Typek Rafal, Dybowski Michal P, Holowinski Piotr, Dawidowicz Andrzej L
Department of Chromatography, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie Sklodowska University in Lublin, 20-031 Lublin, Poland.
Department of Chromatography, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie Sklodowska University in Lublin, 20-031 Lublin, Poland.
J Chromatogr A. 2025 Oct 11;1760:466298. doi: 10.1016/j.chroma.2025.466298. Epub 2025 Aug 15.
The most common method for enhancing the sensitivity of chromatographic analysis to the compound under study is its prior derivatization, typically achieved through silylation or acylation. Studies performed with the use of ortho-allylphenol and its derivatives, compounds possessing an alkene chain and a phenolic group, i.e. the moieties capable of the internal mutual reaction, prove that it is possible to increase their GC-MS signal not only by their silylation and acylation but also by their initial cyclization at the sample preparation stage. While the silylation of individual ortho-allylphenols, depending on the type and number of substituents in the ortho-allylphenol core, results in a 3- to 6-fold increase in their GC-MS signal, the signal enhancement caused by the cyclization of each of these compounds is significantly greater than that induced by silylation alone, ranging from 5- to 11-fold. The procedure for enhancing the GC-MS signal of ortho-allylphenols through their preliminary cyclization is simple, workable, and effective, as demonstrated by the results of their analyses in blood, urine, saliva, and various food and cosmetic products. The presented results suggest that the GC-MS signal strength of almost any molecule can be enhanced by cyclization if it has an appropriate structure (i.e. possesses an alkene chain and a phenolic group - moieties capable of internal mutual reaction) and undergoes cyclization in the MS ionization chamber (the energy required for cyclization is lower than the energy of electrons in the standard GC-MS EI source).
提高色谱分析对所研究化合物灵敏度的最常见方法是对其进行预先衍生化，通常通过硅烷化或酰化来实现。使用邻烯丙基苯酚及其衍生物（具有烯烃链和酚羟基的化合物，即能够发生分子内相互反应的部分）进行的研究表明，不仅可以通过硅烷化和酰化来提高它们的气相色谱-质谱（GC-MS）信号，还可以在样品制备阶段通过其初始环化来提高。虽然单个邻烯丙基苯酚的硅烷化根据邻烯丙基苯酚核心中取代基的类型和数量会使它们的GC-MS信号增强3至6倍，但这些化合物各自环化所导致的信号增强明显大于单独硅烷化所引起的增强，增幅为5至11倍。通过邻烯丙基苯酚的初步环化来增强其GC-MS信号的方法简单、可行且有效，这在对血液、尿液、唾液以及各种食品和化妆品的分析结果中得到了证明。所呈现的结果表明，如果几乎任何分子具有合适的结构（即具有烯烃链和酚羟基——能够发生分子内相互反应的部分）并且在质谱电离室中发生环化（环化所需的能量低于标准GC-MS电子轰击电离源中电子的能量），那么通过环化都可以增强其GC-MS信号强度。
