高效液相色谱法同时测定防晒类化妆品中15种紫外线吸收剂

建立了一种反相高效液相色谱同时测定防晒类化妆品中15种紫外线吸收剂的分析方法。化妆水、乳液、膏霜和蜡质样品中首先加入四氢呋喃(含2 g/L氢氧化铵),涡旋、振荡、混匀(若蜡质样品仍分散不完全,可超声振荡加热至50 ℃),再加入80%(v/v)甲醇水溶液振荡混匀、超声提取、离心、过滤后,采用XTerra MS C₁₈柱分离,经水(含0.1%(v/v)甲酸)和甲醇(含0.1%(v/v)甲酸)梯度洗脱,以二极管阵列检测器检测,检测波长为280 nm和311 nm,外标法定量。实验中对不同基质类型样品的前处理条件(样品分散溶剂、萃取溶剂和萃取时间等)进行了重点优化。结果表明,15种紫外线吸收剂在各自的线性范围内呈良好的线性关系(r²≥0.9991),方法的定量限为1.2~5.1 μg/g,在低、中、高3个添加水平下的回收率为84.2%~100.7%,相对标准偏差(RSD)为0.9%~9.5%。该分析方法分离效果好、灵敏度高、定量准确,可用于防晒类化妆品的实际检测。     

高效液相色谱法测定防晒化妆品中甲酚曲唑和甲酚曲唑三硅氧烷

建立了防晒化妆品中甲酚曲唑和甲酚曲唑三硅氧烷的反相高效液相色谱分析测定方法。防晒化妆品经水-四氢呋喃-甲醇溶剂提取,过滤,用Agilent C18柱(250 mm×4.6 mm,5μm)分离,以甲酸/水(0.1%)-甲醇-四氢呋喃(2:9:9,V/V/V)为流动相等度洗脱,检测波长为340 nm,高效液相色谱-二极管阵列检测器(HPLC-DAD)进行定性定量分析。两种防晒剂质量浓度在5.0~500 mg/L范围内,线性关系良好,相关系数0.999,定量限为5.0 mg/kg,回收率达到90%~110%,相对标准偏差(n=6)小于10%。方法适用于防晒化妆品中甲酚曲唑和甲酚曲唑三硅氧烷的同时测定。     

气相色谱-质谱法测定化妆品中13种防晒剂

防晒剂广泛应用于化妆品中,是目前化妆品监管的重点。建立了同时测定化妆品中13种防晒剂的气相色谱-质谱(GC-MS)方法。化妆品样品经二氯甲烷提取后,涡旋超声后稀释。采用程序升温模式,经HP-5ms毛细管色谱柱(30 m×250 μm×0.25 μm)在30 min内对13种防晒剂实现分离,经电子轰击(EI)源电离后采用选择离子监测模式(SIM)扫描测定,外标法定量。比较了6种常用有机溶剂的基质效应和平均回收率,二氯甲烷的基质效应弱,平均回收率较高。13种防晒剂在相应的线性范围内线性关系良好,相关系数均大于0.998,检出限(LOD, S/N=3)为0.04~0.63 mg/g,定量限(LOQ, S/N=10)为0.12~2.10 mg/g。实验选取了两种基质,在3个水平下验证方法的回收率和精密度,13种防晒剂在霜类基质中的加标回收率为88.7%~103.6%,相对标准偏差(RSD, n=6)为1.7%~4.9%,在乳类基质中的加标回收率为88.4%~102.3%, RSD(n=6)为1.2%~3.9%。美白类化妆品常添加防晒剂成分,为监管盲区,采用该方法检测了5批含有防晒剂的美白类化妆品,其所含5种防晒剂的含量为0.8%~5.2%,符合相关要求。该方法操作简单,灵敏度高,回收率好,测定的13种防晒剂均为我国《化妆品安全技术规范》2015版规定的常用的限用组分,可以用于各类化妆品中13种防晒剂的定性定量测定,为市场监管和实验室检测提供新的技术支持。     

