Preheat oven to 180°C. Line twenty-four 1/3 cup (80ml-capacity) muffin pans with paper cases.
Combine the flour, cocoa powder, sugar and bicarbonate of soda in a large bowl. Make a well in the centre.
Whisk the butter, milk, vinegar and vanilla together in a jug. Pour into the well and use a wooden spoon to gently stir until mixture is just combined. Spoon evenly among the lined pans.
Bake in preheated oven for 20 minutes or until a skewer inserted in the centres comes out clean. Remove from oven and set aside to cool.
To make the chocolate icing, place the chocolate and butter in a heatproof bowl over a saucepan of simmering water. Stir with a metal spoon for 3-5 minutes or until chocolate and butter melt and mixture is smooth. Remove from heat. Add the icing sugar and stir well until combined. Set aside for 15-20 minutes or until icing is firm. Use a wooden spoon to beat until smooth. Spread over each muffin and serve immediately.
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