Lv Zhengxian, You Jinmao, Lu Shuaimin, Sun Weidi, Ji Zhongyin, Sun Zhiwei, Song Cuihua, Chen Guang, Li Guoliang, Hu Na, Zhou Wu, Suo Yourui
Key Laboratory of Life-Organic Analysis of Shandong Province, Qufu Normal University, Qufu 273165, People's Republic of China; Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine of Shandong Province, Qufu Normal University, Qufu 273165, People's Republic of China.
Key Laboratory of Life-Organic Analysis of Shandong Province, Qufu Normal University, Qufu 273165, People's Republic of China; Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine of Shandong Province, Qufu Normal University, Qufu 273165, People's Republic of China; Northwest Plateau Institute of Biology, Chinese Academy of Sciences, Xining 810001, People's Republic of China.
J Chromatogr A. 2017 Mar 31;1491:98-107. doi: 10.1016/j.chroma.2017.02.042. Epub 2017 Feb 24.
As the key aroma compounds, varietal thiols are the crucial odorants responsible for the flavor of wines. Quantitative analysis of thiols can provide crucial information for the aroma profiles of different wine styles. In this study, a rapid and sensitive method for the simultaneous determination of six thiols in wine using d/d-acridone-10-ethyl-N-maleimide (d/d-AENM) as stable isotope-coded derivatization reagent (SICD) by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) has been developed. Quantification of thiols was performed by using d-AENM labeled thiols as the internal standards (IS), followed by stable isotope dilution HPLC-ESI-MS/MS analysis. The AENM derivatization combined with multiple reactions monitoring (MRM) not only allowed trace analysis of thiols due to the extremely high sensitivity, but also efficiently corrected the matrix effects during HPLC-MS/MS and the fluctuation in MS/MS signal intensity due to instrument. The obtained internal standard calibration curves for six thiols were linear over the range of 25-10,000pmol/L (R≥0.9961). Detection limits (LODs) for most of analytes were below 6.3pmol/L. The proposed method was successfully applied for the simultaneous determination of six kinds of thiols in wine samples with precisions ≤3.5% and recoveries ≥78.1%. In conclusion, the developed method is expected to be a promising tool for detection of trace thiols in wine and also in other complex matrix.
作为关键香气化合物，品种硫醇是决定葡萄酒风味的重要气味物质。硫醇的定量分析可为不同葡萄酒风格的香气特征提供关键信息。本研究建立了一种快速灵敏的方法，以d/d -吖啶酮-10-乙基-N-马来酰亚胺（d/d -AENM）为稳定同位素编码衍生试剂（SICD），采用高效液相色谱-电喷雾电离-串联质谱法（HPLC-ESI-MS/MS）同时测定葡萄酒中的六种硫醇。硫醇的定量分析以d-AENM标记的硫醇为内标物（IS），随后进行稳定同位素稀释HPLC-ESI-MS/MS分析。AENM衍生化结合多反应监测（MRM）不仅由于极高的灵敏度实现了硫醇的痕量分析，而且有效校正了HPLC-MS/MS过程中的基质效应以及仪器导致的MS/MS信号强度波动。六种硫醇获得的内标校准曲线在25 - 10,000 pmol/L范围内呈线性（R≥0.9961）。大多数分析物的检测限（LOD）低于6.3 pmol/L。该方法成功应用于葡萄酒样品中六种硫醇的同时测定，精密度≤3.5%，回收率≥78.1%。总之，所建立的方法有望成为检测葡萄酒及其他复杂基质中痕量硫醇的有力工具。
