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Capillary electrophoresis (CE) method for the baseline separation of structurally similar flavonolignans silybin A, silybin B, isosilybin A, isosilybin B, silychristin, silydianin, and their precursor taxifolin in silymarin complex has been developed and validated. The optimized background electrolyte was 100 mmol/L boric acid (pH 9. containing 5 mmol/L heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin and 10% (v/v) of methanol. The separation was carried out in an 80.5/72 cm (50 μm id) fused silica capillary at + 25 kV with UV detection at