Monitoring of para-phenylenediamine Presents in Some Adulterated Henna Preparations

Transcription

1 Middle East Journal of Applied Sciences Volume : 08 Issue :02 April-June 2018 Pages: Monitoring of para-phenylenediamine Presents in Some Adulterated Henna Preparations Naglaa M. Abd ElRahman 1, 2 and Rozan Mahdy Alsourory 1 1 Chemistry Dept., Faculty of Science, Jazan University, KSA, 2 Permanent address: Department of Green Chemistry, National Research Centre, 33 EL Bohouth St. (former El Tahrir St.), Dokki, Giza 12622, Egypt Received: 11 July 2017/ Accepted: 08 Jan. 2018/ Publication date: 10 April 2018 Extracts of fifteen Henna preparations collected from the local markets of Gizan, KSA were chromatographed on silicagel using dichloromethane/ ethyl acetate as an eluent. p-phenylenediamine (2) was detected only in the adulterated samples and in concentrations which are much higher than the ratios recommended for the hair dye cosmetics. This may be the reason of the hazardous affects associated with usage of certain readymade black Henna preparations in changing grey color of hair to black. Key words: Black Henna, Temporary Tattoo, p-phenylenediamine, Katam Introduction Natural Henna (Lawsonia inermis, family Lythraceae) has been used In Egypt, Africa and India as a hair dye since thousands of years (Pan fili et al., 2017; Goldenberg and Jacob, 2015 and Calogiuri et al.,2017). The active ingredient in plant leave which is responsible for the red color is 2-hydroxy-1,4-pnaphthoquinone (Lawsone, 1) (Sedki et al., 2001). Only the ground leaves of henna that can color the skin or hair upon mixing with water or solutions such as tea, coffee, lemon etc., to produce the active coloring material (1), which is gradually released from the wet paste of Henna to bind with the hair or skin protein. O OH O 1 2 (PPD) Depending on the ph of the henna paste medium, the produced color ranges from orange to dark red. Nowadays, however, different readymade preparations of black Henna are found in the markets for the usage as temporary tattooing dyes and to change the grey color of hair to black (Jindal and Davis, 2012; www2.dupont.com and Özkaya and Topkarci, 2016). However, producers of black Henna adulterate natural Henna by certain additives which may be of hazardous nature. As a consequence, certain diseases, strong skin irritations and even cancer, are associated with usage of cosmetics based on Henna (cf. Figure 1) (Boonchai et al., 2016; Choovichian et al., 2015; Skiftesvik et al.,2015; Waton et al., 2017; Chung et al., 2002; Brancaccio et al., 2002; Bernth et al., 2005; Jindal and Davis, 2003; Gaura et al., 2017; Boonsong and Laohakunjit, 2012; Ashraf et al., 1994; Hudari et al., 2014 and Kind et al., 2013). Therefore, the present investigation has been endeavored to unravel the nature of ingredients responsible for the hazardous effects of adulterated Henna samples which were collected from different Gizan local sources. Corresponding Author: Naglaa M. Abd ElRahman naglaa_r@yahoo.com 355

2 Materials and Methods Left hand at presentation Fig. 1: Inflammation caused by Tattoo Left hand at 3 weeks The infrared spectra were recorded in potassium bromide disks on Pye Unicam SP 3300 and Shimadzu FT IR 8101 PC infrared spectrophotometers. The 1 HNMR spectra were recorded on a Varian Mercury VX-300 NMR spectrometer in CDCl3. Chemical shifts were related to TMS. The EI- Ms analysis was carried out using gas chromatography mass spectrometry instrument stands at the Central Laboratory, National Research Center, Egypt with the following specifications. Instrument: a TRACE GC Ultra Gas Chromatographs (THERMO Scientific Corp., USA), coupled with a THERMO mass spectrometer detector (ISQ Single Quadrupole Mass Spectrometer). Mass spectrum was obtained by electron ionization (EI) at 70 ev, using a spectral range of m/z TLC Silica gel 254F (20x20) plates and neutral alumina for column chromatography separation were purchased from Merck Company. TLC plates were monitored by the UV-lamp (365/ standard p- phenylediamine 99% (PPD) was purchased from Sigma- Aldrich. Fifteen samples of Henna were purchased from different places in the local market in Gizan City, KSA. These samples represent all types of Henna (natural henna, black henna, black stones, powder henna for nails and hair dyeing, readymade paste for temporary Tattoo). Sample extraction 50 ml of absolute ethanol was added to 5 g of the sample. After stirring for 2-3 minutes, the sample was filtered off. After removal of the solvent under reduced pressure, the residue was chromatographed on silica gel using dichloromethane / ethyl acetate as an eluent. Fraction (65%- 60% dichloromethane) afforded p-phenylenediamine (PPD, 2). m.p., mixed m.p., comparative IR and 1 H NMR. Thin layer chromatography of different samples versus PPD: The standard PPD and extracts from the different samples of Henna were applied to the silica gel chromatography plates. The plates were eluted with the mobile phase (CH 2Cl 2 and ethyl acetate). Results and Discussion Fifteen Henna cosmetic preparations of different trade marks were collected from Gizan markets. Five grams of the sample was extracted with ethanol. The organic layer left after evaporation of the solvent till dryness, in vacuo, was subjected to column chromatography to give a material proved to be p-phenylenediamine, PPD (2) ( for the following 356

