Analysis of vitamin E in commercial cosmetic preparations by HPLC

Aly Nada; Yellela S. R. Krishnaiah; Abdel-Azim Zaghloul; Ibrahim Khattab

HPLC ANALYSIS OF VITAMIN E IN COSMETICS 365 (13) International Conference on Harmonization (ICH) of Technical Requirements for Registration of Phar- maceuticals for Human Use, Harmonized Triplicate Guideline on Validation of Analytical Procedures: Meth- odology. Recommended for Adoption at Step 4 of the ICH Process by the ICH Steering Committee, IFPMA, Switzerland, November 1996. (14) C. Molto-Puigmarti, A. I. Castellote, and M. C. Lopez-Sabater, Ultra-high-pressure liquid chromato- graphic method for the analysis of tocopherols in human colostrum and milk, J. Chrom. A, 1216, 4388–4394 (2009).

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HPLC ANALYSIS OF VITAMIN E IN COSMETICS 365 (13) International Conference on Harmonization (ICH) of Technical Requirements for Registration of Phar- maceuticals for Human Use, Harmonized Triplicate Guideline on Validation of Analytical Procedures: Meth- odology. Recommended for Adoption at Step 4 of the ICH Process by the ICH Steering Committee, IFPMA, Switzerland, November 1996. (14) C. Molto-Puigmarti, A. I. Castellote, and M. C. Lopez-Sabater, Ultra-high-pressure liquid chromato- graphic method for the analysis of tocopherols in human colostrum and milk, J. Chrom. A, 1216, 4388–4394 (2009).

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J. Cosmet. Sci., 61, 367–376 (September/October 2010) 367 High-performance thin-layer chromatographic determination of ketoconazole in pharmaceutical formulations SUWANNA SAYSIN, BOONSOM LIAWRUANGRATH, and SAISUNEE LIAWRUANGRATH, Department of Pharmaceutical Science, Faculty of Pharmacy (S.S., B.L.) and Department of Chemistry, Center for Innovation in Chemistry, and Institute for Science and Technology Research and Development, Faculty of Science (S.L.), Chiang Mai University, Chiang Mai 50200, Thailand. Accepted for publication June 30, 2010. Synopsis A high-performance thin-layer chromatographic method was developed for the determination of ketoconazole. The sample was separated on a silica gel 60 F254 plate and developed in ethanol-acetone-1.0 mol l-1 H2SO4 by means of an automatic multiple-development system. The area of the spot was quantifi ed by a TLC scanner at a wavelength of 298 nm. A linear calibration curve was established over the range of 3–20 mg/ml of ketocon- azole, with a correlation coeffi cient of 0.9992. The relative standard deviations for intraday and interday preci- sions, for three replicate determinations, were found to be 1.72% and 0.69% for 5 mg/ml and 2.18% and 0.94% for 10 mg/ml of ketoconazole, respectively. The average percentage recoveries of ketoconazole shampoos (Nora, Kenalyn, and Nizoral) and ketoconazole creams (Nizoral, Fungasin, and Ketazon) were found to be 96.10, 97.06, and 99.58, and 96.77, 97.26, and 95.74, respectively. This method has been applied to the de- termination of ketoconazole in various pharmaceutical dosage forms. Common excipients in formulations do not interfere. This method is simple, precise, accurate, and inexpensive. It should be used for routine analysis. INTRODUCTION Ketoconazole (cis-1-acetyl-4-[4-2-(2,4-di-chlorophenyl)-2-(1H-imidazole-1-yl methyl- 1,3-dioxolan-4-yl] methoxy piperazine) is an imidazole antifungal agent (Figure 1) (1). As with other imidazoles, it has a fi ve-membered ring structure containing two nitrogen atoms. Ketoconazole is available in many drug dosage treatment forms: cream, sham- poo, solution, gel/jelly, and foam. The side effects of ketoconazole treatment products are rash, itching, nausea, vomiting, abdominal pain, headache, dizziness, fatigue, im- potence, and blood count abnormalities (1). Rarely do the treatment products of keto- conazole have serious allergic reactions (anaphylaxis). Ketoconazole 2% shampoo is used to treat dandruff and it is used to treat “sun fungus” (4–5). Ketoconazole sham- poos may cause abnormal hair texture, scalp pustules (pimples), dry skin, and itching. There may also be oiliness and dryness of the hair and scalp. Rarely, there may be some Address all correspondence to Boonsom Liawruangrath.

