Simultaneous de Novo Identification of Molecules in Chemical Mixtures by Doubly Indirect Covariance NMR Spectroscopy
Simultaneous de Novo Identification of Molecules in Chemical Mixtures by Doubly Indirect Covariance NMR Spectroscopy
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DOI：
10.1021/ja106781r
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发表时间：
2010-12-01
影响因子：
15
通讯作者：
Brueschweiler, Rafael
中科院分区：
文献类型：
--
作者：
Zhang, Fengli;Bruschweiler-Li, Lei;Brueschweiler, Rafael
复杂分子混合物的详细表征在现代化学的许多领域中起着关键作用。在这里，我们报道了一种新的核磁共振波谱方法，它将复杂的有机分子混合物同时分解成单独的组分，并描述它们的化学结构，而不需要对组分进行物理分离。引入双间接协方差谱，并将其应用于二维C-13-H-1HSQC和二维H-1-H-1 COSY谱，得到了具有前所未有的高分辨率的C-13-C-13二维谱。这种重组的光谱确实是一张碳连接性图，可以直接用基本图论进行分析，以获得单个混合物组分或其碎片的骨架结构。以从癌细胞中提取的模型混合物和天然产物混合物为例，验证了该方法。它对自动化的适用性使得这种方法对于分析各种天然或合成产品的混合物很有吸引力。
The detailed characterization of complex molecular mixtures plays a key role in many areas of modern Chemistry. Here we report a novel NMR spectroscopic method that deconvolutes a complex mixture of organic molecules simultaneously into individual components and depicts their chemical structure without requiring physical separation of the components. Doubly indirect covariance spectroscopy is introduced and applied to 2D C-13-H-1 HSQC and 2D H-1-H-1 COSY spectra, which results in a C-13-C-13 2D spectrum with unprecedented high resolution. This reconstituted spectrum is indeed a carbon-connectivity map that can be directly analyzed with basic graph theory to obtain the skeletal structures of individual mixture components or their fragments. The method is demonstrated for a model mixture and a natural product mixture extracted from cancer cells. Its suitability for automation makes this approach attractive for the analysis of a broad range of mixtures of natural or synthetic products.