Marshall Alan G, Rodgers Ryan P
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA.
Acc Chem Res. 2004 Jan;37(1):53-9. doi: 10.1021/ar020177t.
Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry has recently revealed that petroleum crude oil contains heteroatom-containing (N,O,S) organic components having more than 20,000 distinct elemental compositions (C(c)H(h)N(n)O(o)S(s)). It is therefore now possible to contemplate the ultimate characterization of all of the chemical constituents of petroleum, along with their interactions and reactivity, a concept we denote as "petroleomics". Such knowledge has already proved capable of distinguishing petroleum and its distillates according to their geochemical origin and maturity, distillation cut, extraction method, catalytic processing, etc. The key features that have opened up this new field have been (a) ultrahigh-resolution FT-ICR mass analysis, specifically, the capability to resolve species differing in elemental composition by C(3) vs SH(4) (i.e., 0.0034 Da); (b) higher magnetic field to cover the whole mass range at once; (c) dynamic range extension by external mass filtering; and (d) plots of Kendrick mass defect vs nominal Kendrick mass as a means for sorting different compound "classes" (i.e., numbers of N, O, and S atoms), "types" (rings plus double bonds), and alkylation ((-CH(2))(n)) distributions, thereby extending to >900 Da the upper limit for unique assignment of elemental composition based on accurate mass measurement. The same methods are also being applied successfully to analysis of humic and fulvic acids, coals, and other complex natural mixtures, often without prior or on-line chromatographic separation.
超高分辨率傅里叶变换离子回旋共振质谱法最近揭示，石油原油含有含杂原子（N、O、S）的有机成分，其独特的元素组成（C(c)H(h)N(n)O(o)S(s)）超过20000种。因此，现在有可能设想对石油的所有化学成分及其相互作用和反应性进行最终表征，我们将这一概念称为“石油组学”。这样的知识已被证明能够根据石油及其馏分的地球化学来源和成熟度、馏分切割、提取方法、催化加工等对其进行区分。开启这一新领域的关键特性包括：（a）超高分辨率傅里叶变换离子回旋共振质谱分析，具体而言，能够分辨元素组成相差C(3) 与SH(4)（即0.0034 Da）的物种；（b）更高的磁场，可一次性覆盖整个质量范围；（c）通过外部质量过滤扩展动态范围；以及（d）绘制肯德里克质量缺陷与标称肯德里克质量的关系图，作为对不同化合物“类别”（即N、O和S原子的数量）、“类型”（环加双键）和烷基化（(-CH(2))(n)）分布进行分类的手段，从而将基于精确质量测量的元素组成唯一分配的上限扩展到>900 Da。同样的方法也成功应用于腐殖酸和富里酸、煤以及其他复杂天然混合物的分析，通常无需事先或在线色谱分离。
