New protocol for rapid,automatic,and high-throughput isolation of phosphopeptides (PPs) is required for point-of-care (POC) testing.Miniaturization provides the means for the production of small,fast and easy-to-operate devices for reduced-cost sample testing at the POC.Generation of nanostructures on the inner wall of microchannels is crucial for the development of functional microfluidic devices,such as cell separators[1],DNA separators[2] and photocatalytic microreactors[3].Unique architectures of 1D materials with high surface to volume ratios are suitable for the development of functional integrated microfluidic devices especially for high-throughput identification and characterization of biological molecules[1].Nanomaterial surfaces can be engineered with varied functional groups to provide binding sites for selected proteins or protein fragments.Here,a capillary microchannel (CM) containing ZnO/TiO2 nanorod arrays was applied as a novel microfluidic device to selectively bind and enrich PPs.The device was prepared by pumping a TiO2 sol into a CM containing preformed ZnO nanorod arrays.Different thicknesses of the TiO2 coating were obtained by controlling the flow duration of TiO2 sol.The modified CM achieved uninterrupted high-throughput introduction,capture and enrichment of PPs using continuous-flow operation.The microfluidic device based on the modified CM showed great selectivity,sensitivity and durability for the enrichment of PPs from tryptic protein digests.These results suggest that microfluidic chips employing this strategy can be used for rapid and high-throughput enrichment of PPs from complex mixtures.