3 reasons: (a) microanalysis and molecular weight determination corresponding to C 6 H 8 N 2, MS: m/z 108, 97% (cf. Figure 2 ). (b) Its IR spectrum (KBr, cm -1 ) was super imposable with that of a reference sample. (c) Its 1 H NMR spectrum (DMSO, δ ppm) showed a D 2 O exchangeable signal at δ 3.48 (4H, s, 2 ). The AB-system of the 1, 4-disubstituted benzene ring (4H) gave two doublets (each with J HH = 7.8 Hz) at δ = 6.55and δ = 7.26 ppm. Besides, its m.p. and mixed m.p. with a reference sample was C. PPD was isolated from ten Henna samples out of 15 samples collected from different shops in the local Gizan market (cf. Table 1). Fig. 2: MS spectrum of PPD extracted from Henna sample Table 1: Percentage PPD (2) in Katam and Henna samples purchased from Gizan local market Sample No. Source Wt %PPD 1 Natural Henna ND 2 Natural Henna ND 3 Natural Henna ND 4 Katam ND 5 Katam Readymade henna paste Readymade henna paste Readymade henna paste Readymade henna paste Black Stone powder Henna for skin powder Henna for skin Black Henna (Powder) Black Henna (Powder) Black Henna (Shampoo) 53.6 ND, not detected 357

4 Conclusion It could be concluded that most of the examined Henna samples contained appreciable amounts of PPD (9.1-88%) due to its high ability to bind with hair protein. Apparently, this may be the causal of the hazardous effect of adulterated Henna samples since PPD is known to possess marked toxic and carcinogenic effects besides; its use is restricted by laws (Sukuroglu et al., 2017 and Brancaccio et al., 2002). However, The European Union does not permit the presence of PPD more than 6% in hair dye products and disallow using PPD on skin, eyelashes and brows. On the other hand, according to Food and Drug Administration (FDA), USA, Canada, New Zealand, and Australia, using PPD on skin, is forbidden. Recommendations It is strongly recommended that people should avoid using adultrated black henna and relevant tattoos. They may cause potent skin / scalp sensitization which may lead to serious carcinogenic consequence due to presence of PPD (2) in their cosmetic preparation Moreover, consumers should ensure the absence of other carcinogenic organic amines ((Jindal and Davis, 2012; www2.dupont.com and Özkaya and Topkarci, 2016) listed in Figure 3 in black Henna and tattoo preparations. 2-naphthalene 4-aminobiphenyl N N 4-dimethylaminoazobenzene 3,2'-4-aminobiphenyl Acknowledgement H 2 N NH benzidine Fig. 3: Some selected carcinogenic organic amine The authors thank The Deanship of Scientific Research Project of Future Scientists, Jazan University, KSA, for funding this study. H 3 C CO References Ashraf, W., S. Dawling and L.J. Farrow, Systemic Paraphenylenediamine (PPD) Poisoning: A Case Report and Review". Human & Experimental Toxicology, 13(3):167. Bernth, N., O.C. Hansen, S.F. Hansen and E. Pedersen, Survey of chemical substances in kohl and henna products. Danish EPA: Survey of Chemical Substances in Consumer Products, No

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