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OT-CEC separation efficiency of the drugs was dramatically enhanced because the block co-polymer could self-assemble in the solution and form pseudo-micelles, which further increased the interactions between the P(St-GMA) and these drugs. Our results not only reveal the great potential of block co-polymer coatings in OT-CEC for the analysis of drugs in real biological samples, but also serve asa platform for the preparation of diverse block co-polymers to be used in OT-CEC analysis. We believe that in the near future, the peak tailing prob