Detection  Vol.1 No.2 , October 2013
A Rapid Separation and Highly Determination of Paraben Species by Ultra-Performance Liquid Chromatography —Electrochemical Detection
In this study, a new technique was developed using rapid ultra-performance liquid chromatography (UPLC)-based separation coupled with electrochemical detection by a boron-doped diamond (BDD) electrode for the detection and quantification of three commonly used parabens (methylparaben (MP), ethylparaben (EP) and propylparaben (PP)). We aimed to reduce the analysis time by using UPLC coupled with a short reverse phase C 18 monolithic column (25 mm×4.6 mm). Operating the monolithic column at low back-pressure resulted in high flow rates. A mobile phaseconsisting of a 25:75 (v/v) ratio of acetonitrile:0.05 Mphosphate buffer (pH 5) at a flow rate of 2.5 mL·min?1 was used to perform the separation. The amperometric detection with the BDD electrode was found to be optimal and reliably reproducible at a detection potential of 1.5 V vs. Ag/AgCl. Under these conditions, the separation of the three targetanalytes (MP, EP and PP) was achieved in 2 min and was linear within a sample concentration range of 0.1 to 50.0 mg·L?1 (r2 values of 0.9970, 0.9994 and 0.9994 for MP, EP and PP, respectively). This method was successfully applied to determine the concentrations of each parabeninsix real samples with therecoveries ranging from of 80.3% - 98.9% for all three parabensfrom samples spiked at 12, 22 and 32 mg·L?1. Therefore, the proposed method can be used as an alternative rapid and selective method for the determination of paraben levels in real samples.

Cite this paper
M. Chuto, S. Chaiyo, W. Siangproh and O. Chailapakul, "A Rapid Separation and Highly Determination of Paraben Species by Ultra-Performance Liquid Chromatography —Electrochemical Detection," Detection, Vol. 1 No. 2, 2013, pp. 21-29. doi: 10.4236/detection.2013.12004.
[1]   Q. Chu. J. Wang, D. Zhang and J. Ye, “Sensitive Determination of Parabens in Soy Sauces by Capillary Zone Electrophoresis with Amperometric Detection,” European Food Research and Technology, Vol. 231, No. 6, 2010, pp. 891-897.

[2]   M. G. Soni, I. G. Carabin and G. A. Burdock, “Safety Assessment of Esters of p-Hydroxybenzoic Acid (Parabens),” Food and Chemical Toxicology, Vol. 43, No. 7, 2005, pp. 985-1015.

[3]   B. Saad, M. F. Bari, M. I. Saleh, K. Ahmad and M. K. M. Talib, “Simultaneous Determination of Preservatives (Benzoic Acid, Sorbic Acid, Methylparaben and Propylparaben) in Foodstuffs Using High-Performance Liquid Chromatography,” Journal of Chromatography A, Vol. 1073, No. 1-2, 2005, pp. 393-397.

[4]   I. Marquez-Sillero, E. Aguilera-Herrador, S. Cardenas and M. Valcarcel, “Determination of Parabens in Cosmetic Products Using Multi-Walled Carbon Nanotubes as Solid Phase Extraction Sorbent and Corona-Charged Aerosol Detection System,” Journal of Chromatography A, Vol. 1217, No. 1, 2010, pp. 1-6.

[5]   D. Casoni, I. A. Tuhutiu and C. Sarbu, “Simultaneouse Determination of Parabens in Pharmaceutical Preparations Using High-Performance Thin-Layer Chromatography and Image Analysis,” Journal of Liquid Chromatography & Related Technologies, Vol. 34, No. 10-11, 2011, pp. 805-816.

[6]   M. G. Soni, G. A. Burdock, S. L. Taylor and N. A. Greenberg, “Safety Assessment of Propyl Paraben: A Review of the Published Literature,” Food and Chemical Toxicology, Vol. 39, No. 6, 2001, pp. 513-532.

[7]   Q. Zhang, M. Lian, L. Liu and H. Cui, “High-Performance Liquid Chromatographic Assay of Parabens in Wash-Off Cosmetic Products and Foods Using Chemiluminescence Detection,” Analytica Chimica Acta, Vol. 537, No. 1-2, 2005, pp. 31-39.

[8]   J. R. Byford, L. E. Shaw, M. G. B. Drew, G. S. Pope, M. J. Sauer and P. D. Darbre, “Oestrogenic Activity of Parabens in MCF7 Human Breast Cancer Cells,” Journal of Steroid Biochemistry & Molecular Biology, Vol. 80, No. 1, 2002, pp. 49-60.