JOURNAL OF COSMETIC SCIENCE 368 hair loss. Ketoconazole is the only member of the immidazole class that is currently used for treatment of systemic infections. Ketoconazole was more widely used before the development of newer, less toxic, and more effective triazole compounds, fl uconazole and itraconazole, and its use has now been limited. It now appears as an alternative drug for specifi c indications. Ketoconazole works principally by inhibition of cytochrome P450 14a-demethylase (P45014DM). This enzyme is in the sterol biosynthesis pathway that leads from lanosterol to ergosterol (2). The affi nity of ketoconazole for fungal cell mem- branes is less than that of fl uconazole and itraconazole. Ketoconazole has thus more po- tential to affect mammalian cell membranes and to induce toxicity (3). The offi cial method normally involves titration in non-aqueous solvent (4–5). Various analytical methods have been reported for the determination of ketoconazole. They are spectrophotometric methods (6–11,13,14), spectrofl uorimetric methods (12), high-per- formance liquid chromatography (15–28), the stripping voltammetric and polarographic method (24), capillary zone electrophoresis (30), and high-performance thin-layer chro- matography (31,32). Very few high-performance thin-layer chromatographic methods (HPTLC) have been reported in the literature and there is no report on the determination of this drug in shampoo formulations. It has the advantages of being sensitive, selective, rapid, accurate and reproducible. The HPTLC method can be used for identifi cation and for control of batch-to-batch consistency in the stability testing of drugs and for purposes of control throughout the entire manufacturing process of drugs, as well as for quality control of the fi nished product. This communication describes the development of the HPTLC method and its applica- tions to the quantitative analysis of ketoconazole in pharmaceutical treatment products such as anti-dandruff shampoos and creams. EXPERIMENTAL REAGENTS AND CHEMICALS Ketoconazole (reference standard assay ³ 98%, Sigma, Switzerland), ethanol, acetone, and ethyl acetate (BDH Laboratory Supplies, England), glacial acetic acid, hydrochloric acid, and sulfuric acid (Farmitalia Carlo Erba, Italy) were used. Ethanol-acetone-1.0 mol/l H2SO4 (80:10:10, v/v/v) was the solvent used for TLC development. The preparation of standard and sample solutions was as follows: Preparation of standard solutions. The required quantities of the ketoconazole standard were accurately weighed and dissolved in ethanol to a fi nal concentration of 1000 mg/ml. Figure 1. Structure of ketoconazole.

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J. Cosmet. Sci., 61, 367–376 (September/October 2010) 367 High-performance thin-layer chromatographic determination of ketoconazole in pharmaceutical formulations SUWANNA SAYSIN, BOONSOM LIAWRUANGRATH, and SAISUNEE LIAWRUANGRATH, Department of Pharmaceutical Science, Faculty of Pharmacy (S.S., B.L.) and Department of Chemistry, Center for Innovation in Chemistry, and Institute for Science and Technology Research and Development, Faculty of Science (S.L.), Chiang Mai University, Chiang Mai 50200, Thailand. Accepted for publication June 30, 2010. Synopsis A high-performance thin-layer chromatographic method was developed for the determination of ketoconazole. The sample was separated on a silica gel 60 F254 plate and developed in ethanol-acetone-1.0 mol l-1 H2SO4 by means of an automatic multiple-development system. The area of the spot was quantifi ed by a TLC scanner at a wavelength of 298 nm. A linear calibration curve was established over the range of 3–20 mg/ml of ketocon- azole, with a correlation coeffi cient of 0.9992. The relative standard deviations for intraday and interday preci- sions, for three replicate determinations, were found to be 1.72% and 0.69% for 5 mg/ml and 2.18% and 0.94% for 10 mg/ml of ketoconazole, respectively. The average percentage recoveries of ketoconazole shampoos (Nora, Kenalyn, and Nizoral) and ketoconazole creams (Nizoral, Fungasin, and Ketazon) were found to be 96.10, 97.06, and 99.58, and 96.77, 97.26, and 95.74, respectively. This method has been applied to the de- termination of ketoconazole in various pharmaceutical dosage forms. Common excipients in formulations do not interfere. This method is simple, precise, accurate, and inexpensive. It should be used for routine analysis. INTRODUCTION Ketoconazole (cis-1-acetyl-4-[4-2-(2,4-di-chlorophenyl)-2-(1H-imidazole-1-yl methyl- 1,3-dioxolan-4-yl] methoxy piperazine) is an imidazole antifungal agent (Figure 1) (1). As with other imidazoles, it has a fi ve-membered ring structure containing two nitrogen atoms. Ketoconazole is available in many drug dosage treatment forms: cream, sham- poo, solution, gel/jelly, and foam. The side effects of ketoconazole treatment products are rash, itching, nausea, vomiting, abdominal pain, headache, dizziness, fatigue, im- potence, and blood count abnormalities (1). Rarely do the treatment products of keto- conazole have serious allergic reactions (anaphylaxis). Ketoconazole 2% shampoo is used to treat dandruff and it is used to treat “sun fungus” (4–5). Ketoconazole sham- poos may cause abnormal hair texture, scalp pustules (pimples), dry skin, and itching. There may also be oiliness and dryness of the hair and scalp. Rarely, there may be some Address all correspondence to Boonsom Liawruangrath.

