Thread a short skewer (4 or 6 inches) through each pineapple chunk and arrange on a large, parchment-paper-lined baking sheet. Working over a double boiler, heat chocolate, stirring constantly, until just melted; stir in cayenne. Working with one skewer at a time, pat pineapple dry with a paper towel, and then dip in chocolate, covering about halfway. Transfer to baking sheet, sprinkle lightly with salt and repeat with remaining pineapple and chocolate. Chill until set, about 45 minutes.
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