[9]   P. D. Darbre, A. Aljarrah, W. R. Miller, N. G. Coldham, M. J. Sauer and G. S. Pope, “Concentrations of Parabens in Human Breast Tumours,” Journal of Applied Toxicology, Vol. 24, No. 1, 2004, pp. 5-13.

[10]   E. J. Routledge, J. Parker, J. Odum, J. Ashby and J. P. Sumpter, “Some Alkyl Hydroxy Benzoate Preservatives (Parabens) Are Estrogenic,” Toxicology and Applied Pharmacology, Vol. 153, No. 1, 1998, pp. 12-19.

[11]   C. Lemini, G. Silva, C. Timossi, D. Luque and A. Valverde, M. Gonzalez-Martinez, A. Hernandez, C. Rubio-Poo, B. C. Lara and F. Valenzuela, “Estrogenic Effects of p-Hydroxybenzoic Acid in CD1 Mice,” Environmental Research, Vol. 75, No. 2, 1997, pp. 130-134.

[12]   X. Ye, A. M. Bishop, L. L. Needham and A. M. Calafat, “Automated On-Line Column-Switching HPLC-MS/MS Method with Peak Focusing for Measuring Parabens, Triclosan and Other Environmental Phenols in Human Milk,” Analytica Chimica Acta, Vol. 622, No. 1-2, 2008, pp. 150-156.

[13]   G. Shanmugam, B. R. Ramaswamy, V. Radhakrishnan and H. Tao, “GC-MS Method for the Determination of Paraben Preservatives in the Human Breast Cancerous Tissue,” Microchemical Journal, Vol. 96, No. 2, 2010, pp. 391-396.

[14]   M. Ganzera, A. Aberham and H. Stuppner, “Development and Validation of an HPLC/UV/MS Method for Simultaneous Determination of 18 Preservatives in Grapefruit Seed Extract,” Journal of Agricultural and Food Chemistry, Vol. 54, No. 11, 2006, pp. 3768-3772.

[15]   A. Zotou, I. Sakla and P. D. Tzanavaras, “LC-Determination of Five Paraben Preservatives in Saliva and Toothpaste Samples Using UV Detection and a Short Monolithic Column,” Journal of Pharmaceutical and Biomedical Analysis, Vol. 53, No. 3, 2010, pp. 785-789.

[16]   G. A. Shabir, “Method Development and Validation of Pereservatives Determination (Benzyl Alcohol, Ethylene Glycol Monophenyl Ether, Methyl Hydroxybenzoate, Ethyl Hydroxybenzoate, Propyl Hydroxybenzoate, and Butyl Hydroxybenzoate) using HPLC,” Journal of Liquid Chromatography & Related Technologies, Vol. 30, No. 13, 2007, pp. 1951-1962.

[17]   N. Memon, M. I. Bhanger and M. Y. Khuhawer, “Determination of Preservatives in Cosmetics and Food Samples by Micellar Liquid Chromatography,” Journal of Separation Science, Vol. 28, No. 7, 2005, pp. 635-638.

[18]   G. A. Shabir, “A New Validated HPLC Method for the Simultaneous Determination of 2-Phenoxyethanol, Methylparaben, Ethylparaben and Propylparaben in a Pharmaceutical Gel,” Indian Journal of Pharmaceutical Sciences, Vol. 72, No. 4, 2010, pp. 421-425.

[19]   B. R. Ramaswamy, G. Shanmugam, G. Velu, B. Rengarajan and D. G. J. Larsson, “GC-MS Analysis and Ecotoxicological Risk Assessment of Triclosan, Carbamazepine and Parabens in Indian Rivers,” Journal of Hazardous Materials, Vol.186, No. 2-3, 2011, pp. 1586-1593.

[20]   L. Wang, X. Zhang, Y. Wang and W. Wang, “Simultaneous Determination of Preservatives in Soft Drinks, Yogurts and Sauces by a Novel Solid-Phase Extraction Element and Thermal Desorption-Gas Chromatography,” Analytica Chimica Acta, Vol. 577, No. 1, 2006, pp. 62-67.

[21]   T.-J. Yang, F.-J. Tsai, C.-Y. Chen, T. C.-C. Yang and M.-R. Lee, “Determination of Additives in Cosmetics by Supercritical Fluid Extraction On-Line Headspace Solidphase Microextraction Combined with Gas Chromatography—Mass Spectrometry,” Analytica Chimica Acta, Vol. 668, No. 2, 2010, pp. 188-194.

