Malaysian
Journal of Analytical Sciences Vol 21 No 6 (2017): 1289 - 1298
DOI:
10.17576/mjas-2017-2106-10
EXTRACTION OF METHYLPARABEN IN COSMETICS USING DISPERSIVE
LIQUID-LIQUID MICROEXTRACTION BASED ON SOLIDIFICATION OF FLOATING ORGANIC DROP
COUPLED WITH GAS CHROMATOGRAPHY FLAME IONIZATION DETECTOR
(Pengekstrakan Metilparaben dalam
Kosmetik Menggunakan Pengekstrakan Mikro
Cecair-Cecair Serakan Berdasarkan
Pemejalan Organik Terampai Berganding dengan Kromatografi Gas Pengesan Nyala Pengionan)
Dyia
Syaleyana Md Shukri*, Nurul Asma Hamedan, Nur Shakirah Hussin, Wan Izhan Nawawi
Faculty of
Applied Sciences,
Universiti
Teknologi MARA, 02600 Arau, Perlis, Malaysia
*Corresponding author:
dyia839@perlis.uitm.edu.my
Received:
16 August 2016; Accepted: 4 November 2017
Abstract
A simple and
efficient method called dispersive liquid–liquid microextraction based on
solidification of floating organic droplets (DLLME-SFO) method coupled with gas
chromatography flame ionization detector (GC-FID) was developed for the
extraction of methylparaben (MP) in cosmetics. In the optimized DLLME-SFO
method, a mixture of n-hexadecane (70 μL) as an extraction solvent and methanol
(0.25 mL) as a disperser solvent was rapidly injected into a 5 mL sample
solution (pH 6) containing 4 % (w/v) NaCl.
After 4 minutes of centrifugation at 4000 rpm, the mixture was separated
into two phases with the fine droplets of n-hexadecane floating at the top of
the sample solution. Then, the test tube was placed in an ice bath for cooling
and solidification purposes. The solidified extract was transferred into a
small vial where it melted and injected into GC-FID system. The DLLME-SFO
method gave a good linearity over the concentration range from 0.1 – 8 µg/mL
with coefficient of estimation (r2)
from 0.9996. The method also provides a low limit of detections (LODs) which is
0.0048 µg/mL. Methylparaben
was detected in both samples at the concentration level of 0.06 µg/mL
for sample 1 and 0.42 µg/mL for sample 2 respectively.
Keywords: dispersive liquid–liquid microextraction,
solidification of floating organic droplets, gas chromatography flame
ionization detector, methylparaben, cosmetic
Abstrak
Kaedah yang senang dan berkesan iaitu pengekstrakan mikro cecair-cecair serakan berdasarkan
pemejalan organik terampai (DLLME-SFO) berganding dengan kromatografi gas
dengan dengan pengesan nyala pengionan (GC-FID) telah dihasilkan bagi penentuan
metilparaben dalam alatan kosmetik. Dalam kaedah DLLME-SFO yang telah
dioptimumkan, campuran n-heksadekana (70 μL) sebagai pelarut pengekstrak dan
metanol (0.25 mL) sebagai pelarut penyebar disuntik segera ke dalam 5 mL larutan
sampel (pH 6) yang mengandungi 4% (w/v) NaCl. Selepas pengemparan selama 4 min
pada 4000 rpm, campuran terpisah kepada dua fasa di mana titisan halus
n-heksadekana terapung di atas larutan sampel. Kemudiannya, tabung uji
diletakkan di dalam rendaman ais untuk penyejukan dan pemejalan. Ekstrak yang
beku dimasukkan ke dalam vial di mana ia mencair dan disuntik ke dalam sistem
GC-FID. Kaedah DLLME-SFO memberikan kelinearan yang baik untuk kepekatan
diantara, 0.1 – 8 μg/mL dengan
pekali penentuan (r2) 0.9996. Kaedah ini juga menunjukkan had
pengesanan (LODs) rendah iaitu 0.0048 μg/mL. Metilparaben telah dikesan dalam kedua-dua sampel pada
tahap kepekatan 0.06 μg/mL untuk sampel 1 dan 0.42 μg/mL untuk sampel 2.
Katakunci: pengekstrakan mikro cecair-cecair serakan, pemejalan
organik terampai, gas kromatografi pengesan pengionan nyala, metilparaben,
kosmetik
References
1. Kang, S. H. and Kim, H. (1997). Simultaneous determination of
methylparaben, propylparaben and thimerosal by high-performance liquid
chromatography and electrochemical detection. Journal of Pharmaceutical and Biomedical
Analysis, 15: 1359 – 1364.
2. Reisch, M. S.
(2005). Keeping well-preserved: Cosmetic preservatives makers offer
alternatives as widely used parabens come under scrutiny. Chemical Engineering News, 25 – 26.
3. Hirose,
M., Tanaka, Y., Tamano, H., Tamano, S., Kato, T. and Shirai, T. (1998).
Carcinogenicity of antioxidants BHA, caffeic acid, sesamol, 4-methoxyphenol and
catechol at low doses, either alone or in combination, and modulation of their
effects in a rat medium-term multi-organ carcinogenesis model. Carcinogenesis,
19: 207 – 212.