JOURNAL OF COSMETIC SCIENCE 368 hair loss. Ketoconazole is the only member of the immidazole class that is currently used for treatment of systemic infections. Ketoconazole was more widely used before the development of newer, less toxic, and more effective triazole compounds, fl uconazole and itraconazole, and its use has now been limited. It now appears as an alternative drug for specifi c indications. Ketoconazole works principally by inhibition of cytochrome P450 14a-demethylase (P45014DM). This enzyme is in the sterol biosynthesis pathway that leads from lanosterol to ergosterol (2). The affi nity of ketoconazole for fungal cell mem- branes is less than that of fl uconazole and itraconazole. Ketoconazole has thus more po- tential to affect mammalian cell membranes and to induce toxicity (3). The offi cial method normally involves titration in non-aqueous solvent (4–5). Various analytical methods have been reported for the determination of ketoconazole. They are spectrophotometric methods (6–11,13,14), spectrofl uorimetric methods (12), high-per- formance liquid chromatography (15–28), the stripping voltammetric and polarographic method (24), capillary zone electrophoresis (30), and high-performance thin-layer chro- matography (31,32). Very few high-performance thin-layer chromatographic methods (HPTLC) have been reported in the literature and there is no report on the determination of this drug in shampoo formulations. It has the advantages of being sensitive, selective, rapid, accurate and reproducible. The HPTLC method can be used for identifi cation and for control of batch-to-batch consistency in the stability testing of drugs and for purposes of control throughout the entire manufacturing process of drugs, as well as for quality control of the fi nished product. This communication describes the development of the HPTLC method and its applica- tions to the quantitative analysis of ketoconazole in pharmaceutical treatment products such as anti-dandruff shampoos and creams. EXPERIMENTAL REAGENTS AND CHEMICALS Ketoconazole (reference standard assay ³ 98%, Sigma, Switzerland), ethanol, acetone, and ethyl acetate (BDH Laboratory Supplies, England), glacial acetic acid, hydrochloric acid, and sulfuric acid (Farmitalia Carlo Erba, Italy) were used. Ethanol-acetone-1.0 mol/l H2SO4 (80:10:10, v/v/v) was the solvent used for TLC development. The preparation of standard and sample solutions was as follows: Preparation of standard solutions. The required quantities of the ketoconazole standard were accurately weighed and dissolved in ethanol to a fi nal concentration of 1000 mg/ml. Figure 1. Structure of ketoconazole.

HPLC ANALYSIS OF VITAMIN E IN COSMETICS 363 statistical difference between the two investigated methods of extraction as indicated by t-test (t=0.215 and p=0.834) and the non-parametric Mann-Whitney test ( p=0.814). Fur- thermore, to further assess the extraction effi ciency of method 2, known quantities (2.5 μg) of T and TA were added to a 500-mg sample of the commercial cosmetic product and the percent recovery of T/TA was estimated. The percent recoveries of T and TA with extrac- tion method 2 were 99.05% and 96.01%, respectively (Table VII). Since both methods were of similar extraction effi ciency, only method 2 was applied throughout the present study. The negative effect of hexane may be avoided by evaporating the solvent mixture and reconstituting with methanol. However, method 2 remains simpler, needs less pro- cessing time, and maintains the column's integrity, ultimately with equal extraction effi ciency. In summary, the advantages of the present method in comparison with the previously described method by Guaratini et al. (8) include the following: (a) there is simultaneous determination of both T and TA, which was achieved by modifying the mobile phase (methanol-water, 97:3 %v/v) instead of pure methanol, (b) the previous method was tested in a gel–cream base that does not resemble the complex nature of commercial products, containing diverse oily, fatty, and waxy ingredients, (c) the use of isopropanol as extraction solvent in the reported method (8) was unsuccessful in extraction of T and TA from the preparations tested in the present study, and (d) other reported methods for T and TA analysis in dosage forms like tablets, capsules, injctions, etc. (9) were unsuc- cessful due to the different nature of the matrices compared with cosmetic products. Table VII Extraction Effi ciency by Methanol (method 2) of Commercial Product (C) after Addition of Known Amount of Tocopherol (T) and Tocopherol Acetate (TA) Tocopherol Tocopherol acetate Nominal conc. (μg/ml) Found conc., mean ± S.D (% CV), n = 3 Extraction effi ciency (%) Nominal conc. (μg/ml) Found conc., mean ± S.D (% CV), n = 3 Extraction effi ciency (%) 10 9.905 ± 0.054 (0.55) 99.05 20 19.201 ± 0.44 (2.34) 96.01 Table VI Mean Extraction Effi ciency of Tocopherol (T) and Tocopherol Acetate (TA) From Experimental Cream Formulations Based on Nominal and Found Concentrations (mean ± %RSD) (n=4) Vitamin Method 1 Method 2 Nominal conc. (%) Found conc. (%) Recovery (%) Nominal conc. (%) Found conc. (%) Recovery (%) T 0.5319 0.5312 99.87 0.5319 0.5172 97.24 (4.71) (4.84) TA 0.5394 0.5315 98.54 0.5394 0.5282 97.89 (1.803) (0.809)