高效液相色谱法测定防晒类化妆品中20种防晒剂的含量

称取混合均匀的防晒类化妆品样品0.200 0g于50mL具塞比色管中,用甲醇-四氢呋喃-水-高氯酸(350+550+100+0.067)溶液溶解,超声提取30min,移取2.0mL上述溶液,用甲醇-四氢呋喃-水-高氯酸(250+450+300+0.2)溶液稀释至10.0mL,经0.45μm滤膜过滤,弃去初虑液至少2mL,取续虑液作为待测液。采用高效液相色谱法测定其中20种防晒剂的含量,利用二极管阵列检测器检测。结果表明:20种防晒剂的质量浓度在一定范围内与其对应的峰面积之间呈线性关系,检出限(3S/N)在0.006 0～0.28mg·L-1之间。以阴性防晒剂化妆品样品为基质,按照标准加入法进行回收试验,回收率在93.2%～107%之间,测定值的相对标准偏差(n=6)在0.10%～1.7%之间。     

超高效液相色谱法测定化妆品中聚硅氧烷-15等7种脂溶性防晒剂的含量

建立了一种超高效液相色谱法测定聚硅氧烷-15等7种脂溶性防晒剂含量的方法,样品使用乙醇-四氢呋喃(体积比3∶1)混合溶剂超声提取,经Waters Symmetry C18(150×4.6 mm, 3.5μm)色谱柱分离,以异丙醇-四氢呋喃(体积比90∶10)-水为流动相进行梯度洗脱,流速0.7 mL/min,柱温为25℃,检测波长311 nm。结果表明,7种脂溶性防晒剂在相应的质量浓度范围内线性关系良好(r≥0.9999),不同基质类型的样品在低、中、高3个浓度水平的平均加标回收率为94.4%～103.0%,相对标准偏差为0.4%～4.4%,检出限和定量限范围分别为0.002%～0.009%和0.005%～0.03%,各成分在48 h内稳定。采用该方法测定市售30批化妆品中的防晒剂,测定结果与《化妆品安全技术规范》(2015版)方法相比,检出的亚甲基双-苯并三唑基四甲基丁基酚、双-乙基己氧苯酚甲氧苯基三嗪等脂溶性防晒剂提取效果优于《规范》方法。该方法准确、快速、灵敏度高、稳定性好,可用于化妆品中脂溶性防晒剂的测定。     

QuEChERS结合高效液相色谱-串联质谱法测定饲料中的18种β-兴奋剂

建立了饲料中克仑特罗、莱克多巴胺、喷布特罗、妥布特罗等18种β-兴奋剂的QuEChERS结合高效液相色谱-串联质谱的检测方法。饲料样品加水分散后经4%(v/v)氨水乙腈提取,加入25 mg十八烷基硅烷(C18)和50mg N-丙基乙二胺(PSA)吸附剂分散固相萃取净化后,以高效液相色谱-串联质谱进行定性和定量分析。采用Agilent Zorbax Eclipse XDB-C18(50 mm×4.6 mm,1.8μm)分析柱,以甲醇-0.1%(v/v)甲酸水溶液为流动相进行梯度洗脱,串联质谱在多反应监测(MRM)正离子模式下进行检测,基质外标法定量。结果表明,18种待测物在质量浓度为5~200μg/L范围内线性关系良好,相关系数为0.9912~0.9995;在0.05、0.1、0.5 mg/kg 3个浓度加标水平下,饲料中18种β-兴奋剂的平均回收率为78.4%~107.1%,相对标准偏差(RSD)为3.5%~12.3%,定量限(以信噪比≥10计)均为0.05 mg/kg。该方法准确、灵敏,前处理简单,可作为饲料中克仑特罗等18种β-兴奋剂筛选和确认的检测方法。     

高效液相色谱法同时检测化妆品中38种限用着色剂

建立了高效液相色谱法同时测定化妆品中颜料红4等38种限用着色剂的检测方法。样品经四氢呋喃、甲醇、乙酸铵水溶液混合溶剂超声提取后,经离心、氮吹和复溶,于Agilent zorbax SB-Aq色谱柱(150 mm×3.0 mm, 3.5 μm)上进行反相液相色谱分离,以乙腈和含0.075%(v/v)甲酸的30 mmol/L乙酸铵溶液为流动相进行梯度洗脱。选择254、416、484、514、590和620 nm作为检测波长进行定量分析。结果表明:在1~10 mg/L的质量浓度范围内,38种限用着色剂的色谱峰面积与质量浓度呈线性相关,相关系数(r)大于0.999, LOQ值为5~50 μg/g。在100 μg/g和500 μg/g两个加标水平下,各目标化合物回收率均在93.2%~107.6%之间,相对标准偏差(RSD)小于10%(n=6)。该方法简便、快速、灵敏度高、重现性好,适合于化妆品中限用着色剂的定性与定量检测。     

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.     

