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We here report a development of polymer-modified space in a few hundreds nanometer-sized channel (so-called extended nanospace) utilizing surface-initiated atom transfer radical polymerization (SI-ATRP) for novel separation device.Recently, high efficient separation method for ultra-low volume of samples is required for various applications such as single cell analysis and proteomics.We have been focused on extended nanospace, and developed extended nanochromatography that utilizes surface of extended nanochannel as stationary phase.It has large number of theoretical plates (106 plate/m) and achieves high separation capability for ultra-low volume of sample.However, it is difficult to apply extended nanochromatography to separation of various biomacromolecules, since effects of the surface of channel are not enough to separate clearly these samples.The objective of our study is to develop polymer-modified extended nanospace by SI-ATRP for novel separation mode, which utilizes multiple effects of polymer.