Preheat the oven to 350 degrees F.
Sift the flour, cocoa powder, baking soda, salt and baking powder. Set aside.
In the bowl of a stand mixer with a paddle attachment, cream the sugar and butter until fluffy, 2 to 3 minutes. Slowly add the eggs and vanilla extract. Combine the buttermilk and espresso. Alternate adding the dry and wet ingredients. Start and end with the dry. Remove the bowl from the mixer and scrape down the mixture into the pans, filling the pans to just over half. Place the pans in the oven and bake, 15 to 18 minutes. Remove from the oven and cool on a rack to room temperature, when they can be popped out of the molds.
In a bowl of a stand mixer fitted with the whip attachment, begin making the fluff by whipping the corn syrup and egg whites on medium speed, about 1 minute. Increase the speed to high and whip until the eggs are fluffy and firm, an additional 3 to 4 minutes. To the bowl add the confectioners' sugar and vanilla and whip on low speed until fully incorporated, about 1 minute. Remove the bowl from the mixer and with a spatula fold in the chopped almonds. Set aside.
Melt the chocolate and keep warm. Place the coconut in a small bowl. Set aside. Place 2 to 3 tablespoons of the marshmallow fluff on top of the baked Twinkie. With a small offset spatula, evenly coat each Twinkie. Generously press the coconut all over the Twinkie except for the bottom. Really pack on as much as will stick. Place the finished Twinkies on a tray. Set aside and keep at room temperature.
Dip the reserved whole toasted almonds in the warm melted chocolate, and with a fork, lift the nuts allowing the excess chocolate to drip back in the bowl. Place the chocolate dipped almonds on a lined baking pan. Chill until firm and can be lifted off the paper, 15 to 20 minutes.
Place one almond on top of each Twinkie. Heaven!