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建立了化妆品中11种二苯酮类紫外线吸收剂的高效液相色谱分析方法。采用四氢呋喃-甲醇-水或二氯甲烷-水体系提取化妆品中二苯酮类紫外线吸收剂,经离心(5000 r/min),上清液过0.22μm 滤膜后,进入高效液相色谱分析。采用 C18色谱柱进行分离,以0.1%(体积分数)甲酸水溶液(含10 mmol/L 乙酸铵)为流动相 A,以0.1%(体积分数)甲酸甲醇为流动相 B,梯度洗脱。方法加标回收率( n=7)为93.4%~103.8%,相对标准偏差为0.1%~4.2%,方法的检出限为4.0~30μg/g,方法的定量限为15~100μg/g。采用该方法对42种市售化妆品检测分析发现,有5种二苯酮类紫外线吸收剂被检出,其中防晒隔离液中二苯酮-3和香水中二苯酮-2的检出量分别为2785μg/g和2106μg/g。研究结果表明,所建立的方法具有良好的回收率、重现性和较高的灵敏度,可用于化妆品中多种二苯酮类紫外线吸收剂的分析。

A sample preparation and analytical method with liquid-liquid extraction( LLE)and high performance liquid chromatography( HPLC ) was developed to detect 11 benzophenone ultraviolet-filters in cosmetics. The target compounds were extracted by the mixed solutions of tetrahydrofuran ( THF )/methanol/water or dichloromethane/water at proper ratios. The extracts were centrifuged and filtered to remove matrix compounds,and then analyzed by HPLC. The separation of analytes was carried out on a Diamonsil-C18 column( 150 mm × 4. 6 mm,5 μm)with 0. 1%( v/v)formic acid aqueous solution( containing 10 mmol/L ammonium acetate)as mobile phase A and methanol containing 0. 1%(v/v)formic acid as mobile phase B. The spiked recoveries of the method( n=7)were 93. 4%-103. 8% with the relative standard de-viations of 0. 1%-4. 2%. The limits of detection( LODs)were in the range of 4. 0-30 μg/g and the limits of quantitation( LOQs)ranged from 15 to 100 μg/g. The method was applied to the determination of 42 cosmetic samples randomly purchased from the supermarket in Dalian. Five benzophenone series were always detected,in which the content of benzophenone-3 in sun-screen cream and the content of benzophenone-2 in perfume were very high and reached 2 785μg/g and 2 106 μg/g,respectively. The results showed that the developed method is efficient, reliable and sensitive,which can be applied to the determination of benzophenones in cosmetics.

参考文献

[1] Weisbrod CJ;Kunz PY;Zenker AK;Fent K.Effects of the UV filter benzophenone-2 on reproduction in fish.[J].Toxicology and Applied Pharmacology,20073(3):255-266.
[2] Zucchi S;Bluthgen N;Ieronimo A;Fent K.The UV-absorber benzophenone-4 alters transcripts of genes involved in hormonal pathways in zebrafish (Danio rerio) eleuthero-embryos and adult males.[J].Toxicology and Applied Pharmacology,20112(2):137-146.
[3] Kunz PY;Fent K.Estrogenic activity of ternary UV filter mixtures in fish (Pimephales promelas) - an analysis with nonlinear isobolograms.[J].Toxicology and Applied Pharmacology,20091(1):77-88.
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