JOURNAL OF COSMETIC SCIENCE 364 CONCLUSIONS 1. The described analytical procedure proved to be accurate, precise, and suitable for simultaneous determination of T and TA in real commercial cosmetic products. 2. Both tested methods of extraction proved to be accurate and precise and statistically indifferent for the extraction of T and TA in cosmetic preparations. 3. Methanol alone (method 2) is equally as effi cient as a mixture of methanol with 10% hexane (method 1) in terms of extraction effi ciency. 4. Method 2 is simpler and less time-consuming. 5. Method 2 maintains column integrity and thus is more suitable for routine determi- nation of T and TA in cosmetic preparations. 6. The use of highly non-polar solvents, e.g., hexane, should be avoided unless the ex- tract is evaporated, reconstituted with methanol, and centrifuged before injection into the HPLC column. ACKNOWLEDGMENTS This work was supported by Kuwait University, Research Grant No. [PP01/05]. The authors appreciate the sincere efforts of Dr. F. Bandarkar, Mrs. E. Abraham, Mr. S. Abraham, and Mrs. D. Nabil, as well as those of Mrs. L. Varghese and Mrs. A. Thomas. REFERENCES (1) A. Chiu and A. B. Kimball, Topical vitamins, minerals and botanical ingredients as modulators of envi- ronmental and chronological skin damage, Br. J. Dermatol., 149, 68–69 (2003). (2) F. Nachbar and H. C. Korting, The role of vitamin E in normal and damaged skin, J. Mol. Med., 73, 7–17 (1995). (3) W. Gehring, J. Fluhr, and M. Gloor, Infl uence of vitamin E acetate on stratum corneum hydration, Arzneimittelforschung, 48, 772–775 (1998). (4) H. L. Gensler and M. Magdaleno, Topical vitamin E inhibition of immunosuppression tumorigenesis induced by ultraviolet irradiation, Nutr. Cancer, 15, 97–106 (1991). (5) J. J. Thiele, C. Schroeter, S. N. Hsieh, M. Podda, and L. Packer, The antioxidant network of the stratum corneum, Curr. Probl. Dermatol., 29, 26–42 (2001). (6) J. Z. Huo, H. J. Nelis, P. Lavens, P. Sorgeoloos, and A. P. De Leenheer, Simultaneous determination of α-tocopheryl acetate and tocopherols in aquatic organisms and fi sh feed, J. Chrom. B, 724, 249–255 (1999). (7) S. Wielinski and A. Olszanowski, Development and validation of HPLC method for simultaneous determination of fat soluble vitamins in capsules, J. Liq. Chrom. Rel. Technol., 24, 201–213 (2001). (8) T. Guaratini, M. D. Gianeti, and P. M. Campos, Stability of cosmetic formulations containing esters of vitamins E and A: Chemical and physical aspects, Int. J. Pharm., 327, 12–16 (2006). (9) F. G. Ruperes, D. Martin, E. Herrera, and C. Barbas, Chromatographic analysis of α-tocopherol and re- lated compounds in various matrices, J. Chrom. A, 935, 45–69 (2001). (10) M. M. Almeida, J. M. P. Alves, D. C. S. Patto, C. R. R. C. Lima, J. S. Qenca-Guillen, M. I. R. M. Santoro, and E. R. M. Kedor-Hackmann, Determination of tocopheryl acetate and ascorbyl tetraisopalmitate in cosmetic formulations by HPLC, Int. J. Cosmet. Sci., 31, 445–450 (2009). (11) A. Dingler, R. P. Blum, H. Niehus, R. H. Muller, and S. Gohla, Solid lipid nanoparticles (SLNTM/ Lipopearls™) a pharmaceutical and cosmetic carrier for the application of vitamin E in dermal products, J. Microencapsul., 16, 751–767 (1999). (12) A. A. Zaghloul, H. H. El-Shattawy, A. A. Kassem, E. A. Ibrahim, I. K. Reddy, and M. A. Khan, Honey, a prospective antibiotic: Extraction, formulation, and stability studies, Pharmazie, 56, 643–647 (2001).

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