4. Soni, M. G., Burdock, G. A., Taylor, S. L. and Greenberg, N. A.
(2002). Evaluation of the health aspects of methylparaben: A review of the
published literature. Food Chemical
Toxicology. 40: 1335 – 1373.
5. Alshana, U., Ertas, N. and Goger, N. G. (2015). Determination of
parabens in human milk and other food samples by capillary electrophoresis
after dispersive liquid-liquid microextraction with back-extraction. Food Chemistry, 181: 1 – 8.
6. Darbre, P. D., Aljarrah, A., Miller, W. R., Coldham, N. G., Sauer, M.
J. and Pope, G. S. (2004). Concentrations of parabens in human breast tumours. Journal of Applied Toxicology, 24 (1):
5 – 13.
7. Canosa, P., Rodriguez,
I., Rubi, E., Bollain, M. H. and Cela, R. (2006). Optimization of a solid-phase microextraction method for the
determination of parabens in water samples at low ng per litre level. Journal of Chromatography A, 1124 (1-2):
3 – 10.
8. Darbre, P. D. and Harvey, P. W. (2008). Paraben esters: review
of recent studies of endocrine toxicity, absorption, esterase and human
exposure, and discussion of potential human health risks. Journal of Applied
Toxicology, 28: 561
– 78.
9. Routledge, E. J., Parker, J., Odum, J., Ashby, J. and Sumpter, J. P.
(1998). Some alkyl hydroxy benzoate preservatives (parabens) are estrogenic. Toxicology and
Applied Pharmacology, 153: 12 – 19.
10. Cabaleiro, N., Calle,
I., Bendicho, C. and Lavilla, I. (2014). An
overview of sample preparation for the determination of parabens in cosmetics. Trends
in Analytical Chemistry, 57: 34 – 46.
11. Salvador, A. and Chisvert, A. (2007). Analysis of cosmetic products,
Elsevier, Netherlands.
12. Wang, P. and Liu, Y. (2007). Cosmetic preservatives and analysis
methods used in China. Journal of
Environmental Health, 24: 557 – 559.
13. Cabaleiro, N., Calle,
I., Bendicho, C. and Lavilla, I. (2013). Current
trends in liquid-liquid and solid-liquid extraction for cosmetic analysis: A
review. Analytical Methods, 5: 323 –
340.
14. Cabaleiro, N., Calle,
I., Bendicho, C. and Lavilla, I. (2013). Solid
phase extraction and solid-phase microextraction in cosmetic analysis: A
review. Science Letter Journal, 2: 1
– 21.
15. Malika, J. N. N., Thiruveengadarajan, V. S. and Gopinath, C. (2013).
A review on various analytical method developments for the identification of
methyl paraben present in cosmetics. International
Journal of Review in Life Sciences, 3: 5 – 19.
16. Rezaee, M., Assadi, Y., Milani M. R., Hosseini, E., Aghaee, F.,
Ahmadi, S. and Berijani, S. (2006). Determination of organic compounds in water
using dispersive liquid-liquid microextraction. Journal of Chromatography A, 1116: 1 – 9.
17. Berijani, S., Assaddi, Y., Anbia. M., Milani, M. R., Hosseini, E. and
Aghaee, F. (2006). Dispersive liquid-liquid microextraction combines with gas
chromatography-flame photometric detection. very simple, rapid, and sensitive
method for the determination of organophosphorus pesticides in water. Journal of Chromatography A, 1123: 1 –
9.
18. Leong, M. I. and Huang, S. D. (2008). Dispersive liquid-liquid
microextraction method based on solidification of floating organic drop
combined with gas chromatography with electron capture or mass spectrometry
detection. Journal of Chromatography A,
1211: 8 – 12.
19. Juybari, M. B., Mehdinia, A., Jabbari, A. and Yamini, Y. (2011).
Dispersive liquid-liquid microextraction based on solidification of floating
organic drop followed by gas chromatography-electron capture detector for
determination of some pesticides in water samples. Chromatography Research
International, 2011: 1 – 8.
20. Jamali, M. R., Rahimpour, S. and Rahnama, R. (2012).
Determination of cobalt in natural water samples after separation and preconcentration
by dispersive liquid-liquid microextraction based on the solidification of
floating organic drop. Applied Chemistry, 23: 21 – 27.
21. Toraj, A-J., Nazir, F. and Mojtaba, S. (2014). Rapid
extraction and determination of amphetamines in human urine samples using
dispersive liquid-liquid microextraction and solidification of floating organic
drop followed by high performance liquid chromatography. Journal of Pharmaceutical and Biomedical Analysis, 94: 145 – 151.
22. Vinas, P., Campillo, N. and Andruch, V. (2015). Recent achievements
in solidified organic drop extraction. Trends
in Analytical Chemistry, 68: 48 – 77.
23. Sanagi, M. M., Abbas, H. H., Ibrahim, W. A. W. and Aboul-Enien, H. Y.
(2012). Dispersive liquid-liquid microextraction method based on solidification
of floating organic droplet for the determination of triazine herbicides in
water and sugarcane samples. Food
Chemistry, 133: 557 – 562.