Determination of glutathione in pharmaceuticals and cosmetics by HPLC with UV and fluorescence detection

Summary A selective HPLC determination of reduced glutathione (GSH) in pharmaceutical and cosmetic formulations is described based on prechromatographic derivatization with 4-(6-methylnaphthalen-2-yl)-4-oxo-2-buteneoic acid. The derivatization reaction is rapid under mild reaction conditions (10 min at ambient temperature and pH 7.5) and the excess reagent can be removed by liquid-liquid extraction. The thiol adducts were chromatographed on a C-8 column using 0.05 M triethylammonium phosphate (pH 4.0) — acetonitrile 68∶32 (v/v), as the mobile phase; UV and fluorescence detection (l_em 450 nm, l_exc 300 nm) were both used. The structure of the thiol adducts was confirmed by¹H and¹³C NMR spectra using sodium methanethiolate as thiol nucleophile. This work constitutes part of the thesis for the “Dottorato di ricerche” of Dr. Roberto Gotti.     

超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱法快速检测化妆品中22种功效成分北大核心CSCD

建立了超高效液相色谱-线性离子阱/静电场轨道阱高分辨质谱法同时测定化妆品中的22种功效成分。样品采用甲醇超声提取,C18色谱柱(100 mm×2.1 mm,1.8μm)分离,以0.1%(v/v)甲酸水溶液和乙腈为流动相进行梯度洗脱。在正离子模式下,以保留时间和一级母离子精确质量数进行定量分析,以高能碰撞诱导解离获得的二级碎片离子精确质量数进行确证。结果表明,该方法线性关系良好,检出限(LOD)为0.003~2.01 mg/kg;定量限(LOQ)为0.02~4.36 mg/kg;水、乳、霜3种基质中3个添加水平的回收率范围为63.2%~125.1%,相对标准偏差为0.18%~10.9%。对标示含有烟酰胺、抗坏血酸葡糖苷、咖啡因、泛醇及甘草类(光果甘草根茎叶、甘草根、胀果甘草根)、麦冬根、人参根、黄芪根、虎杖根、苦参根、地黄根、积雪草、茶叶提取物的54批样品进行检测,标示单体功效成分的样品均有检出,标示不同植物提取物的46批样品中,24批检出植物提取物的功效成分。该方法简便快速、定性定量可靠,适用于化妆品中22种功效成分的定量测定。     

气相色谱-质谱法同时测定化妆品中18种氯代烃类有机溶剂

建立了同时测定化妆品中18种氯代烃类有机溶剂的气相色谱-质谱(GC-MS)检测方法。样品在饱和氯化钠溶液中由正十四烷振荡提取后,以Agilent J&W DB-624超高惰性毛细管柱(30 m×0.25 mm×1.4 μm)为分离色谱柱进行分析,以电子轰击(EI)源、SIM模式进行质谱监测,外标法定量。结果表明,18种化合物在19 min内完成色谱分离分析,检出限(LOD, S/N=3)和定量限(LOQ, S/N=10)分别为0.033~0.049 mg/L和0.10~0.15 mg/L, 18种氯代烃类有机溶剂在0.2~100 mg/L线性范围内线性关系良好,相关系数(R²)均不小于0.9992。以阴性样品口红(固体)和漱口水(液体)为样品基质,在不同添加水平下,18种氯代烃类有机溶剂的平均回收率分别为92.4%~103.1%和93.3%~102.4%,相对标准偏差(RSD, n=6)分别为3.1%~5.3%和2.8%~5.4%。采用该方法对115个化妆品样品进行测定,3个指甲油样品均检测出四氯乙烯,测定值为11.4~42.0 g/kg。研究建立的方法采用高沸点溶剂作为进样溶剂,取消溶剂延迟时间,使只能在溶剂延迟时间出峰的化合物得到有效色谱分离,分析时间短,且重复性好,灵敏度高,可同时检测各种化妆品中多种氯代烃类有机溶剂。该方法的建立为我国化妆品中氯代烃类有机溶剂检测标准的制订和质量安全监控提供了参考。     

Multi-Target Strategy to Uncover Unexpected Compounds in Rinse-Off and Leave-On Cosmetics

The wide range and complexity of cosmetic formulations currently available on the market poses a challenge from an analytical point of view. In addition, during cosmetics manufacture, impurities coming from raw materials or formed by reaction of different organic compounds present in the formulation may be present. Their identification is mandatory to assure product quality and consumer health. In this work, micro-matrix solid-phase dispersion (μMSPD) is proposed as a multi-target sample preparation strategy to analyze a wide number of unexpected families of compounds including polycyclic aromatic hydrocarbons (PAHs), pesticides, plasticizers, nitrosamines, alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analytical determination was performed by gas chromatography-mass spectrometry (GC-MS) for the determination of 51 target compounds in a single run, whereas liquid chromatography tandem mass spectrometry (LC-MS/MS) was employed for the analysis of six APs and APEOs. Both methodologies were successfully validated in terms of linearity, accuracy, and precision in leave-on and rinse-off cosmetics. Limits of detection (LODs) were calculated in the low ng g⁻¹, showing their suitability to determine trace levels of impurities and banned compounds with different chemical natures, providing useful tools to cosmetic control laboratories and companies.     

