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Mistress Mare-Vellous, better known as Applejack from MLP: FIM. The episode is called Power Ponies. Spike gets an enchanted comic book that transports him and the Mane 6 into the comic book world where they assume the personas of super heroes from the comic book. Eventually, they confront the Mane-iac, who has her hideout at an abandoned shampoo factory (the place where she fell into a vat of shampoo and became evil).