CE features superior separation efficiency, small solvent consumption, as well as the ability to analyze most biomolecules with an open tube fused-silica column. When coupled with MS, the separation power of CE is enhanced by adding another separation dimension based on mass-to-charge ratios. CE-MS reduces the dependence on CE separation so that faster analysis can be achieved. It also yields higher sensitivity as well as the capability for analyte identification and structural elucidation. The use of CE-MS for biomolecule analysis has increased significantly in the last 5 years. New methods are being developed for large molecules, while analyses of smaller molecules are moving toward the study in more complex tissues and other matrices. In this article, the applications of CE-ESI-MS for complex samples in 2007-2011 are reviewed. The applications are categorized according to the types of analytes studied, including the analysis for proteins and peptides, carbohydrates, and small biomolecules. Sample preparation methods, coatings for capillary inner wall, online processing strategies, and other aspects are also reviewed in each category.

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