Department of Environmental Science and Analytical Chemistry, Stockholm University, SE-106 91, Sweden.
Department of Environmental Science and Analytical Chemistry, Stockholm University, SE-106 91, Sweden.
J Chromatogr A. 2018 Sep 7;1566:102-110. doi: 10.1016/j.chroma.2018.06.056. Epub 2018 Jun 22.
A two-dimensional non-comprehensive high-performance liquid chromatographic (HPLC) system coupled to electrospray ionization tandem mass spectrometry was developed for the determination of skin allergenic hydroperoxides of limonene and linalool. These compounds are some major components behind skin sensitization and contact (skin) allergy to fragrances. Fragrance hydroperoxides usually occur in complex compositions, often as constituents of the natural essential oils added to a large number of commercial products. Their similarities to interfering compounds, many with identical elemental composition, make the determination difficult even when using selective detection methods like mass spectrometry. In this work, a first-dimension chromatographic heart-cut isolation of the hydroperoxides on a reversed-phase HPLC system was combined with a second-dimension normal-phase HPLC system for separation of the hydroperoxides. The intersystem transfer was made by trapping the heart-cut fraction on a short graphitized carbon column, exchanging the mobile phase and back-flushing the hydroperoxides into the second dimension. Each analysis was performed within 60 min without any pretreatment, except dilution, prior to injection. The obtained instrumental limits of detection (LODs) at a signal-to-noise ratio of 3 were lower than 1.2 ng injected on column and method LODs were below 0.3 ppm. An after-shave product was shown to contain the highest concentrations of the measured hydroperoxides, with 445 ± 23 ppm of total linalool hydroperoxides. This level is likely able to elicit skin reactions in already sensitized individuals.
建立了一种二维非全面高效液相色谱（HPLC）系统，与电喷雾串联质谱联用，用于测定柠檬烯和芳樟醇的皮肤过敏原过氧化物。这些化合物是导致香料皮肤致敏和接触（皮肤）过敏的一些主要成分。香料过氧化物通常存在于复杂的成分中，通常是添加到大量商业产品中的天然精油的成分。即使使用选择性检测方法，如质谱法，由于它们与干扰化合物相似，许多化合物具有相同的元素组成，因此其测定仍然很困难。在这项工作中，首先在反相 HPLC 系统上进行了过氧化物的一维色谱心切割分离，然后与正相 HPLC 系统结合，对过氧化物进行分离。通过将心切割部分捕获在短石墨化碳柱上，实现了体系间转移，然后交换流动相并将过氧化物反冲洗到第二维。每个分析在 60 分钟内完成，除了稀释外，在注入之前不需要任何预处理。在信噪比为 3 时，获得的仪器检测限（LOD）低于 1.2ng 柱上注入，方法 LOD 低于 0.3ppm。事实证明，须后水含有测量过氧化物的最高浓度，总芳樟醇过氧化物含量为 445±23ppm。这个水平可能会引发已经敏感的个体的皮肤反应。