超高效合相色谱法测定化妆品中7种防晒剂

采用超高效合相色谱法(UPC2)分离和测定化妆品中的7种防晒剂。样品经甲醇-水(8+2)混合液超声提取后,选用Waters Hss C18SB色谱柱分离,以超临界二氧化碳-甲醇混合物为流动相进行梯度洗脱。紫外检测波长为276nm和310nm。7种防晒剂的线性范围均为1.0~80.0mg·L~(-1),检出限(3S/N)均为200mg·kg~(-1)。加标回收率在90.2%~103%之间,测定值的相对标准偏差(n=6)在1.6%~5.2%之间。     

超高效液相色谱-三重四极杆质谱法同时测定美术颜料中33种游离态初级芳香胺

建立了超高效液相色谱-三重四极杆质谱法(UPLC-MS/MS)同时测定水粉画颜料、油画颜料、丙烯画颜料等美术颜料中33种初级芳香胺(PAAs)的检测方法。样品中的初级芳香胺用乙腈提取,经离心分离、氮吹浓缩后,以甲醇-水(1:9, v/v)定容至2 mL, 0.22 μm膜过滤后上机检测。采用BEH Phenyl柱(100 mm×2.1 mm, 1.7 μm),以含0.07%(v/v)甲酸的甲醇溶液-水(1:9, v/v)为流动相,梯度洗脱分离,UPLC-MS/MS多反应监测模式(MRM)检测,同位素内标法定量。方法优化了色谱分离条件、质谱碎裂电压、碰撞能量等,并考察了提取时间、提取溶剂、浓缩方式等对回收率的影响。33种初级芳香胺的方法检出限为5~50 μg/kg,定量限为15~150 μg/kg, 3种不同基质样品在3个添加水平的平均回收率为70.1%~115.8%,相对标准偏差(RSD)为2.1%~15%。本方法操作简便、快速、准确、灵敏度高,能满足相关测定的要求。     

Simple Extraction and HPLC Determination of UV-A and UV-B Filters in Sunscreen Products

The determination of 11 organic UV filters, worldwide authorised in sunscreen formulations, was performed by HPLC with UV spectrophotometric detection. The filters determined were: phenylbenzimidazole sulfonic acid, benzophenone-4, benzophenone-3, 4-methylbenzylidene camphor, ethylhexyl methoxycinnamate, octocrylene, methylene bis-benzotriazolyl tetramethylbutyl phenol, butyl methoxydibenzoylmethane, bis-ethylhexyloxyphenol methoxyphenyltriazine, ethylhexyl triazone, and diethylamino hydroxybenzoyl hexyl benzoate. Three analytical methods were developed which were based on an ultrasonic extraction of the sample in methanol/1% aqueous acetic acid (70:30, v/v) or dimethylacetamide/propan-2-ol (1:1, v/v) in dependence of the water or fat-solubility of the filter, followed by HPLC separation and quantitation. HPLC was carried out using three different columns and eluting conditions. Standard calibration curves were linear for all the analytes over the concentration range 0.5–100 μg mL^?1. UV measurements were carried out at 280, 300, 310 or 360 nm with the aid of a diode array detector in dependence on the maximum absorption of each filter. Quantitative recoveries were obtained for all sunscreen compounds determined in homemade formulations. The proposed analytical procedure has been successfully applied for the analysis of commercial samples in order to check the presence of UV filters and to determine their concentration.     

