbon protons
Glycerol (triglycerides)
CHO(β)
CH=CH
Glycerol (triglycerides)
Olefinic protons
Ackee
Arilli
δ ppm
0.84 (m)
1.22 (s)
1.58 (m)
2.28 (t)
3.63 (s)
4.13(dd)
4.29 (dd)
5.25 (m)
5.33 (m)
Ackee
Seed
δ ppm
0.82 (m)
1.20 (s)
1.55 (m)
2.25(t)
3.60 (s)
4.10(dd)
4.27(dd)
5.21(m)
5.27 (m)
Ackee
Pod
δ ppm
0.82 (m)
1.19 (s)
1.56 (m)
2.23 (m)
3.65 (s)
4.10 (dd)
4.26 (dd)
5.21 (m)
5.22 (m)
Ackee
Raphe
δ ppm
0.84 (m)
1.22 (s)
1.56 (m)
2.27 (t)
3.62 (s)
4.12 (dd)
4.25 (dd)
5.23 (m)
5.30 (m)
13C
Characteristic
NMR spectrum of
ackee oil extracts
1,2-Dioleylpalmitin
1,2-Dioleylpalmitin was identified as the major triglyceride in the arilli of the fruit.
1H NMR revealed the presence of two doublet of doublets and a multiplet, which are
consistent with the protons of the glyceryl moiety.
A singlet at δ 3.60 may be used to predict the presence of linoleic acid in extracts of the
fruit (Thoss et al. 2012).
Characteristic IR absorbance bands for lipids were observed at 1744, 1466 and 1163
cm-1.
Waste Utilization
There has been an increase in energy demand due to urbanization and industrial development.
Energy sources have predominantly been that of fossil fuel which are nonrenewable and may
lead to environmental damage.
Alternative energy sources such as edible and non edible vegetable oils are currently being
investigated.
Waste generated from the ackee industry may be considered as a source of biodiesel.
Transesterification of lipid extracts could be further investigated to improve their combustibility.
Conclusion
Oleic acid was identified as the major fatty acid in the arilli, pod and raphe of the fruit
Gondoic acid was identified as the major fatty acid in the seed of the fruit
High levels of C20 fatty acids were identified in the seed of the fruit (gondoic C20, and arachidic
C20:1)
Linoleic acid was only identified in small quantities in extracts of the fruit
The proposed link between the consumption of ackees, linoleic acid content and prostate
cancer is therefore invalid
NMR spectroscopy is a facile method to determine the presence of linoleic in lipid extracts of the
ackee fruit
A singlet at δ 3.60 in the 1H NMR due to bis allylic protons may be used to predict the presence of
linoleic acid in extracts from the ackee fruit
The iodine value of different extracts of the fruit was predicted
The waste generated from the processing of ackees can be considered for use for other industrial
applications.
Cryogenic freezing may be utilized in the processing of ackees
References
Bowen-Forbes, C.S., & Minott, D.A. (2011). Tracking hypoglycins A and B over different maturity stages: Implications for detoxification of
ackee (Blighia sapida K.D. Koenig) fruits. J Agr Food Chem, 59, 3869-3875.
Dundee, S.J.S. and Minott, D.A. 2012 Impact of seed size on residual hypoglycin levels in ackee. Food Research International, 47:306-309.
Emanuel, M.A., Gutierrez-Orozco, F. Yahia, E.M. & Benkeblia, N. (2013). Assessment and profiling of the fatty acids in two ackee fruit
(Blighia sapida Koenig) varieties during different ripening stages. J Sci Food Agric, 93, 722–726.
Kyriakidis, N. B. & Katsiloulis, T. (2000). Calculation of iodine value from measurements of fatty acid methyl esters of some oils:
Comparison with the relevant American Oil Chemists Society method. Journal of the American Oil Chemists' Society, 77, 1235-1238.
Masood, A., Stark, K.D., Salem, N. (2005). A simplified and efficient method for the analysis of fatty acid methyl esters suitable for large
clinical studies. Journal of Lipid Research, 46, 2299-2305.
Odutuga, A.A., Asemoto H.N., Musac, I., Golden K.D., Kean E.A. (1992). Fatty acid composition of arilli from ackee fruit (Blighia sapida ).
Jam J Sci Tech, 3, 30-32.
Ritch, C. R., Wan, R. L., Stephens, L. B., Taxy, J. B., Huo, D., Gong, E. M., Zagaja, G. P. & Brendler, C. B. (2007). Dietary fatty acids correlate
with prostate cancer biopsy grade and volume in Jamaican men. Journal of Urology, 177, 97-101.
STATIN (2010). External trade (January to December 2009). External trade statistical bulletin, 2. (pp. 9) Kingston, Jamaica: The Statistical
Institute of Jamaica.
Acknowledgements
Department of Chemistry, University of the West Indies, Jamaica
Louisiana State University, USA
Dr S. Sathivel
Dr D. Minott Kates