• Pillar array columns was applied to α-keto acids analysis. α-Keto were derivatized with 1,2-diamino-4,5-methylenedioxybenzene for fluorescence detection. Four separated on pillar in 160 s. Three branched-chain human plasma samples successfully quantified. Branched-chain (BCKAs, namely, α-ketoisovaleric acid (KIV), α-ketoisocaproic (KIC), and α-keto-β-methylvaleric (KMV)) are related many dise...