[22]   A. M. C. Ferreira, M. Moder and M. E. F. Laespada, “GC-MS Determination of Parabens, Triclosan and Methyl Triclosan in Water by in Situ Derivatisation and Stir-Bar Sorptive Extraction,” Analytical and Bioanalytical Chemistry, Vol. 399, No. 2, 2011, pp. 945-953.

[23]   J. B. Claver, M. C. Valencia and L. F. Capitan-Vallvey, “Analysis of Parabens in Cosmetics by Low Pressure Liquid Chromatography with Monolithic Column and Chemiluminescent Detection,” Talanta, Vol. 79, No. 2, 2009, pp. 499-506.

[24]   A. Myint, Q. Zhang, L. Liu and H. Cui, “Flow Injection-Chemiluminescence Determination of Paraben Preservative in Food Safety,” Analytica Chimica Acta, Vol. 517, No. 1-2, 2004, pp. 119-124.

[25]   W. Jinyan, Z. Dongli, C. Qingcui and Y. Jiannong, “Simultaneous Determination of Phenolic Additives in Cosmetics by Micellarelectrokinetic Capillary Chromatogramphy with Electrochemical Detection,” Chinese Journal of Chemistry, Vol. 28, No. 2, 2010, pp. 313-319.

[26]   Y. Yu, Q. Huang, J. Cui, K. Zhang, C. Tang and X. Peng, “Determination of Pharmaceuticals, Steroid Hormones and Endocrine-Disrupting Personal Care Products in Sewage Sludge by Ultra-High-Performance Liquid Chromatography—Tandem Mass Spectrometry,” Analytical and Bioanalytical Chemistry, Vol. 399, No. 2, pp. 891-902.

[27]   T. Wu, C. Wang, X. Wang and Q. Ma, “Simultaneous Determination of 21 Preservatives in Cosmetics by Ultraperformance Liquid Chromatography,” International Journal of Cosmetic Science, Vol. 30, No. 5, 2008, pp. 367-372.

[28]   M. Mincea, I. Lupsa, I. Talpos and V. Ostafe, “UPLC Analysis of Common Parabens in Cosmetic Products,” Acta Chromatographica, Vol. 21, No. 4, 2009, pp. 591-60.

[29]   L. Xiu-Qin, J. Chao, Y. Wei, L. Yun, Y. Min-Li and C. Xiao-Gang, “UPLC-PDAD Analysis of Simultaneous Determination of Ten Synthetic Preservatives in Foodstuff,” Chromatographia, Vol. 68, No. 1-2, 2008, pp. 57-63.

[30]   J. G. Jimenez, M. C. Valencia and L. F. Capitan-Vallvey, “Parabens determination with a hybrid FIA/HPLC system with ultra-short monolithic column,” Journal of Analytical Chemistry, Vol. 65, No. 2, 2010, pp. 188-194.

[31]   S. Dalibor, S. Petr, C. Petr and K. Rolf, “Monolithic columns-a new concept of separation in the sequential injection technique,” Analytica Chimica Acta, Vol. 499, No. 10, 2003, pp. 205-214.

[32]   L.-P. Labranche, A. Tousignant, D. Abran and A. Carrier, “Fast Determination of 4-Hydroxybenzoic Acid in Different Matrices Using Monolithic Column Separation,” Journal of Liquid Chromatography & Related Technology, Vol. 31, No.17, 2008, pp. 2575-2586.

[33]   S. H. Kang and H. Kim, “Simultaneous Determination of Methylparaben, Propylparaben and Thimerosal by High-Performance Liquid Chromatography and Electrochemical Detection,” Journal of Pharmaceutical and Biomedical Analysis, Vol. 15, No. 9-10, 1997, pp. 1359-1364.

[34]   I. Martins, F. C. Carreira, L. S. Canaes, F. A. S. C. Campos, L. M. S. Cruz and S. Rath, “Determination of parabens in shampoo using high performance liquid chromatography with amperometric detection on a boron-doped diamond electrode,” Talanta, Vol. 85, No. 1, 2011, pp. 17.

[35]   L. S. Andrade, M. C. Moraes, R. C. Rocha-Filho, O. Fatibello-Filho and Q. B. Cass, “A Multidimensional High Performance Liquid Chromatography Method Coupled with Amperometric Detection Using a Boron-Doped Diamond Electrode for the Simultaneous Determination of Sulfamethoxazole and Trimethoprim in Bovine Milk,” Analytica Chimica Acta, Vol. 654, No. 2, 2009, pp. 127-132.