Preheat the oven to 180 degrees/160 degrees fan forced and line ten 125ml (1/2 cup) muffin pans with paper cases.
Microwave the chocolate, butter and hot water in a microwave safe bowl on high, stirring occasionally, for 3-5 minutes or until melted. Stir in the sugar and vanilla.
Whisk in the combined flours,cocoa and egg until well combined. Divide the mixture evenly between the cases and bake for 20-25 minutes or until a skewer inserted into the centre comes out clean. Transfer to a wire rack to cool completely, then spread a little chocolate frosting over each one.
Combine the caramel popcorn and peanuts in a large heatproof bowl. Stir the jersey caramels and cream in a small saucepan over low heat for 5 minutes or until melted and smooth. Pour two-thirds of the caramel mixture over the popcorn mixture and stir to combine. Set aside for about 3 minutes.
While the popcorn mixture is still warm, spoon and shape mounds of it over the cakes. Set aside for 5 minutes to set.
Warm the remaining caramel mixture over low heat and drizzle over the cupcakes along with melted chocolate to decorate.