Capillary electrophoresis to investigate biopharmaceuticals and pharmaceutically-relevant binding properties

•CE modes in the analysis of biopharmaceuticals are discussed.•Aspects of CE and ACE including method development and validation are reviewed.•Recent binding studies by ACE are described.•Optimal CE and ACE assays for various scenarios are compared with other techniques.

This review provides an overview of the use of different modes of capillary electrophoresis (CE) for the analysis of biopharmaceuticals and pharmaceuticals from biological fluids. We describe the effective use of CE for assays of the main compound and impurity assessment and for binding assays (Affinity CE). We compare the performance of CE with other frequently used techniques.