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Supercritical fluid extraction (SFE) and high-speed counter-current chromatography (HSCCC) were successfully used for extraction, separation and purification of alkaloids from corydalis decumbens.The preparative SFE system under the conditions of 35MPa, 70℃, a sample particle sized 40-80 mesh and modified CO2 with dehydrated alcohol.HSCCC separation was used under the conditions of the optimal two-phase solvent system, which was composed of a mixture of chloroform- methanol-0.2M HCL (4:1:2, v/v) by eluting the lower mobile phase at a flow-rate of 2 ml/min and a revolution of 800 rpm.Three alkaloids were isolated by HSCCC and analyzed by high performance liquid chromatography (HPLC).Those alkaloids yielded total of 87.10 mg of xtw-2 (d-tetrahydropalmatine) at 99.7% purity, 52.25 mg of xtw-6 ((+)-Kikemanine) at 99.0% purity and 115.40 mg of xtw-4 (Protopine) at 99.48% purity.Those chemical structures were identified by UV, IR, MS, NMR.It should be mentioned that the K-value of HSCCC for xtw-4 (Protopine) is not 0.5 to 2 as normal but 10.For its large K-value, its retention time is long.While other undesired compounds were eluted out by mobile phase, the purified Protopine was obtained from stationary phase.Present study provides a new method of separation with HSCCC.