Determination of water-soluble UV-filters in sunscreen sprays by liquid chromatography

Liquid chromatography was used for the determination of the three most used water-soluble UV filters, benzophenone-4 (BZ4), terephthalylidene dicamphor sulfonic acid (TDS), and phenylbenzimidazole sulphonic acid (PBS), in aqueous sunscreen sprays. A C18 stationary phase and an isocratic mobile phase of EtOH-20 mM sodium acetate buffer of pH 4.6 (30:70, v/v) were used at a flow-rate of 0.5 ml min(-1). Mobile phase was also used as solvent for samples and standards. UV detection was at 313 nm. The analytical run took 5.5 min. The limits of detection were 0.5, 0.9 and 2 microg ml(-1) for BZ4, TDS and PBS, respectively. The proposed method does not involve highly toxicsolvents.     

Development of a HPLC method for determination of four UV filters in sunscreen and its application to skin penetration studies

This study describes the development, validation and application of a high‐performance liquid chromatography (HPLC) method for the simultaneous determination of the in vitro skin penetration profile of four UV filters on porcine skin. Experiments were carried out on a gel‐cream formulation containing the following UV filters: diethylamino hydroxybenzoyl hexyl benzoate (DHHB), bis‐ ethylhexyloxyphenol methoxyphenyl triazine (BEMT), methylene bis‐ benzotriazolyl tetramethylbutylphenol (MBBT) and ethylhexyl triazone (EHT). The HPLC method demonstrated suitable selectivity, linearity (10.0–50.0 μg/mL), precision, accuracy and recovery from porcine skin and sunscreen formulation. The in vitro skin penetration profile was evaluated using Franz vertical diffusion cells for 24 h after application on porcine ear skin. None of the UV filters penetrated the porcine skin. Most of them stayed on the skin surface (>90%) and only BEMT, EHT and DHHB reached the dermis plus epidermis layer. These results are in agreement with previous results in the literature. Therefore, the analytical method was useful to evaluate the in vitro skin penetration of the UV filters and may help the development of safer and effective sunscreen products.     

反相高效液相色谱法测定化妆品中的防晒剂

用反相高效液相色谱法在２０ｍｉｎ内同时测定化妆品中１１种防晒剂。色谱柱为ＹＷＧ－Ｃ１８柱,流动相为甲醇－四氢呋喃－水－高氯酸（２００２００１６００．１,Ｖ／Ｖ）,检测波长为３１１ｎｍ。报告了对１０３种防晒化妆品测定的结果。     

气相色谱-质谱法测定水体中5种典型有机紫外防晒剂

建立了水体中5种典型有机紫外防晒剂甲氧基肉桂酸乙基己酯（ethylhexyl methoxycinnamate,EHMC）、二苯酮-3（benzophenone-3,BP-3）、4-甲基苄亚基樟脑（4-methylbenzylidene camphor,4-MBC）、奥克立林（octocrylene,OC）和胡莫柳酯（homosalate,HMS）的气相色谱-质谱检测方法。对HMS、BP-3衍生化条件进行了系统的优化。以100 μL双（三甲基硅烷基）三氟乙酰胺（N,O-bis（trimethylsilyl） trifluoroacetamide,BSTFA）为衍生化试剂,在100 ℃下反应100 min。水样固相萃取选用Oasis HLB萃取柱（0.5 g）,洗脱溶剂为乙酸乙酯-二氯甲烷（1：1,v/v）,水样pH 3~5。该方法对5种化合物的检出限范围为0.5~1.2 ng/L,定量限范围为1.4~4.0 ng/L。最佳实验条件下,加标水样回收率为87.85%~102.34%,相对标准偏差（n=3）均小于5%。该方法成功地应用于昆明市第一污水厂进出口水样中目标物质的分析。     

Electrochemical Determination of Sunscreens Agents in Cosmetic Using Square Wave Voltammetry

