Ultrasound‐assisted emulsification microextraction coupled with high‐performance liquid chromatography for the simultaneous determination of fragrance allergens in cosmetics and water

A simple, inexpensive, and environmentally friendly method based on ultrasound‐assisted emulsification microextraction followed by solidification of floating organic drop and high‐performance liquid chromatography coupled to diode array detection was developed for the simultaneous determination of 18 potentially allergenic fragrance substances. Several parameters affecting the microextraction process were investigated in detail by the “one‐variable‐at‐a‐time” approach. Optimal conditions were the following: 50 μL of 2‐dodecanol as extraction solvent, 10 mL of sample containing 150 g/L of salt, and 5 min of sonication at 35°C. Under the optimized conditions, method showed good linearity in the selected ranges, with squared correlation coefficients ranging from 0.948 to 0.999. Limits of detection ranged from 0.001 to 0.154 μg/mL and enrichment factors from 9 to 237. Precision of the method, expressed as relative standard deviation, was checked at two levels obtaining good results (3.3–14.4%). Recovery studies were made in baby bath water and in eau de cologne showing acceptable accuracy. Finally, the developed method was successfully applied to different commercial cosmetic and water samples. The most commonly found analyte was linalool followed by cinnamal and lilial. Most of the analyzed samples contained at least one of the target compounds.     

高效液相色谱法测定化妆品中5种荧光增白剂

采用高效液相色谱法测定化妆品中5种荧光增白剂的含量。样品经甲醇超声提取,以C18色谱柱为分离柱,以甲醇和5mmol·L-1四丁基硫酸氢铵溶液以不同比例混合的溶液为流动相进行梯度洗脱,用荧光检测器测定。5种荧光增白剂在一定的质量浓度范围内与其峰面积呈线性关系,方法的测定下限(10S/N)在0.1~2.0μg·g-1之间。以空白样品为基体进行加标回收试验,所得回收率在85.1%~97.1%之间,测定值的相对标准偏差(n=6)在1.4%~5.7%之间。     

高效液相色谱法测定化妆品中7种甘草成分

建立了一种测定化妆品中7种甘草成分的高效液相色谱法。样品经甲醇(7+3)溶液提取,采用ODS-2HYPERSIL色谱柱进行分离,以乙腈-0.05%(φ)磷酸溶液为流动相进行梯度洗脱,采用光电二极管阵列检测器在237nm处进行检测。7种组分的质量浓度在1~200mg·L-1范围内与其峰面积呈线性关系,检出限(3S/N)在0.6~1.0ng之间。对空白样品进行加标回收试验,回收率在92.5%~103%之间,测定值的相对标准偏差(n=6)在0.09%~1.8%之间。     

基于精确质量数筛选的超高效液相色谱-线性离子阱/静电场轨道阱质谱法快速鉴别化妆品中的邻苯二甲酸酯

采用超高效液相色谱-线性离子阱/静电场轨道阱组合式高分辨质谱联用(UPLC-LTQ Orbitrap MS),结合邻苯二甲酸酯(PAEs)精确质量数,建立了快速筛选、定性识别化妆品中PAEs的分析方法。不同种类的化妆品样品经甲醇提取,Waters ACQUITY UPLC BEH C18色谱柱(100×2.1mm,1.7μm)分离,以乙腈-水(含5mmol/L乙酸铵和0.1%甲酸)为流动相梯度洗脱。通过UPLC-LTQ/Orbitrap MS的正离子模式全扫描分析,获得提取物中PAEs化合物母离子和主要碎片离子精确质量数,实现对化妆品的快速筛选。以保留时间和数据依赖扫描(Data Dependent Scan)模式获得的子离子质谱图进行定性确证。所发展的UPLC-LTQ Orbitrap MS方法分离度高、灵敏度好,所考察的14种常见PAEs的精确质量数相对偏差小于5.0×10-6,线性良好,相关系数大于0.99,14种PAEs的检出限在0.05~0.5mg/kg范围内,能满足化妆品实际样品的分析要求。对50种化妆品实际样品进行筛选,结果良好,说明该方法是化妆品中PAEs快速筛选、定性识别的有效方法。     

Determination of Whiteners in Cosmetics by Microdialysis and High-Performance Liquid Chromatography

A simple method was developed for the determination of hydrophilic whitening agents (ascorbyl glucoside, magnesium ascorbyl phosphate, arbutin, hydroquinone, and kojic acid) in bleaching cosmetics by high performance liquid chromatography with electrochemical detection. The samples were prepared using microdialysis and were separated within ten minutes using isocratic elution. Linear calibration was achieved for concentrations between 0.10 and 10.00 micromolar. The limits of detection were from 0.6 to 2.0 nanomolar; the recoveries were between 91.43 and 108.04 percent, and the relative standard deviation was less than 6.88 percent. This method was used to determine whitening compounds in several cosmetics with on-line microdialysis and the zero net flux method. The procedure was fast, simple, selective, and suitable for routine analysis.     

