DETERMINATION OF SUNSCREEN AGENTS BY UPLC AND HPLC 479 Table V Theoretical Concentrations (TC), Observed Concentrations (OC), and Recovery for Accuracy Studies by HPLC and UPLC Sunscreen TC oc Recovery agent Instrument (µg ml- 1 ) (µg ml- 1 ) (%) IMC HPLC 43.22/47 .58/5 7 .19 42.88/48.19/57 .57 99.20/101.28/100.67 UPLC 42.99/48.15/5 7 .63 99.47 /101.20/100.77 OMC HPLC 130.97 /143.13/170.97 130.35/145.44/172.57 99.5 3/101.61/100.98 UPLC 130.45/141.96/172.33 99 .60/99.18/100.80 OS HPLC 95.26/108.31/130.35 96.36/109.90/131.97 101.15/101.47 /101.24 UPLC 95 .84/109.18/131.25 100.61/100.80/100.69 OT HPLC 41.5 7 /47 .12/57.45 41.15/47 .57 /5 7. 74 99.00/100.96/100.51 UPLC 41.99/47.95/57.34 101.08/101. 76/99.81 TM HPLC 22.81/25 .23/29. 78 23.13/25.50/29.89 101.64/101.07 /100.38 UPLC 22.93/25.10/29.94 100.5 3/99.48/100.54 TS HPLC 31.28/34.21/41.41 31.05/34.77 /45.54 99.26/101.64/100.32 UPLC 31.33/34.56/41.3l 100.16/101.02/99.76 using the proposed HPLC and UPLC methods in this study. The test data corresponded exactly with the indicated ingredients of the cosmetics. The results are tabulated in Table VI. Table VI Determination of Sunscreen Agents in Suncare Products by HPLC and UPLC Label claim % Found % Found Product UV filter (%, w/w) in HPLC* in UPLC* Cream A IMC 2.0 2.1 2.1 OMC 5.0 5.3 5.3 OS 4.5 4.7 4.7 OT 2.0 2.2 2.2 Cream B IMC 2.0 2.0 2.0 OMC 5.7 5.8 5.7 TM 1.0 1.1 1.0 TS 2.0 2.0 2.0 Lotion A IMC 2.0 2.1 2.1 OMC 7.0 7.2 7.1 Lotion B IMC 2.0 2.2 2.1 OMC 5.0 5.1 5.1 TM 1.0 1.1 1.1 TS 2.0 2.0 1.9 Foundation A IMC 2.0 2.1 2.0 OMC 5.0 5.0 5.0 TS 3.0 3.2 3.1 Foundation B OMC 3.0 3.2 3.2 TS 6.0 6.4 6.2 Makeup base A IMC 3.0 3.1 3.1 Makeup base B IMC 2.0 2.1 3.1 OMC 7.0 7.2 7.0 OS 4.5 4.6 4.5 TS 3.0 3.1 3.1 Lipstick A IMC 2.0 1.9 2.0 OMC 5.0 5.0 5.1 Lipstick B OMC 7.0 7.3 7.2 * Values are the average of 3x determination.
480 JOURNAL OF COSMETIC SCIENCE CONCLUSIONS The proposed HPLC and UPLC methods have been evaluated over specificity, linearity, repeatability, system stability, intermediate precision, and accuracy. They were proved to be convenient and effective for the determination of six sunscreen agents of different chemical behaviors in suncare products. With the proposed HPLC and UPLC methods, TM and TS can be determined along with OMC, IMC, OS, and OT in a single analysis. Fast and efficient separation of six sunscreen agents and the simplification of sample preparation are also possible with the methods. The proposed methods can provide high accuracy and high productivity in the quality control of six sunscreen agents in suncare products. REFERENCES (1) E. Chatelain and B. Gabard, Photochem. Photobiol. 74, 401-406 (2001). (2) D.R. English, B. K. Armstrong, A. Kricker, et al., Cancer Causes Control, 8, 271-283 (1997). (3) F. R. De Gruijl, Skin cancer and solar UV radiation, Eur.]. Cancer, 35, 2003-2009 (1999). (4) J. Krutmann, Ultraviolet A radiation-induced biological effects in human skin: Relevance for photo- aging and photodermatosis,J. Dermatol. Sci., 23, S22-S26 (2000). (5) B. Musial and J. Sherma,J. Planar Chromatogr. Mod. TLC, 10, 368 (1997). (6) D. D. Orsi, G. Giannini, L. Gagliardi, D. Tonelli, et al., Chromatographia, 64, 509-515 (2006). (7) S. Santo, Determination of sunscreen agents in cosmetic products by supercritical fluid extraction and high-performance liquid chromatography,]. Chromatogr. A, 870, 199-205 (2000). (8) A. Chisvert, M. C. Pascual-Marti, and A. Salvador, Determination of the UV filters worldwide au thorised in sunscreens by high-performance liquid chromatography: Use of cyclodextrins as mobile phase modifier,]. Chromatogr. A, 921, 207-215 (2001). (9) C. G. Smyrniotakis and H. A. Archontaki,J. Chromatogr. A, 1031, 319-324 (2004). (10) S. Simeoni, R. Tursilli, A. Bianchi, and S. Scalia, Assay of common sunscreen agents in suncare products by high-performance liquid chromatography on a cyanopropyl-bonded silica column,]. Pharm. Biomed. Anal., 38, 250-255 (2005). (11) D. J. Schakel, D. Kalsbeek, and K. Boer, Determination of sixteen UV filters in suncare formulations by high-performance liquid chromatography,]. Chromatogr. A, 1049, 127-130 (2004). (12) K. Ikeda, S. Suzuki, and Y. Watanabe, Determination of sunscreen agents in cosmetic products by gas chromatography and gas chromatography-mass spectrometry,]. Chromatogr A, 513, 321-326 (1990). (13) C. G. Hayden, M. S. Roberts, and H. A. E. Benson, Sunscreens: Are Australians getting the good oil?, Aust. N.Z.]. Med, 28, 639-646 (1998). (14) D. Steinberg, Cosmet. Toiletr., 118, 81 (2003). (15) European Economic Community Council Directive. 76/768. Annex VII (1976). (16) S. A. C. Wren, Peak capacity in gradient ultra performance liquid chromatography (UPLC),j. Pharm. Biomed. Anal., 38, 337-343 (2005).
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