Sunscreen agents and in particular UV filters are compounds added in different cosmetic formulations, that has the function of preventing damage caused by sun exposition. Therefore, this paper proposes the development of a simple, fast and reliable electroanalytical method utilizing square wave voltammetry (SWV) to the determination of Benzophenone‐3 (BZ‐3), camphor 4‐methylbenzylidene (MBC) and 2‐ethylhexyl‐4‐methoxycinnamate (OMC) in cosmetic samples. The electrochemical system consisted of a cell with three electrodes: work – gold electrode modified, reference – Ag/AgCl_(sat) and auxiliary – platinum, using as supporting electrolyte 4.0 mL of Britton Robinson Buffer 0.04 mol L^?1 (pH=4.0), 1.0 mL of methanol and 5.50×10^?4 mol L^?1 of cetyltrimethylammonium bromide (CTAB). The method was validated using three commercial sunscreen samples and the results showed recovery values between 83 and 98 %. The average values found for the analysed samples were 3.49 % m/m (728 mg L^?1) to BZ‐3, 0.56 % m/m (113 mg L^?1) to MBC and 0.99 % m/m (208 mg L^?1) to OMC. The detection (DL) and quantification (QL) limits were 0.47 mg L^?1 and 1.56 mg L^?1 to BZ‐3, 0.77 mg L^?1 and 2.58 mg L^?1 to MBC and 0.78 mg L^?1 and 2.59 mg L^?1 to OMC, respectively. The sunscreen protector samples were also evaluated by high‐performance liquid chromatography (HPLC) demonstrating a good correlation between the results and compared the results with allowed concentration.     

高效液相色谱法测定化妆品中11种二苯酮类紫外线吸收剂

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0.22 μm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4.0~30 μg/g,方法的定量限为15~100 μg/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2785 μg/g和2106 μg/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。     

Development of a fully automated sequential injection solid-phase extraction procedure coupled to liquid chromatography to determine free 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid in human urine

2-Hydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid, commonly known as benzophenone-3 (BZ3) and benzophenone-4 (BZ4), respectively, are substances widely used as UV filters in cosmetic products in order to absorb UV radiation and protect human skin from direct exposure to the deleterious wavelengths of sunlight. As with other UV filters, there is evidence of their percutaneous absorption.This work describes an analytical method developed to determine trace levels of free BZ3 and BZ4 in human urine. The methodology is based on a solid-phase extraction (SPE) procedure for clean-up and pre-concentration, followed by the monitoring of the UV filters by liquid chromatography-ultraviolet spectrophotometry detection (LC-UV). In order to improve not only the sensitivity and selectivity, but also the precision of the method, the principle of sequential injection analysis was used to automate the SPE process and to transfer the eluates from the SPE to the LC system. The application of a six-channel valve as an interface for the switching arrangements successfully allowed the on-line connection of SPE sample processing with LC analysis.The SPE process for BZ3 and BZ4 was performed using octadecyl (C18) and diethylaminopropyl (DEA) modified silica microcolumns, respectively, in which the analytes were retained and eluted selectively. Due to the matrix effects, the determination was based on standard addition quantification and was fully validated. The relative standard deviations of the results were 13% and 6% for BZ3 and BZ4, respectively, whereas the limits of detection were 60 and 30 ng mL⁻¹, respectively. The method was satisfactorily applied to determine BZ3 and BZ4 in urine from volunteers that had applied a sunscreen cosmetic containing both UV filters.     

Sequential injection analysis for benzophenone-4 and phenylbenzimidazole sulphonic acid in sunscreen sprays by solid-phase extraction coupled with ultraviolet spectrometry

A sequential injection UV method was developed to determine benzophenone-4 (BZ4) and phenylbenzimidazole sulphonic acid (PBS) simultaneously, these being the most commonly used UV-filters in aqueous formulations used as sunscreen sprays. The selective elution of both was performed by on-line solid-phase extraction, by retention on a SAX microcolumn and separation by varying the pH of elution. The sensitivity obtained was 0.042±0.001 ml μg⁻¹ for PBS and 0.0159±0.0003 ml μg⁻¹ for BZ4. The limit of detection was 1.6 μg ml⁻¹ for PBS and 0.6 μg ml⁻¹ for BZ4. The R.S.D. of the results was 1-6% for PBS and 1-12% for BZ4. The method was validated using commercial sunscreen formulations with concentrations determined by a liquid chromatographic procedure. The two procedures gave comparable results. Automation of the method means the amount of reagents used and residues generated are decreased. The system allows the required analysis sequence to be programmed using suitable software.