Nusret ERTAŞ, Usama ALSHANA, Malek HASSAN

Dispersive liquid-liquid microextraction of parabens from pharmaceuticals and personal care products prior to their determination using HPLC-DAD

Dispersive liquid–liquid microextraction followed by a back-extraction step was combined with HPLC-DADfor the determination of four parabens (i.e. methyl-, ethyl-, propyl-, and butylparaben). Optimum extraction conditions were found as follows: 225 µL of chloroform, 0.75 mL of ethanol, 7.5 mL of aqueous solution and within an extraction time of 15 s. Back-extraction into 100 µL of 50 mM sodium hydroxide solution within 20 s resulted in a reversed-phase HPLC-compatible extract. The analytes were separated at 20 ◦ C using methanol (A) and water (B), 40:60 (A:B, v/v) as the mobile phase, a flow rate of 1.0 mL min −1 and an injection volume of 20 µL. DAD was set at 258 nm to monitor the analytes. Limits of detection and quantitation were as low as 0.1 and 0.3 µg mL −1, respectively. Coefficients of determination (R2 ) were higher than 0.9950 and percentage relative recoveries were found in the range of 86.5–114.5% for the four parabens from pharmaceuticals and personal care products.

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1. Soni MG, Carabin IG, Burdock GA. Safety assessment of esters of p-hydroxybenzoic acid (parabens). Food and Chemical Toxicology 2005; 43 (7): 985-1015. doi: 10.1016/j.fct.2005.01.020
2. Farajzadeh MA, Djozan D, Bakhtiyari RF. Use of a capillary tube for collecting an extraction solvent lighter than water after dispersive liquid-liquid microextraction and its application in the determination of parabens in different samples by gas chromatography-Flame ionization detection. Talanta 2010; 81 (4-5): 1360-1367. doi: 10.1016/j.talanta.2010.02.035
3. Pugazhendhi D, Pope GS, Darbre PD. Oestrogenic activity of p-hydroxybenzoic acid (common metabolite of paraben esters) and methylparaben in human breast cancer cell lines. Journal of Applied Toxicology 2005; 25 (4): 301-309. doi: 10.1002/jat.1066
4. Kang KS, Che JH, Ryu DY, Kim TW, Li GX et al Decreased sperm number and motile activity on the F1 offspring maternally exposed to butyl p-hydroxybenzoic acid (butyl paraben). Journal of Veterinary Medical Science 2002; 64 (3): 227-235. doi: 10.1292/jvms.64.227
5. Barr L, Metaxas G, Harbach CAJ, Savoy LA, Darbre PD. Measurement of paraben concentrations in human breast tissue at serial locations across the breast from axilla to sternum. Journal of Applied Toxicology 2012; 32 (3): 219-232. doi: 10.1002/jat.1786
6. Turk SC, Satana E, Basan H, Goger NG. Determination of ibuprofen and paraben in pharmaceutical formulations using flow-injection and derivative spectrophotometry. Journal of Analytical Chemistry 2015; 70 (1): 50-54. doi: 10.1134/s1061934815010141
7. Liu Y-C, Chang S-W, Chen C-Y, Chien IC, Lin C-H. Separation and determination of cold medicine ingredients by capillary zone electrophoresis using sulfated beta-cyclodextrin as an electrolyte modifier and chiral selector. Journal of the Chinese Chemical Society 2015; 62 (2): 191-196. doi: 10.1002/jccs.201400276
8. Jain R, Mudiam MKR, Chauhan A, Ch R, Murthy RC et al Simultaneous derivatisation and preconcentration of parabens in food and other matrices by isobutyl chloroformate and dispersive liquid-liquid microextraction followed by gas chromatographic analysis. Food Chemistry 2013; 141 (1): 436-443. doi: 10.1016/j.foodchem.2013.03.012
9. Ye N, Shi P, Li J, Wang Q. Application of graphene as solid phase extraction absorbent for the determination of parabens in cosmetic products by capillary electrophoresis. Analytical Letters 2013; 46 (13): 1991-2000. doi: 10.1080/00032719.2013.784916
10. Bhosale DM, Nikalje APG. Stability-indicating UPLC method for the estimation of nadifloxacin, terbinafine hydrochloride, mometasone furoate, methyl paraben, and propyl paraben in topical pharmaceutical dosage form. Journal of AOAC International. 2017; 100 (5): 1407-1413. doi: 10.5740/jaoacint.16-0254
11. Gao W, Legido-Quigley C. Fast and sensitive high performance liquid chromatography analysis of cosmetic creams for hydroquinone, phenol and six preservatives. Journal of Chromatography A 2011; 1218 (28): 4307-4311. doi: 10.1016/j.chroma.2011.04.064
12. Zotou A, Sakla I, Tzanavaras PD. 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 2010; 53 (3): 785-789. doi: 10.1016/j.jpba.2010.05.018
13. Rezaee M, Yamini Y, Faraji M. Evolution of dispersive liquid-liquid microextraction method. Journal of Chromatography A 2010; 1217 (16): 2342-2357. doi: 10.1016/j.chroma.2009.11.088
14. Tsai TF, Lee MR. Determination of antioxidants and preservatives in cosmetics by SPME combined with GC-MS. Chromatographia 2008; 67 (5-6): 425-431. doi: 10.1365/s10337-007-0514-1
15. Ding MZ, Liu WX, Peng J, Liu XH, Tang Y. Simultaneous determination of seven preservatives in food by dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry. Food Chemistry 2018; 269: 187-192. doi: 10.1016/j.foodchem.2018.07.002
16. Fontanals N, Marce RM, Borrull F. New materials in sorptive extraction techniques for polar compounds. Journal of Chromatography A 2007; 1152 (1-2): 14-31. doi: 10.1016/j.chroma.2006.11.077
17. Rezaee M, Assadi Y, Hosseinia MRM, Aghaee E, Ahmadi F et al Determination of organic compounds in water using dispersive liquid-liquid microextraction. Journal of Chromatography A 2006; 1116 (1-2): 1-9. doi: 10.1016/j.chroma.2006.03.007
18. Fan X, Kubwabo C, Rasmussen P, Jones-Otazo H. Simultaneous quantitation of parabens, triclosan, and methyl triclosan in indoor house dust using solid phase extraction and gas chromatography-mass spectrometry. Journal of Environmental Monitoring 2010; 12 (10): 1891-1897. doi: 10.1039/c0em00189a
19. Perez RA, Albero B, Miguel E, Sanchez-Brunete C. Determination of parabens and endocrine-disrupting alkylphenols in soil by gas chromatography-mass spectrometry following matrix solid-phase dispersion or in-column microwave-assisted extraction: a comparative study. Analytical and Bioanalytical Chemistry 2012; 402 (7): 2347- 2357. doi: 10.1007/s00216-011-5248-0
20. Zanjani MRK, Yamini Y, Shariati S, Jonsson JA. A new liquid-phase microextraction method based on solidification of floating organic drop. Analytica Chimica Acta 2007; 585 (2): 286-293. doi: 10.1016/j.aca.2006.12.049
21. Leong MI, Huang SD. 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 2008; 1211 (1-2): 8-12. doi: 10.1016/j.chroma.2008.09.111