鼠李糖脂应用于微乳毛细管电动色谱快速测定化妆品中激素类物质

采用生物表面活性剂鼠李糖脂建立了无需助表面活性剂的微乳体系,并应用于微乳毛细管电动色谱快速分析化妆品中皮质类激素泼尼松、泼尼松龙和氢化可的松。考察了pH值、鼠李糖脂浓度、离子强度、油相种类和浓度、分离温度、分离电压及进样电压和时间的影响,得出微乳体系最佳组成为0.1%(w/w)鼠李糖脂+0.8%(w/w)正庚烷+99.1%(w/w)硼砂缓冲液(80 mmol/L,pH 9.2)。分离温度20℃,分离电压20kV,电动进样10 kV×3 s,泼尼松、氢化可的松和泼尼松龙在9.4 min内可基线分离。重复进样7次,迁移时间和峰面积的RSD分别小于0.2%和5.0%。3种分析物线性范围均为5～100 mg/L;检出限分别为1.0,1.1和1.3 mg/L(S/N=3)。仅需简单萃取即可用于化妆品样品测定,回收率为81.6%～108%;RSD均小于4.8%。     

Minimum Evaporation Model of Dermatological Delivery Systems. Lamellar Liquid Crystal Formulations Containing Brazilian Nut (Bertholletia excelsa HBK) Vegetable Oil and Guarana Glycolic Extract

Formulations with lyotropic liquid crystals were prepared from a Brazilian nut vegetable oil, guarana extract and combination of sorbitan monooleate (Span 80) and sorbitan monolaurate ethoxylate EO 20 (Tween 20) in the ratio 1:3 (surfactant component) and their physical–chemical aspects and rheological properties were determined. Compositions with liquid crystals were found in the pseudoternary diagram in a surfactant range of 70–90% and polarized light microscopy, small-angle x-ray scattering (SAXS) showed them to be lamellar. The preparations were furthermore characterized rheologically by shear stress shear rate sweeps finding plastic and pseudoplastic behavior without thixotropy. Electric conductivity and pH measurements demonstrated a potential for future application as dermatological delivery system of the active compounds in the Bertholletia excelsa and Paullinia cupana.      

固相萃取-高效液相色谱法测定化妆品中的鞣花酸含量

建立了固相萃取-高效液相色谱法测定化妆品中鞣花酸的含量。样品用甲醇-水(1+1)溶液提取,超声提取10min,以10 000r·min-1转速离心5min,移取5.00mL上清液,经MAX固相萃取柱处理,用甲酸-甲醇(5+95)溶液洗脱。MG C18柱(250mm×4.6mm,5μm)为固定相,以0.2%(体积分数)磷酸-乙腈(18+82)溶液为流动相进行洗脱,检测波长为254nm。线性范围为0.5~100mg·L-1,测定下限(10S/N)为20mg·kg-1,应用该方法对化妆品中鞣花酸的含量进行检测,加标回收率在83.5%~100%之间。     

Trace element determination in beauty products by k0-instrumental neutron activation analysis

A recent study on trace elements in beauty products and cosmetics sold on the Asian market has shown the presence of high levels of U, Th and rare earth elements in so called “Hormesis cosmetics.” For the purpose of comparison, some more information about trace elements in European cosmetics would be useful. In this paper the results obtained using k ₀-standardised Instrumental Neutron Activation Analysis (k ₀-INAA) for more than 20 trace elements in 20 different beauty products collected from the European market are presented. We found traces of Ba, As and Sb which is in breach with European legislation. For some of the other elements like Cr and Co further speciation is needed in order to evaluate their presence in beauty products.     

化妆品中碘丙炔醇丁基氨甲酸酯的高效液相色谱检测及质谱确证

建立了高效液相色谱(HPLC)-二极管阵列检测器(DAD)测定化妆品中碘丙炔醇丁基氨甲酸酯的方法.化妆品样品经超声提取后,高效液相色谱-二极管阵列扫描检测,并在235 nm波长进行分析.用保留时间结合紫外光谱定性,外标法定量,并采用液相色谱-质谱法确证.碘丙炔醇丁基氨甲酸酯的回收率为92.7%～99.8%,相对标准偏差在0.8%～2.1%之间,定量限为20 mg/kg.