超高效液相色谱-串联质谱法测定化妆品中新型糖皮质激素氯倍他索乙酸酯

采用超高效液相色谱-串联质谱法建立了化妆品中氯倍他索乙酸酯的检测方法,适用于膏霜乳类、凝胶类、泥类、贴膜类和液体(水)类5种常见化妆品基质。对影响被测物质的前处理方法、提取溶剂、提取时间等因素和色谱、质谱条件等进行了考察。最终建立方法为样品经乙腈涡旋分散、超声提取、过滤后用超高效液相色谱-串联质谱仪测定,采用Waters CORTECS C₁₈色谱柱(150 mm×2.1 mm, 2.7 μm),以水和乙腈作为流动相分离,在电喷雾正离子模式(ESI⁺)下,以多反应监测(MRM)方式采集,采用基质匹配标准曲线进行定量分析。5种基质类型下,被测物质在0.9~37 μg/L的范围内线性拟合良好,线性相关系数(R²)均超过0.99。方法的检出限为0.03 μg/g,定量限为0.09 μg/g。在定量限、2倍定量限和10倍定量限3个水平下的加标回收率试验中,被测物质在5种基质中的回收率范围为83.2%~103.2%,相对标准偏差(RSD, n=6)范围为1.4%~5.6%。采用该方法对不同基质类型的化妆品样品进行筛查,共发现5批阳性样品,其中氯倍他索乙酸酯的含量范围为1.1~48.1 μg/g。该方法操作简单,灵敏可靠,适用于不同基质类型化妆品的高通量定性定量筛查分析,为监测化妆品中的非法添加提供了技术支持及理论依据。     

化妆品样品前处理与检测技术研究进展

随着我国经济和人民生活水平的不断提高,作为日常消费品的化妆品产业发展迅猛,其安全性日益受到广泛关注。随之而来的化妆品检测量的大幅增长对检测技术提出了更高的要求。传统样品前处理和检测技术因有机试剂消耗量大,检测通量低、检测周期长已无法满足当前绿色化学发展和高通量检测的需求。对此,科研人员开发了一系列环境友好型前处理技术以及高通量现场快速检测方法,为化妆品质量安全保驾护航。该文综述了当前化妆品样品前处理及检测技术的研究进展,并展望了其发展趋势和应用前景,以期为从事化妆品检测的科研和检验人员提供技术参考。     

化妆品中氯胺T的超声辅助水解/液相色谱检测及质谱确证

建立了化妆品中氯胺T的超声辅助水解/高效液相色谱分析方法,并采用液相色谱-串联质谱进行确证.将不同类型(膏霜、水剂、散粉、香波、牙膏)化妆品样品分散于盐酸溶液中,超声波辅助提取并水解氯胺T,水解液用乙醚萃取后,采用高效液相色谱分离分析,以Agilent Extend C18 (4.6 mm×250 mm,5μm)为色谱...     

Recent Advances in Sample Preparation for Cosmetics and Personal Care Products Analysis

The use of cosmetics and personal care products is increasing worldwide. Their high matrix complexity, together with the wide range of products currently marketed under different forms imply a challenge for their analysis, most of them requiring a sample pre-treatment step before analysis. Classical sample preparation methodologies involve large amounts of organic solvents as well as multiple steps resulting in large time consumption. Therefore, in recent years, the trends have been moved towards the development of simple, sustainable, and environmentally friendly methodologies in two ways: (i) the miniaturization of conventional procedures allowing a reduction in the consumption of solvents and reagents; and (ii) the development and application of sorbent- and liquid-based microextraction technologies to obtain a high analyte enrichment, avoiding or significantly reducing the use of organic solvents. This review provides an overview of analytical methodology during the last ten years, placing special emphasis on sample preparation to analyse cosmetics and personal care products. The use of liquid–liquid and solid–liquid extraction (LLE, SLE), ultrasound-assisted extraction (UAE), solid-phase extraction (SPE), pressurized liquid extraction (PLE), matrix solid-phase extraction (MSPD), and liquid- and sorbent-based microextraction techniques will be reviewed. The most recent advances and future trends including the development of new materials and green solvents will be also addressed.     

实时直接分析-高分辨质谱法快速检测化妆品中的氯霉素

建立了一种用于化妆品中氯霉素快速检测的实时直接分析-高分辨质谱法。样品以乙醇为提取溶剂超声、振荡萃取,纯水稀释1倍后,采用12 Dip-it Samplers模式进样,在负离子模式下,以全扫描-平行反应监测(Full MS-PRM)模式进行直接定量分析。离子化温度为500 ℃,进样速度为0.3 mm/s。结果表明,氯霉素在0～100 mg/L范围内具有良好的线性关系,相关系数(r)为0.998　4,方法定量下限(LOQ)为3.0 mg/kg。在3.0、6.0、30 mg/kg 3个加标水平下的回收率为70.2%～119%,相对标准偏差(RSD)为8.4%～17%。该方法具有样品前处理简单、分析速度快、基质干扰小等优点,适用于化妆品中氯霉素的快速检测。     

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。