Departamento de Química, Universidade de Aveiro, 3810-193 Aveiro, Portugal.
J Chromatogr A. 2009 Nov 20;1216(47):8398-403. doi: 10.1016/j.chroma.2009.09.061. Epub 2009 Oct 1.
Two novel methodologies for quantification of C(13) norisoprenoids in wines were developed. The first methodology, method A (reference method) was based on the headspace solid-phase microextraction combined with gas chromatography-quadrupole mass spectrometry operating in selected ion monitoring mode (HS-SPME-GC-qMS-SIM). This methodology allowed to select the GC conditions for an adequate chromatographic resolution of wine components. The second methodology, method B (rapid method) was based on the HS-SPME-GC-qMS-SIM, using GC conditions that allowed to obtain a C(13) norisoprenoid volatile signature. In the later, the GC capillary column of 30 m at 220 degrees C was used acting as a transfer line of the components sorbed by the SPME coating fibre to the mass spectrometer, which acts as a sensor for m/z fragments 142 and 192. It does not require any pre-treatment of the sample, and the C(13) norisoprenoid composition of the wine was evaluated based on the chromatographic profile and specific m/z fragments, without complete chromatographic separation of its components. For quantification purposes, external calibration curves were constructed with beta-ionone chemical standard. Calibration curves with regression coefficient (r(2)) of 0.9940 and 0.9968, RSD of 1.08% and 12.51%, and detection limits of 1.10 and 1.57 microg L(-1) were obtained for methods A and B, respectively. These methodologies were applied to seventeen white and red table wines. Two vitispirane isomers (158-1529 microg L(-1)) and 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN) (6.42-39.45 microg L(-1)) were quantified. The data obtained for vitispirane isomers and TDN using the two methods were highly correlated (r(2) of 0.9756 and 0.9630, respectively). Associated to the fast and robust character of the proposed rapid method B and considering the extraction time, it is important to focus its selectivity and potential applicability if specific m/z fragments would be established for new analytes.
开发了两种用于定量葡萄酒中 C(13)法呢基倍半萜的新方法。第一种方法 A（参考方法）基于顶空固相微萃取结合气相色谱-四极杆质谱在选择离子监测模式下操作（HS-SPME-GC-qMS-SIM）。该方法允许选择 GC 条件以实现葡萄酒成分的充分色谱分离。第二种方法 B（快速方法）基于 HS-SPME-GC-qMS-SIM，使用允许获得 C(13)法呢基倍半萜挥发性特征的 GC 条件。在后一种方法中，使用 220°C 下 30 m 的 GC 毛细管柱作为 SPME 涂层纤维吸附的成分转移到质谱仪的传输线，质谱仪作为 m/z 片段 142 和 192 的传感器。它不需要对样品进行任何预处理，并且基于色谱图和特定的 m/z 片段评估葡萄酒中的 C(13)法呢基倍半萜组成，而无需对其成分进行完全色谱分离。为了定量目的，使用β-紫罗兰酮化学标准构建外部校准曲线。方法 A 和 B 分别得到回归系数（r(2)）为 0.9940 和 0.9968、RSD 为 1.08% 和 12.51%以及检测限为 1.10 和 1.57μg L(-1)的校准曲线。这些方法应用于十七种白葡萄酒和红葡萄酒。两种大根香叶二烯异构体（158-1529μg L(-1)）和 1,1,6-三甲基-1,2-二氢萘（TDN）（6.42-39.45μg L(-1)）进行了定量。使用两种方法获得的大根香叶二烯异构体和 TDN 数据高度相关（r(2)分别为 0.9756 和 0.9630）。考虑到拟议的快速方法 B 的快速和稳健特性以及提取时间，如果为新分析物建立特定的 m/z 片段，那么关注其选择性和潜在适用性非常重要。
